Pyrazole derivative and herbicide containing it

Information

  • Patent Grant
  • 4948887
  • Patent Number
    4,948,887
  • Date Filed
    Monday, March 14, 1988
    36 years ago
  • Date Issued
    Tuesday, August 14, 1990
    34 years ago
Abstract
A pyrazole derivative having the formula: ##STR1## wherein A is alkyl, alkenyl or alkynyl; B is hydrogen, alkyl, halogen, haloalkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl or alkoxycarbonyl; X is alkyl, alkoxy, halogen, nitro, cyano, haloalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl substituted by hydrogen or alkyl, haloalkoxy, alkylthio or alkylthioalkyl; Y is --COOR1 (wherein R1 is hydrogen, alkyl, etc.), --COO--L--OR1 (wherein L is alkylene which may be substituted), --COO--L--R2 (wherein R2 is phenyl group which may be substituted), --COO--M (wherein M is 3 to 6-membered alicyclic residue containing not more than 2 sulfur or oxygen atoms), --COO--L--M, --COO--L--O--L--R2, --COO--L--S(O).sub.n --CON (R3) (R4) (wherein each of R3 and R4 is hydrogen, alkyl, etc.), a --CON--(CH.sub.2).sub.n, ##STR2## wherein R5 is alkyl), ##STR3## --CONHSO.sub.2 CH.sub.3, --CONHSO.sub.2 CF.sub.3, --COO--L--N(R3) (R4), --COO--L--CO--R1, --COO--L--CO--O--R1, --COO--L--CN, --Coo--L--NO.sub.2 --COOSi (R5).sub.3, --COO--N.dbd.(R6) (R7) (wherein each of R6 and R7 is alkyl), --COO--N.dbd.C--(CH.sub.2).sub.n, --COO--L--O--SO.sub.2 --R1, --Coo--L--O--CO--R1, --COO--L--O--L--O--R1, --COO--L--Si (R5).sub.3, --C(O)S--R1, --C(S)O--R1, --C(S)S--R1, --L--O--R1, --L--O--L--O--R8 (wherein R8 is hydrogen or alkyl), --L--O--M, --L--O--L--M, --L--NR8R9 (wherein R9 is alkyl group), --L--O--CH.sub.2 Ph, --L--O--L--COOR9, --L--CN, --L--S(O).sub.n --R1, --L--S--L--O--R9, --L--O--COR9, --L--O--SO.sub.2 R9, --L--COOR8, --C.dbd.CHOR8 or --L--O--L--CN; Z is halogen, nitro, alkoxy, trifluoromethyl, cyano or --S(O).sub.n R10 (wherein R10 is alkyl or haloalkyl); V is a hydrogen atom, a halogen atom, an alkyl group having from 1 to 4 carbon atoms or an alkoxy group having from 1 to 4 carbon atoms; W is a hydrogen atom, a halogen atom, an alkyl group having from 1 to 4 carbon atoms, a haloalkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, an alkoxyalkyl group having from 2 to 6 carbon atoms, an alkoxycarbonyl group having from 2 to 5 carbon atoms, a haloalkoxy group having from 1 to 3 carbon atoms, a nitro group, a cyano group or a --S(O).sub.n --R group (wherein n is as defined above and R is an alkyl group having from 1 to 4 carbon atoms); Q is hydrogen, alkyl, alkenyl, alkynyl, cyanomethyl, --C(O)--R11 (wherein R11 is phenyl group which may be substituterd, alkyl, alkoxy or hydroxyl), --S(O).sub.2 R11, --P(O) (OR11).sub.2 --L--C(O)--R11, --L--C(O)--N (R12) (R13) (wherein each of R12 and R13 is hydrogen or alkyl), --L--R14 (wherein R14 is phenyl which may be substituted, alkyl, alkoxy or hydroxy), --L--N(R12) (R13), a --L--OR15 (wherein R15 is hydrogen, alkyl or alkenyl), --L--OC(O)R16 (wherein R16 is alkyl or alkoxy), --L--S(O).sub.n R15, --L--SC(O)R12, ##STR4## wherein each of L1 and L2 is methylene, oxygen is sulfur and R16 is hydrogen or alkyl), and a salt thereof, useful as a herbicide.
Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel 0 4-benzoylpyrazole derivatives and selective herbicides containing such derivatives as active ingredients, which are useful particularly as upland field herbicides.
2. Discussion of Background
Various herbicides have been developed for practical use from extensive research and development of herbicides for many years, and such herbicides have contributed to a reduction of the labor force required for controlling weeds or to improvement of the productivity of agricultural or horticultural plants.
Even now, it is still desired to develop a new herbicide having superior herbicidal properties. In particular, it is desired to develop an agricultural or horticultural herbicide which is capable of selectively controlling weeds without adversely affecting the crop plant and at a low dose. However, conventional herbicides do not necessarily provide such desired herbicidal properties.
On the other hand, certain compounds of 4-benzoylpyrazole derivatives are known to have herbicidal activities. For example, pyrazylate (common name) and pyrazoxyfen (common name) are practically used as herbicides for paddy fields. While exhibiting excellent herbicidal activities as paddy field herbicides, these compounds are not suitable as upland herbicides since their herbicidal activities are weak against weeds of upland fields. Among 4-benzoylpyrazole derivatives, it is desired to develop a superior compound useful as an upland field herbicide.
SUMMARY OF THE INVENTION
The present invention provides a pyrazole derivative having the formula: ##STR5## wherein A is an alkyl group having from 1 to 3 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms or an alkynyl group having from 2 to 4 carbon atoms; B is a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, a halogen atom, a haloalkyl group having from 1 to 3 carbon atoms, an alkoxy group having from 1 to 3 carbon atoms, an alkylthio group having from 1 to 3 carbon atoms, an alkoxyalkyl group having from 2 to 4 carbon atoms, an alkylthioalkyl group having from 2 to 4 carbon atoms or an alkoxycarbonyl group having from 2 to 4 carbon atoms; X is an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, a haloalkyl group having from 1 to 6 carbon atoms, an alkoxyalkyl group having from 2 to 6 carbon atoms, an alkylcarbonyl group having from 2 to 6 carbon atoms, an alkoxycarbonyl group having from 2 to 6 carbon atoms, an aminocarbonyl group substituted independently by hydrogen or alkyl having from 1 to 6 carbon atoms, a haloalkoxy group having from 1 to 6 carbon atoms, an alkylthio group having from 1 to 6 carbon atoms or an alkylthioalkyl group having from 2 to 6 carbon atoms; Y is a --COOR1 group (wherein R1 is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms, a cycloalkylalkyl group having from 4 to 8 carbon atoms, an alkynyl group having from 3 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, a halocycloalkyl group having from 3 to 8 carbon atoms, a haloalkynyl group having from 3 to 6 carbon atoms, a haloalkenyl group having from 2 to 6 carbon atoms or a phenyl group which may be substituted by alkyl having from 1 to 3 carbon atoms, halogen, nitro or alkoxy having from 1 to 3 carbon (atoms), a --COO--L--OR1 group (wherein L is an alkylene group having from 1 to 6 carbon atoms which may be substituted by alkyl having from 1 to 3 carbon atoms, and R1 is as defined above), a --COO--L--R2 group (wherein L is as defined above, and R2 is a phenyl group which may be substituted by alkyl having from 1 to 3 carbon atoms, halogen, nitro or alkoxy having from 1 to 3 carbon atoms), a --COO--M group (wherein M is a 3 to 6-membered alicyclic residue containing not more than 2 sulfur or oxygen atoms and formed by a linkage of from 1 to 4 carbon atoms), a --COO--L--M group (wherein L and M are as defined above), a COO--L--O--L--R2 group (wherein L and R2 are as defined above), a --COO--L--S(O).sub. n--R1 group (wherein L and R1 are as defined above, and n is an integer of from 0 to 2), a --CON(R3)(R4) group (wherein each of R3 and R4 is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms, a cycloalkylalkyl group having from 4 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an alkynyl group having from 2 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, a halocycloalkyl group having from 3 to 8 carbon atoms, a haloalkynyl group having from 2 to 6 carbon atoms, a haloalkenyl group having from 2 to 6 carbon atoms or a phenyl group which may be substituted by alkyl having from 1 to 3 carbon atoms, halogen, nitro or alkoxy having from 1 to 3 carbon atoms), a --CON--(CH.sub.2).sub.n group (wherein n is an integer of from 4 to 6), a ##STR6## group (wherein R5 is an alkyl group having from 1 to 3 carbon atoms), a ##STR7## a --CONHSO.sub.2 CH3 group, a --CONHSO.sub.2 CF.sub.3 group, a --COO--L--N(R3)(R4) group (wherein L, R3 and R4 are as defined above), a --COO--L--CO--R1 group (wherein L and R1 are as defined above), a --COO--L--CO13 O--R1 group (wherein L and R1 are as defined above), a --COO--L--CN group (wherein L is as defined above), a --COO--L--NO.sub.2 group (wherein L is as defined above), a --COOSi(R5).sub.3 group (wherein R5 is as defined above), a --COO--N.dbd.C(R6)(R7) group (wherein each of R6 and R7 which may be the same or different is an alkyl group having from 1 to 3 carbon atoms), a --COO--N.dbd.C--(CH.sub.2).sub.n group (wherein n is an integer of from 4 to 6), a --COO--L--O--SO.sub.2 -R1 group (wherein L and R1 are as defined above), a --COO--L--O--CO--R1 group (wherein L and R1are as defined above), a --COO--L--O--L--O--R1 group (wherein L and R1 are as defined above), a --COO--L--Si(R5).sub.3 group (wherein L and R5 are as defined above), a --C(O)S--R1 group (wherein R1 is as defined above), a --C(S)O--R1group (wherein R1 is as defined above), a --C(S)S--R1 group (wherein R1 is as defined above), a --L--O--R1 group (wherein L and R1 are as defined above), a --L--O--L--O--R8 group (wherein L is as defined above, and R8 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms), a --L--O--M group (wherein L and M are as defined above), a --L--O--L--M group (wherein L and M are as defined above), a --L--NR8R9 group (wherein R8 is as defined above, and R9 is an alkyl group having from 1 to 6 carbon atoms), a --L--O--CH.sub.2 Ph group (wherein L is as defined above), --L--O--L--COOR9 group (wherein L and R9 are as defined above), a ----CN group (wherein L is as defined above), a --L--S(O).sub.n --R1 group (wherein L and R1 are as defined above, and n is an integer of from 0 to 2), a --L--S--L--O--R9 group (wherein L and R9 are as defined above), a --L--O--COR9 group (wherein L and R9 are as defined above), a L--O--SO.sub.2 R9 group (wherein L and R9 are as defined above), a --L--COOR8 group (wherein L and R8 are as defined above), a --CH.dbd.CHOR8 group (wherein R8 is as defined above) or a --L--O--L--CN group (wherein L is as defined above); Z is a halogen atom, a nitro group, an alkoxy group having from to 3 carbon atoms, a trifluoromethyl group, a cyano group or a --S(O).sub.n R10 group (wherein R10 is an alkyl group having from 1 to 3 carbon atoms or a haloalkyl group having from 1 to 3 carbon atoms, and n is an integer of from 0 to 2); V is a hydrogen atom, a halogen atom, an alkyl group having from 1 to 4 carbon atoms or an alkoxy group having from 1 to 4 carbon atoms; W is a hydrogen atom, a halogen atom, an alkyl group having from 1 to 4 carbon atoms, a haloalkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, an alkoxyalkyl group having from 2 to 6 carbon atoms, an alkoxycarbonyl group having from 2 to 5 carbon atoms, a haloalkoxy group having from 1 to 3 carbon atoms, a nitro group, a cyano group or a --S(O).sub.n --R group (wherein n is as defined above and R is an alkyl group having from 1 to 4 carbon atoms); Q is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms which may be substituted by halogen, an alkenyl group having from 1 to 6 carbon atoms which may be substituted by halogen, an alkynyl group having from 1 to 6 carbon atoms which may be substituted by halogen, a cyanomethyl group, a --C(O)--R11 group (wherein R11 is a phenyl group which may be substituted by the same or different substituents selected from the group consisting of alkyl having from 1 to 6 carbon atoms, alkenyl having from 1 to 6 carbon atoms, alkynyl having from 1 to 6 carbon atoms, haloalkyl having from 1 to 6 carbon atoms, haloalkenyl having from 1 to 6 carbon atoms, haloalkynyl having from 1 to 6 carbon atoms, halogen, nitro and trifluoromethyl, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms or a hydroxyl group), a --S(O).sub.2 R11 group (wherein R11 is as defined above), a --P(O)(OR11).sub.2 group (wherein R11 is as defined above), a --L--C(O)--R11 group (wherein L and R11 are as defined above), a --L--C(O)--N(R12)(R13) (wherein L is as defined above, each of R12 and R13 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms), a --L--R1l4 group (wherein L is as defined above, R14 is a phenyl group which may be substituted by the same or different substituents selected from the group consisting of halogen, nitro and trifluoromethyl, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms or a hydroxy group), a --L--N(R12)(R13) group (wherein L, R12 and R13 are as defined above), a --L--OR15 group (wherein R15 is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms or an alkenyl group having from 1 to 6 carbon atoms), a --L--OC(O)R16 group (wherein R16 is an alkyl group having from 1 to 6 carbon atoms or an alkoxy group having from 1 to 6 carbon atoms), a --L--S(O).sub.n R15 group (wherein R15 is as defined above, and n is an integer of 0 or 2), a --L--SC(O)R12 group (wherein R12 is as defined above), ##STR8## group (wherein each of L1 and L2 is a methylene group, an oxygen atom or a sulfur atom, R16 is a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, and n is an integer of 2 or 3), and a salt thereof.
The present invention also provides a selective herbicidal composition comprising a herbicidally effective amount of at least one pyrazole derivative of the formula I as defined above or its salt and an agricultural carrier or diluent.
Further, the present invention provides a method for selectively controlling weeds, which comprises applying the pyrazole derivative of the formula I as defined above or its salt to the locus to be protected.
Now, the present invention will be described in detail with reference to the preferred embodiments.
In the compound of the formula I of the present invention, A, B, X, Y, Z and Q are preferably selected from the following substituents, respectively:
A: Me, Et, n-Pr, i-Pr, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 C.tbd.CH
B: H, Me, Et, n-Pr, i-Pr, Cl, Br, CH.sub.2 Cl, CF.sub.3, OMe, OEt, OPr-i, SMe, CH.sub.2 OMe, CH.sub.2 SMe, CO.sub.2 Me, CO.sub.2 Et
X: Me, Et, m-PR, i-pR, m-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, OPr-n, OPr-i, OBu-n, OBu-i, OBu-s, OBu-t, F, Cl, Br, I, NO.sub.2, CN, CH.sub.2 F, CHF.sub.2, CF.sub.3, CH.sub.2 CF.sub.3, CH.sub.2 Cl, CCl.sub.3, CHClMe, CH.sub.2 CH.sub.2 Cl, CHClCH.sub.2 Cl, CH.sub.2 Br, CHBrMe, CH.sub.2 CH.sub.2 Br, CH.sub.2 OMe, CH.sub.2 OEt, CH.sub.2 OPr-n, CH.sub.2 OPr-i, CH.sub.2 OBu-n, CH.sub.2 OBu-i, CH.sub.2 OBu-s, CH.sub.2 OBu-t, CHMeOMe, CHMeOEt, CHMeOPr-n, CHMeOPr-i, CHMeOBu-n, CHMeOBu-i, CHMeOBu-s, CHMeOBu-t, CH.sub.2 CH.sub.2 OMe, CH.sub.2 CH.sub.2 OEt, CH.sub.2 CH.sub.2 OPr-i, Ac, COEt, COP-m, COPr-i, COOMe, COOOEt, COOPr-i, CONHMe, CONHEt, CONMe.sub.2, CONEt.sub.2, CONEtMe, OCHF.sub.2, OCF.sub.3, OCH.sub.2 CF.sub.3, SME, SEt, CH.sub.2 SMe, CH.sub.2 SEt, CHMeSMe, CHMeSEt
Y: CH.sub.2 OH, CH.sub.2 OMe, CH.sub.2 OEt, CH.sub.2 OPr-n, CH.sub.2 OPr-i, CH.sub.2 OBu-n, CH.sub.2 OBu-i, CH.sub.2 OBu-s, CH.sub.2 OBu-t, CH.sub.2 OAm-n, CH.sub.2 OAm-i, CH.sub.2 OAm-t, CH.sub.2 OC.sub.6 H.sub.13 -n, ##STR9## CH.sub.2 OCH.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 CMe.dbd.CH.sub.2, CH.sub.2 OCHMeCH.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 C.dbd.CH, CH.sub.2 OCHMeC.tbd.CH, CH.sub.2 OCMe.sub.2 C.tbd.CH, CH.sub.2 OCH.sub.2 CH.sub.2 F, CH.sub.2 OCH.sub.2 CF.sub.3, CH.sub.2 OCH.sub.2 CH.sub.2 Cl, CH.sub.2 OCH.sub.2 Cl.sub.3, CH.sub.2 OCH.sub.2 CH.sub.2 Br, ##STR10## CH.sub.2 OCH.sub.2 CCl.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 CCl.dbd.CHCl, CH.sub.2 OCH.sub.2 CH.sub.2 OMe, CH.sub.2 OCH.sub.2 CH.sub.2 OEt, CH.sub.2 OCH.sub.2 CH.sub.2 OPr-i, ##STR11## CH.sub.2 OPh, CH.sub.2 OPh-Cl-4, CH.sub.2 OPh-NO.sub.2 -4, CH.sub.2 NHMe, CH.sub.2 NHEt, CH.sub.2 NMe.sub.2, CH.sub.2 NEt.sub.2, CH.sub.2 NEtMe, CH.sub.2 OCH.sub.2 Ph, CH.sub.2 OCH.sub.2 COOMe, CH.sub.2 OCH.sub.2 COOEt, CH.sub.2 OCHMeCOOMe, CH.sub.2 OCH.sub.2 COOBu-t, CH.sub.2 OCHMeCOOEt, CH.sub.2 CN, CH.sub.2 SMe, Ch.sub.2 SEt, CH.sub.2 SPr-n, CH.sub.2 SPr-i, CH.sub.2 SBu-t, CH.sub.2 SCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 SCH.sub.2 C.tbd.CH, ##STR12## CH.sub.2 SCH.sub.2 CH.sub.2 Cl, CH.sub.2 SOMe, CH.sub.2 SOEt, CH.sub.2 SO2Me, CH.sub.2 SO2Et, CH.sub.2 SO2Pr-n, CH.sub.2 S02Pr-i, CH.sub.2 SCH.sub.2 CH.sub.2 OMe, CH.sub.2 SCH.sub.2 CH.sub.2 OEt, CH.sub.2 SPh, CH.sub.2 OAc, CH.sub.2 OCOEt, CH.sub.2 OCOPr-i, CH.sub.2 OSO.sub.2 Me, CH.sub.2 OSO2Et, CH.sub.2 OCH.sub.2 CH.sub.2 CN, CHMeOH, CHMeOMe, CHMeOEt, CHMeOPr-n, CHMeOPr-i, CHMeOBu-n, CHMeOBu-i, CHMeOBu-s, CHMeOBu-t, ##STR13## CHMeOCH.dbd.CH.sub.2, CHMeOCH.sub.2 CH.dbd.CH.sub.2, CHMeOCH.sub.2 C.tbd.CH, CHMeOCH.sub.2 CF.sub.3, CHMeOCH.sub.2 CH.sub.2 Cl, CHMeOCH.sub.2 CCl.sub.3, CHMeOCH.sub.2 CH.sub.2 Br, ##STR14## CHMeOCH.sub.2 CH.sub.2 OMe, CHMeOCH.sub.2 CH.sub.2 Et, ##STR15## CHMeOPh, CHMeNHMe, CHMeNMe.sub.2, CHMeNEt.sub.2, CHMeOCH.sub.2 COOMe, CHMeOCH.sub.2 COOEt, CHMeOCHMeCOOMe, CHMeCN, CHMeSMe, CHMeSEt, CHMeSPr-n, CHMeSPr-i, CHMeSCH.sub.2 CH.dbd.CH.sub.2, CHMeSCH.sub.2 C.dbd.CH, ##STR16## CHMeSCH.sub.2 CH.sub.2 Cl, CHMeSOMe, CHMeSOEt, CHMeSOMe, CHMeSO.sub.2 Et, CHMeSO.sub.2 Pr-i, CHMeSCH.sub.2 CH.sub.2 OMe, CHMeSPh, CHMeOAc, CHMeOCOEt, CHMeOSO.sub.2 Me, CHMeOSO.sub.2 Et, CHMeOCH.sub.2 CH.sub.2 CN, CMe.sub.2 OH, CMe.sub.2 OMe, CMe.sub.2 OEt, CMe.sub.2 OPr-n, CMe.sub.2 OPr-i, CMe.sub.2 OCH=CH.sub.2, CMe.sub.2 OCH.sub.2 CH=CH.sub.2, CMeOCH.sub.2 C.tbd.CH, CMe.sub.2 OCH.sub.2 CH.sub.2 Cl, CMe.sub.2 OCH.sub.2 CH.sub.2 OMe, ##STR17## CMe2NHMe, CMe2NMe2, CMe.sub.2 OCH.sub.2 COOMe, CMe.sub.2 CN, CMeSMe, CMe.sub.2 SEt, CMe.sub.2 S02Me, CMe.sub.2 SO.sub.2 Et, CMe.sub.20 Ac, CMe.sub.2 OSO.sub.2 Me, CH.sub.2 COOMe, CH.sub.2 COOEt, CH.sub.2 COOPr-i, CHMeCOOMe, CHMeCOOEt, CHMeCOOPr-i, CH.sub.2 CH.sub.2 COOMe, CH.sub.2 CH.sub.2 COOEt, CH.sub.2 CH.sub.2 COOPr-i, CH.dbd.CHOMe, CH.dbd.CHOEt, CH.dbd.CHOPr-i, COOH, COOMe, COOEt, COOPr-n, COOPr-i, COOBu n, COOBu-s, COOBu-i, COOBu-t, COOAm-i, ##STR18## COOCH.sub.2 CH.dbd.CH.sub.2, COOCH.sub.2 C.tbd.CH, COOCH.sub.2 CMe.dbd.CH.sub.2, COOCH.sub.2 CH.sub.2 Br, COOCH.sub.2 CH.sub.2 Cl COOCH.sub.2 CH.sub.2 F, COOCH.sub.2 CCl.sub.2, COOCH.sub.2 CHF2, COOCH.sub.2 CF3, ##STR19## COOCH.sub.2 CCl.dbd.CH.sub.2, COOCH.sub.2 CCl.dbd.CHCl, COOCH.sub.2 OMe, COOCH.sub.2 CH.sub.20 Me, COOCH.sub.2 CH.sub.2 OEt, COOCH.sub.2 OEt, COOCH.sub.2 SMe, COOCH.sub.2 CH.sub.2 SMe, COOCH.sub.2 CH.sub.2 SEt, COOCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 C, COOCH.sub.2 SOMe, COOCH.sub.2 CH.sub.2 SOMe, COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl, COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Br, COOCH.sub.2 CH.sub.2 OSO2Me, COOCH.sub.2 CH.sub.2 OSO2Ph-Me-4, COOCH.sub.2 OCH.sub.2 CH.sub.2 OMe, COOCH.sub.2 CH.sub.2 SO.sub.2 Me, COOCH.sub.2 CH.sub.2 SO.sub.2 Et, COOCH.sub.2 SO.sub.2 Me, COOCH.sub.2 CN, COOCH.sub.2 CH.sub.2 CN, COOCH.sub.2 CH.sub.2 CH.sub.2 CN, COOCH.sub.2 CH.sub.2 NHMe, COOCH.sub.2 CH.sub.2 NMe.sub.2, COOCH.sub.2 NMe.sub.2, COOCH.sub.2 CH.sub.2 NO2, COOCH.sub.2 CH.sub.2 CH.sub.2 NO2, COOCH.sub.2 OH, ##STR20## COOCH.sub.2 COMe, COOCH.sub.2 COBu-t, COOCH.sub.2 COPr-i, COOCH.sub.2 COPh, COOCH.sub.2 COOMe, COOCH.sub.2 COOEt, COOCHMeCOOMe, COOCMe2OOMe, COOCH.sub.2 CH.sub.2 OCH.sub.2 CH=CH.sub.2, COOCH.sub.2 CH.sub.2 OCH.sub.2 C.tbd.CH, COOCH.sub.2 CH.sub.2 OPh, COOCH.sub.2 OPh, COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph, COOCH.sub.2 SiMe.sub.2, COOSiMe.sub.2, COOSiEt.sub.2, COOPh, COOPh-C-l.sub.4, COOFh-Me-4, COOPh-OMe-4, COOPh-NO.sub.2 -4, COOCH.sub.hd Ph, COOCH.sub.2 Ph-CL-2, COOCH.sub.2 Ph-Cl-4, COOCHMeFh, COOCH.sub.2 CH.sub.2 Ph, ##STR21## C(O)SMe, C(O)SEt, C(O)SPr-i, C(O)SPr-n, C(O)SBu-n, C(O)SBu-t, C(O)SBu-s, C(O)SBu-i, C(S)OMe, C(S)OEt, C(S)OFr-i, C(S)OPr n, C(S)OBu-n, C(S)OBu-t, C(S)ODu-s, C(S)OBu-i, CSSMe, CSSEt, CSSPr-n, CSSPr-i, CONMe.sub.2, CONHMe, CONEt.sub.2, CONHEt, CONHPr-n, CONHPr-i, CONHBu-t, CONHBu-s, CONHBu-i, CONHBu-n, CONHAm-t, CONPr2-i, CONPr.sub.2 -n, CONHPh, CONHPh-Me-4, CONHPb-NO.sub.2 -4, ##STR22## CONMeOMe, CONHCH.sub.2 CH.dbd.CH.sub.2, CON(CH.sub.2 CH.dbd.CH.sub.2).sub.2, CONHCH.sub.2 C.tbd.CH, CON(CH.sub.2 C.tbd.CH).sub.2, CONMePh, CONEtPh, CON(Me)Ph Me-4, CONHSO.sub.2 Me, CONHSO.sub.2 CF.sub.3, COON.dbd.CMe.sub.2, ##STR23## COOCH.sub.2 OCOMe, COOCH.sub.2 OCOBu-t, Z: F, Cl, Br, I, NO.sub.2, OMe, OEt, OPr-n, OFr-i, CF.sub.3, CN, SMe, SOMe, SO.sub.2 Me, SCF.sub.2, SOCF.sub.2, SO.sub.2 CF.sub.3
Q: H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH.sub.2 CH.sub.2 Cl, CH.sub.2 CF.sub.2, CHClMe, CH.sub.2 CH.sub.2 Br, CHClCH.sub.2 C, CH.sub.2 CH=CH.sub.2, CH.sub.2 CMe.dbd.CH.sub.2, CH.sub.2 CH.dbd.CHMe, CH.sub.2 C.tbd.CH, CH.sub.2 CC.dbd.CH.sub.2, CH.sub.2 CN, CH.sub.2 Ph, CH.sub.2 Ph-Cl-2, CH.sub.2 Ph-Cl-3, CH.sub.2 Ph-Me-2, ##STR24## CH.sub.2 Ph-Me.sub.2 -2,4, CH.sub.2 Ph-Me-4, CHMePh, CHEtPh, CH.sub.2 Ph-NO.sub.2 -2, CH.sub.2 Ph-CF.sub.2 -3, CH.sub.2 OMe, CH.sub.2 OEt, CH.sub.2 OH, CHMeOH, CH.sub.2 NHMe, CH.sub.2 NMe, CH.sub.2 NMe2, CHMeNMe2, CH.sub.2 COPh, CH.sub.2 COPh-NO.sub.2 -4, CH.sub.2 COPh-Me-4, CH.sub.2 COPh Cl-4, CH.sub.2 COPh-Me.sub.2 -2,4, CH.sub.2 COPh-CF.sub.3 -4, CH.sub.2 Ac, CH.sub.2 COEt, CHMeAc, CH.sub.2 CO.sub.2 Me, CH.sub.2 CO.sub.2 Et, CH.sub.2 CO.sub.2 Pr-n, CH.sub.2 CO.sub.2 Fr-i, CH.sub.2 CO.sub.2 Du-t, CH.sub.2 CO.sub.2 H, CHMeCO.sub.2 H, CH.sub.2 CONHMe, CH.sub.2 CONMe.sub.2, CH.sub.2 CONHEt, CH.sub.2 CONEt.sub.2, CH.sub.2 CONPr-n.sub.2, CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 OAc, CH.sub.2 COEt, CH.sub.2 COPr-i, CH.sub.2 COBu-t, CH.sub.2 OCO.sub.2 Me, CH.sub.2 OCO.sub.2 Et, CH.sub.2 OCO.sub.2 Pr-i, CH.sub.2 OCO.sub.2 Bu-t, CH.sub.2 SMe, CH.sub.2 SEt, CH.sub.2 SCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 SAc, CH.sub.2 SCOBu-t, CH.sub.2 SO.sub.2 Me, CH.sub.2 SO.sub.2 Et, CH.sub.2 SO.sub.2 CH.sub.2 CH=CH.sub.2, CH.sub.2 NHCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 NMeCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 NHAc, CH.sub.2 NHCOEt, CH.sub.2 NHCO.sub.2 Me, CH.sub.2 NHCO.sub.2 Et, CH.sub.2 NMeCO.sub.2 Me, COPh, COPh Me-4, COPh NO.sub.2 -2, COPh-Cl.sub.2 -2,4, Ac, COEt, COPr-n, COPr-i, COBu-n, COBu-t, COCH.sub.2 Cl, COCHCl.sub.2, COCC.sub.2, COCF.sub.3, COCH.sub.2 OMe, COCH.sub.2 OPh, COCH.sub.2 CH.dbd.CHCH.sub.3, CO.sub.2 Me, CO.sub.2 Et, CO.sub.2 Bu-t, CO.sub.2 Fr-i, CONHMe, CONMe.sub.2, CONHEt, CONEt.sub.2, CONPr-n.sub.2, CON(CH.sub.2 CH.sub.2).sub.2, CONMePh, ##STR25## CO.sub.2 CH.sub.2 Ph, CO.sub.2 Ph, SO.sub.2 Me, SOMe, SO.sub.2 Et, SO.sub.2 CH.sub.2 CH.dbd.CH.sub.2, SO.sub.2 Ph, SO.sub.2 Ph-Me-4, SO.sub.2 Ph-Cl-4, SO.sub.2 Ph-(NO.sub.2).sub.2 -2,4, SO.sub.2 CF.sub.3, P(.dbd.O)(OMe).sub.2, P(.dbd.O)(OEt).sub.2, P(.dbd.O)(OPr-n).sub.2, P(.dbd.O)(OPr-i).sub.2, P(.dbd.S)(OMe).sub.2, P(.dbd.S)(OEt).sub.2, P(.dbd.O)OMeOPh, P(.dbd.O)(OCH.sub.2 CH.dbd.CH.sub.2).sub.2, P(.dbd.O)OPhOCH.sub.2 CH.dbd.CH.sub.2
When Q is a hydrogen atom, the compound may readily form a salt with a metal or with an organic base.
As such a metal, sodium, potassium, calcium, lithium, barium, magnesium, iron, copper, nickel or manganese may be mentioned.
As such as organic base, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, i-propylamine, di-n-propylamine, n-butylamine, i-butylamine, sec-butylamine, tert-butylamine, piperidine, pyrrolidine, morpholine, pyridine, N,N-dimethylaniline or choline may be mentioned.
In the course of researches on the herbicidal properties of various organic compounds with an aim to develop useful herbicides, the present inventors have found that the above-mentioned compound of the present invention exhibits excellent herbicidal activities against narrow leaf weeds (gramineous and cyperaceous weeds) and against broad leaf weeds and no substantial phytotoxicity against useful plants e.g. crop plants such as Zea mays (corn), Sorghum bicolor (sorgo), Triticum spp (wheat) and Hordeum vulgare (barley). The present invention has been accomplished on the basis of this discovery.
The compound of the present invention exhibits strong herbicidal activities in each of soil treatment, soil incorporation treatment and foliage treatment. On the other hand, it exhibits no phytotoxicity against crop plants such as Zea mays, Sorghum bicolor, Triticum spp and Hordeum vulgare in a practical application in any of soil treatment, soil incorporation treatment and foliage treatment. Thus, the compound of the present invention has high selectivity and it is extremely effective for controlling weeds during the cultivation of these crop plants. Namely, the compound of the present invention exhibits strong herbicidal activities against noxious weeds such as Setaria viridis (green foxtail), Echinochloa crus-galli (barnyardgrass), Amaranthus lividus (livid amaranth), Polygonum longisetum (persicaria blumei gross), Xanthium strumarium (cocklebur), Abutilon theophrasti (velvet leaf) and CVperus esculentus (yellow nutsedge), which develop during the cultivation of Zea mays or Sorghum bicolor. The herbicidal activities against gramineous weeds and Cvperus esculentus are remarkably high and extremely unique. Heretofore, during the cultivation of Zea mays or Sorghum bicolor, it has been common to employ atrazine or cyanazine as a triazine-type herbicide, or alachlor or metolachlor as an acid anilide-type herbicide. However, atrazine and cyanazine have poor herbicidal activities against gramineous weeds although they show high activities against broad leaf weeds, and their activities against Cyperus esculentus are very low. On the other hand, alachlor and metolachlor have poor activities against broad leaf weeds although their activities against gramineous weeds are high, and their activities against Cyperus esculentus are very poor. Thus, it has been difficult to eradicate all the weed species by a single application of such herbicides.
As a result of various studies, the present inventors have found the compound of the present invention which exhibits excellent herbidical effects against a wide range of weeds, and the present invention has been accomplished on the basis of this discovery. The compound of the present invention also has a feature that it exhibits no phytotoxicity against crop plants such as Zea mays, Sorghum bicolor, Triticum spp and Hordeum vulgae and thus can safely be applied to the fields for such crop plants.
Further, the compound of the present invention includes a compound which shows selectivity between Oryza sativa (rice) and Echinochloa crus-galli (barnyardgrass), and it also includes a compound having selectivity for a useful plant such as Gossypium spp (cotton), Beta vulgaris (sugar beat) or Glycine max (soybean).
Heretofore, it has been known that 4-benzoylpyrazole derivatives have excellent herbidical activities. For example, pyrazolate (common name) is commercially available and widely used for practical application. However, such conventional herbicides are restricted in their application to paddy fields, and their activities are very poor in their application to upland fields. Whereas, as a result of extensive research for many years on 4-benzoylpyrazole derivatives, the present inventors have finally found that the compound of the present invention which simultaneously satisfies the various conditions for substituents in the structure as specified above, exhibits strong herbicidal activities in the application to upland fields in each of soil treatment, soil incorporation and foliage treatment. It has been found that the compound of the present invention exhibits particularly high activities against gramineous weeds and Cyperus esculentus.
The compound of the present invention can readily be prepared by any one of the following reactions. ##STR26##
In the above formulas, A, B, X, Y, Z, Q, V and W are as defined above, E is a halogen atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group. Further, ##STR27## and may be represented by either formula. DCC is N,N'-dicyclohexylcarbodiimide.
Reaction scheme (1) represents a reaction wherein benzoic acid having suitable substituents and 5-hydroxypyrazole are reacted in an inert solvent in the presence of DCC and a base to obtain 4-benzoyl-5-hydroxypyrazole. DCC is used in an amount of from 1.0 to 1.5 mols per mol of the benzoic acid and pyrazole. The solvent may be any solvent so long as it is inert to the reaction. Particularly preferred is tert-butyl alcohol, tert-amyl alcohol or isopropyl alcohol. The base may not necessarily be required. However, in general, the yield can be improved by using a base. There is no particular restriction as to the base, but potassium carbonate or sodium carbonate may preferably be employed. The reaction temperature may range from room temperature to the boiling point of the solvent, but is preferably from 50.degree. to 100.degree. C.
The reaction time is usually from 0.5 to 20 hours.
Reaction scheme (2) shows a reaction wherein benzoyl chloride having suitable substituents and 5-hydroxypyrazole are reacted to form a benzoyl ester, which is then rearranged to a 4-benzoyl compound.
The benzoyl esterification can be accomplished in an inert solvent (such as an aromatic hydrocarbon, a fatty acid ester, a halogenated hydrocarbon, an ether, acetonitrile, dimethylsulfoxide or N,N'-dimethylformamide) or in a two phase system with such a solvent and water or in a mixture of such solvents in the presence of a suitable dehydrochlorinating agent (e.g. an inorganic base such as sodium hydroxide, potassium hydroxide or sodium hydrogencarbonate, or an organic base such as pyridine or triethylamine) at a temperature of from room temperature to 100.degree. C. for from 10 minutes to 5 hours.
The rearrangement reaction can be accomplished by means of a Lewis acid such as anhydrous aluminum chloride or a base. As the base, potassium carbonate, calcium hydroxide or sodium carbonate may be used. The Lewis acid or base is used usually in an amount of from 1 to 10 mol times.
No solvent is required. However, in some cases, it is advantageous to use a solvent having a suitable boiling point to improve the operation efficiency or the yield. As such an advantageous example, use of dioxane or diglyme may be mentioned.
The reaction temperature is usually from 50.degree. to 150.degree. C., and the reaction time is usually from 15 minutes to 10 hours.
Reaction scheme (3) shows a reaction wherein 4-benzoyl-5-hydroxypyrazole is condensed with a halide, a methanesulfonic acid ester or a p-toluenesulfonic acid ester.
For this reaction, it is preferred to employ from 1 to 3 mol times of a dehydrohalogenating agent. As such a dehydrohalogenating agent, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate or potassium carbonate, or an organic base such as pyridine or triethylamine, may be mentioned.
There is no particular restriction a to the solvent so long as it is inert to the reaction. A wide range of solvents including an aromatic hydrocarbon, a fatty acid ester, a halogenated hydrocarbon, an ether, a ketone, an aliphatic hydrocarbon, acetonitrile, dimethylsulfoxide and dimethylformamide may be used.
The reaction temperature may be optionally selected within a range of from room temperature to the boiling point of the solvent. The reaction time is usually from 30 minutes to 30 hours.
Reaction scheme (4) shows a reaction wherein 4-benzoyl-5-hydroxypyrazole is converted to a 5-chloro compound by a chlorinating agent, followed by condensation with a suitable alcohol or acid.
As the chlorinating agent, phosphorus oxychloride, phosphorus pentachloride or thionyl chloride may be mentioned.
As the solvent, a wide range of solvents inert to the reaction, such as dimethylformamide, may be employed. However, the reaction can be conducted without any solvent.
The reaction temperature is preferably from 30.degree. to 150.degree. C., and the reaction time is usually from 30 minutes to 10 hours. In some cases, the reaction time may be shortened or the yield may be improved by an addition of a dehydrohalogenating agent.
The condensation reaction with an alcohol or acid is conducted by an addition of a dehydrohalogenating agent.
As such a dehydrohalogenating agent, a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxide or sodium hydride may be employed.
The solvent may be any solvent which is inert to the reaction (such as an aromatic hydrocarbon, an ether, a ketone or N,N'-dimethylformamide). The reaction temperature may be selected within a range of from room temperature to the boiling point of the solvent.
The benzoic acids or benzoyl chlorides used as the starting materials for the compounds of the present invention may readily be prepared by a proper combination of various known syntheses. For instance, compounds wherein the substituent Z in the benzene ring is -S(O).sub.n CH.sub.3 can be prepared in accordance with the following reaction schemes. schemes. ##STR28##
In the above formulas, X, Y, V and W are as defined above, and Hal is a halogen atom.
Now, the preparation of benzoic acids will be described in detail with reference to Reference Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples.
REFERENCE EXAMPLE 1
Preparation of 4-methanesulfonyl-3-methoxymethyl-2-methyl benzoic acid and 3-methoxymethyl-2-methyl-4-methylthio benzoic acid
(1) 2-Methyl-3-nitrobenzyl alcohol
39.0 g (0.2 mol) of methyl 2-methyl-3-nitrobenzoate was dissolved in 600 ml of tert-butanol, and 19.0 g of sodium borohydride was added thereto. Under refluxing, 150 ml of methanol was dropwise added thereto over a period of 1 hour. The refluxing was continued further for 1 hour to complete the reaction. The reaction mixture was left to cool, and then water was added thereto. The solvent was distilled off under reduced pressure. To the residue, water and chloroform were added, and the organic layer was separated and dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 30.7 g of 2-methyl-3-nitrobenzyl alcohol.
(2) 2-Methyl-3-nitrobenzyl methyl ether
30.1 g (0.18 mol) of 2-methyl-3-nitrobenzyl alcohol obtained in the preceding step was dissolved in 200 ml of benzene, and 0.2 g of tetra-n-butylammonium bromide and a 50% aqueous solution of 20.1 g of sodium hydroxide were added thereto sequentially. Then, 27.2 g of dimethyl sulfate was dropwise added thereto at room temperature. Further, the reaction was conducted for 3 hours under stirring. Water was added to the reaction solution, and the organic layer was separated and washed sequentially with water, a 2% hydrochloric acid aqueous solution, water and a saturated sodium chloride aqueous solution. Then, the solvent was distilled off to obtain 30.9 g of 2-methyl-3-nitrobenzyl methyl ether as an oily substance.
(3) 3-Methoxymethyl-2-methylaniline
To 30.7 g (0.17 mol) of the above-mentioned 2-methyl-3-nitrobenzyl methyl ether, 200 ml of methanol was added. After the compound was dissolved in methanol, 92 ml of concentrated hydrochloric acid was gradually added thereto. Then, 30.4 g of iron powder was gradually added so that the reaction temperature became at a level of not higher than 60.degree. C., and the reaction was continued further for 1 hour.
To the reaction solution, 300 ml of water was added, and sodium hydroxide was added until the pH became higher than 8. To the slurry thus obtained, chloroform was added, and the mixture was thoroughly stirred. Then, the solid was separated by filtration, and an organic layer was separated from the filtrate.
This organic layer was washed sequentially with water and a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. Further, the solvent was distilled off under reduced pressure to obtain 23.1 g of 3-methoxymethyl-2-methylaniline as an oily substance.
(4) 3-Methoxymethyl-2-methyl-4-thiocyanoaniline
22.6 g (0.15 mol) of 3-methoxymethyl-2-methylaniline was dissolved in 300 ml of methanol. Then, 36.5 g of sodium thiocyanate was added thereto to obtain a uniform solution. This solution was cooled to 0.degree. C., and 100 ml of a saturated methanol solution of sodium bromide with 25.2 g of bromine was dropwise added thereto so that the reaction temperature did not exceed 5.degree. C. After the dropwise addition, the mixture was stirred at a temperature of not higher than 5.degree. C. for 1 hour and at room temperature for 1 hour to complete the reaction. The reaction solution was poured into 1 liter of water and neutralized with a 5% sodium carbonate aqueous solution. Chloroform was added to extract the oily substance. The chloroform layer was washed with water and a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 29.6 g of the desired product.
(5) 3-Methoxymethyl-2-methyl-4-methylthioaniline
29.1 g (0.14 mol) of 3-methoxymethyl-2-methyl-4-thiocyanoaniline was dissolved in 200 ml of ethanol and mixed with 100 ml of an aqueous solution containing 33.6 g of sodium sulfide nonahydrate at room temperature. Then, 21.9 g of methyl iodide was dropwise added thereto, and the mixture was reacted at room temperature for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and water and chloroform were added to the residue. Then, the organic layer was separated and washed sequentially with water and a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 25.6 g of the desired product as an oily substance.
(6) 3'-Iodo-2'-methyl-6'-methylthiobenzyl methyl ether
To 25.6 g (0.13 mol) of 3-methoxymethyl-2-methyl-4-methylthioaniline, 100 ml of water and 33 ml of concentrated hydrochloric acid were added to convert it to an aniline hydrochloride. This solution was cooled to 0.degree. C., and 30 ml of an aqueous solution containing 9.3 g of sodium nitrite was dropwise added thereto so that the reaction temperature did not exceed 5.degree. C. After completion of dropwise addition, stirring was continued further for 30 minutes to complete diazotization. 100 ml of an aqueous solution containing 33 g of potassium iodide was heated to 70.degree. C., and the aqueous solution of the diazonium salt obtained above was gradually added thereto and decomposed. The reaction solution was stirred further for 1 hour at 70.degree. C. and then left to cool. The oil component was extracted with benzene. The benzene layer was washed sequentially with water, a saturated sodium hydrogensulfite aqueous solution, water and a saturated sodium chloride aqueous solution. Then, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (eluent: benzene) to obtain 30.0 g of the desired product. Melting point: 56.0.degree.-59.0.degree. C.
(7) 3-Methoxymethyl-2-methyl-4-methylthiobenzoic acid
27.7 g (0.09 mol) of 3'-iodo-2'-methyl-6'-methylthiobenzyl methyl ether was dissolved in 100 ml of dried tetrahydrofuran, and 63 ml of a 1.5 M n-butyllithium n-hexane solution was dropwise added thereto at -70.degree. C. After the dropwise addition, the mixture was stirred for 15 minutes at the same temperature, and then dried carbon dioxide gas was thoroughly blown into the reaction solution until the heat generation of the reaction solution stopped. After the reaction, the temperature of the solution was returned to room temperature, and water and diethyl ether were added for liquid separation. The aqueous layer thus obtained was further washed twice with diethyl ether, and then concentrated hydrochloric acid was added to bring the pH<1. Precipitated crystals were collected by filtration, thoroughly washed with water and dried to obtain 14.4 g of the desired product. Melting point: 192.0.degree.-194.0.degree. C.
(8) 4-Methanesulfonyl-3-methoxymethyl-2-methylbenzoic acid
To 11.3 g (0.05 mol) of 3-methoxymethyl-2-methyl-4-methylthiobenzoic acid, 120 ml of acetic acid and 120 ml of a 35% hydrogen peroxide aqueous solution were added, and the mixture was reacted at 80.degree. C. for 1 hour. After cooling, the reaction solution was poured into ice water, whereupon precipitated crystals were collected by filtration, then washed with water and dried to obtain 12.3 g of the desired product. Melting point: 129.0.degree.-131.0.degree. C.
REFERENCE EXAMPLE 2
Preparation of 3-methoxycarbonyl-2-methyl-4-methylthiobenzoic acid and 4-methanesulfonyl-3-methoxycarbonyl-2-methylbenzoic acid
(1) Methyl 3-amino-2-methylbenzoate
40 g of methyl 2-methyl-3-nitrobenzoate was dissolved in 120 ml of methanol, and 157 g of concentrated hydrochloric acid was added thereto. Then, 36.8 g of iron powder was gradually added while maintaining the mixture at a temperature of not higher than 60.degree. C. The mixture was stirred at room temperature for 4 hours and then poured into 1 liter of ice water. The solution was neutralized with sodium carbonate and extracted with chloroform (after filtering off insolubles). The extract was washed with a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 27.8 g of the desired product as an oily substance.
(2) Methyl 3-amino-2-methyl-6-thiocyanobenzoate
While maintaining a solution comprising 27.7 g of methyl 3-amino-2-methylbenzoate, 41.5 g of sodium thiocyanate and 250 ml of methanol at a temperature of not higher than 0.degree. C., 100 ml of sodium bromide-saturated methanol with 28.1 g of bromine was slowly dropwise added thereto. The mixture was stirred at room temperature for 3 hours and then poured into 1 liter of ice water. The solution was neutralized with sodium carbonate and then extracted with chloroform. The extract was washed with a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 34.0 g of the desired product as an oily substance.
(3) Methyl 3-amino-2-methyl-6-methylthiobenzoate
To a solution comprising 39.5 g of sodium sulfide nonahydrate and 110 ml of water, a solution comprising 32.9 g of methyl 3-amino-2-methyl-6-thiocyanobenzoate and 300 ml of ethanol was dropwise added. The mixture was stirred at room temperature for 1.5 hours, and 24.0 g of methyl iodide was dropwise added under cooling with ice. The mixture was stirred further at room temperature for 2 hours and then concentrated under reduced pressure. A saturated sodium chloride aqueous solution was added thereto, and the mixture was extracted with chloroform. The extract was dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 30.1 g of the desired product as an oily substance.
(4) Methyl 3-iodo-2-methyl-6-methylthiobenzoate
28 g of methyl 3-amino-2-methyl-6-methylthiobenzoate was stirred in 150 ml of concentrated hydrochloric acid at room temperature for 2 hours to convert it to a hydrochloride. Then, while maintaining the mixture at a temperature of not higher than 0.degree. C., a solution comprising 11.9 g of sodium nitrite and 20 ml of water was dropwise added thereto to obtain a diazonium salt solution. The diazonium salt solution was dropwise added to a solution comprising 28.4 g of potassium iodide and 90 ml of water while maintaining the solution at 80.degree. C. After completion of the dropwise addition, the mixture was stirred at 80.degree. C. for 15 minutes and left to cool. Water was added thereto, and the mixture was extracted with chloroform. The extract was washed with an aqueous sodium hydrogensulfite solution and water and then dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 40 g of the desired product as a crude product. The crude product was purified by silica gel column chromatography (eluted with benzene) to obtain 36.0 g of a purified product as an oily substance.
(5) 3-Methoxycarbonyl-2-methyl-4-methylthiobenzoic acid
While maintaining a solution comprising 20.0 g of methyl 3-iodo-2-methyl-6-methylthiobenzoate and 70 ml of dried tetrahydrofuran at a temperature of not higher than -60.degree. C. under a nitrogen atmosphere, 42 ml of a 1.5 M n-butyllithium n-hexane solution was dropwise added thereto. Fifteen minutes later, dried carbon dioxide gas was thoroughly blown into the mixture while maintaining it at a temperature of not higher than -50.degree. C. After purging carbon dioxide gas with nitrogen, 12.7 g of diisopropylamine was dropwise added thereto, and the mixture was stirred until the temperature reached room temperature. The mixture was concentrated under reduced pressure. Water was added thereto and the mixture was washed with chloroform. The aqueous solution was acidified with concentrated hydrochloric acid and then extracted with chloroform. The extract was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 7.5 g of the desired product. Melting point: 178.degree.-178.5.degree. C.
(6) 4-Methanesulfonyl-3-methoxycarbonyl-2-methylbenzoic acid
A solution comprising 5.0 g of 3-methoxycarbonyl-2-methyl-4-methylthiobenzoic acid, 25 ml of acetic acid and 25 ml of hydrogen peroxide (35%) was stirred at 80.degree. C. for 3 hours. After cooling, the mixture was poured into ice water and extracted with chloroform. The extract was dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 5.1 g of the desired product. Melting point: 151.degree.-152.degree. C.
REFERENCE EXAMPLE 3
Preparation of 2-chloro-3-ethylthiomethyl-4-methanesulfonylbenzoic acid
(1) Methyl 3-bromomethyl-2-chloro-4-methanesulfonylbenzoate
12.1 g of methyl 2-chloro-4-methanesulfonyl-3-methylbenzoate was dissolved in 250 ml of carbon tetrachloride, and the solution was refluxed under stirring. Then, 7.5 g of bromine and 1 g of benzoyl peroxide were gradually added thereto over a period of 30 minutes, and the solution was further refluxed for 4 hours under heating. After cooling, 200 ml of chloroform was added thereto, and the mixture was washed with a 5% sodium hydrogensulfite aqueous solution. The organic layer was separated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was washed with ethyl ether to obtain 13.2 g of crystals of the desired product. Melting point: 77.degree.-78.degree. C.
(2) Methyl 2-chloro-3-ethylthiomethyl-4-methanesulfonylbenzoate
To 100 ml of tetrahydrofuran, 1.3 g of ethanethiol and 1.5 g of potassium carbonate and then 4.4 g of methyl 3-bromomethyl-2-chloro-4-methanesulfonylbenzoate were added, and the mixture was stirred for 1 day at room temperature. Then, the mixture was stirred further for 1 hour at a temperature of from 50.degree. to 60.degree. C. After cooling, chloroform was added thereto, and the mixture was washed with a dilute potassium carbonate aqueous solution. The chloroform layer was separated and dried. Then, the solvent was distilled off to obtain 4.1 g of methyl 2-chloro-3-ethylthiomethyl-4-methanesulfonylbenzoate as an oily substance.
(3) 2-Chloro-3-ethylthiomethyl-4-methanesulfonylbenzoic acid
To a solution mixture comprising 50 ml of a 10% sodium hydroxide aqueous solution and 150 ml of methanol, 3.9 g of methyl 2-chloro-3-ethylthiomethyl-4-methanesulfonylbenzoate was added, and the mixture was stirred at room temperature for 30 minutes. Methanol was distilled off under reduced pressure, and a dilute hydrochloric acid was added to the residue for acid precipitation. The mixture was extracted with ethyl acetate, and the extract was dried. Then, the solvent was distilled off to obtain 3.5 g of the desired product. Melting point: 172.degree.-174.degree. C.
REFERENCE EXAMPLE 4
Preparation of 2-chloro-4-methanesulfonyl-3-methoxymethylbenzoic acid
(1) Methyl 2-chloro-4-methanesulfonyl-3-methoxymethylbenzoate
To a solution comprising 12.0 g of methyl 3-bromomethyl-2-chloro-4-methanesulfonylbenzoate prepared in Reference Example 3(1) and 100 ml of methanol, 50 ml of a methanol solution containing 1.7 g of sodium methoxide was added, and the mixture was stirred at room temperature overnight. The solvent was distilled off under reduced pressure. Then, dilute hydrochloric acid was added to the residue, and the mixture was extracted with chloroform. The extract was washed with water and dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 9.5 g of the desired product as a crude product. The crude product was purified by silica gel column chromatography (eluted with benzene) to obtain 7.5 g of a purified product as an oily substance.
(2) 2-Chloro-4-methanesulfonyl-3-methoxymethylbenzoic acid
To a solution comprising 3.0 g of methyl 2-chloro-4-methanesulfonyl-3-methoxymethylbenzoate and 20 ml of methanol, a solution comprising 0.57 g of sodium hydroxide (93%) and 2 ml of water was added, and the mixture was stirred at room temperature for 30 minutes. After an addition of 10 ml of water, the mixture was concentrated under reduced pressure. Then, dilute hydrochloric acid was added thereto, and the mixture was extracted with chloroform. The extract was dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 2.6 g of the desired product. Melting point: 137.degree.-141.degree. C.
REFERENCE EXAMPLE 5
Preparation of 2-chloro-4-methanesulfonyl-3-methoxymethylbenzoic acid (alternative method of Reference Example 4)
The desired product was prepared in the same manner as in Reference Example 1. Melting point: 137.degree.-141.degree. C.
The physical properties of the intermediates were as follows:
(1) 2-Chloro-3-nitrobenzyl alcohol: Oily substance
(2) 2'-Chloro-3'-nitrobenzyl methyl ether: Oily substance
(3) 2-Chloro-3-methoxymethylaniline: Oily substance
(4) 2-Chloro-3-methoxymethyl-4-thiocyanoaniline: Melting point: 90.degree.-96.degree. C.
(5) 2-Chloro-3-methoxymethyl-4-methylthioaniline: Oily substance
(6)2'-Chloro-3'-iodo-6'-methylthiobenzyl methyl ether: Melting point: 53.degree.-56.degree. C.
REFERENCE EXAMPLE 6
Preparation of 2-chloro-4-methanesulfonyl-3-methoxycarbonyl benzoic acid
The desired product was prepared in the same manner as in Reference Example 2. Melting point 16020 -162.degree. C.
The physical properties of the intermediates were as follows:
(1) Methyl 3-amino-2-chlorobenzoate: Oily substance
(2) Methyl 3-amino-2-chloro-6-thiocyanobenzoate: Melting point: 80.degree.-83.degree. C.
(3) Methyl 3-amino-2-chloro-6-methylthiobenzoate: Melting point: 70.degree.-72.degree. C.
(4) Methyl 2-chloro-3-iodo-6-methylthiobenzoate: Oily substance
(5) 2-Chloro-3-methoxycarbonyl-4-methylthiobenzoic acid: Melting point: 176.degree.-179.degree. C.
REFERENCE EXAMPLE 7
Preparation of 4-methanesulfonyl-3-[(2-methoxyethyl)oxycarbonyl]-2-methylbenzoic acid
The desired compound was prepared in the same manner as in Reference Example 2. Melting point: 118.degree.-121.degree. C.
The physical properties of the intermediates were as follows:
(1) 2-Methoxyethyl 3-amino-2-methylbenzoate: Oily substance
(2) 2-Methoxyethyl 3-amino-2-methyl-6-thiocyanobenzoate: Melting point: 79.degree.-81.degree. C.
(3) 2-Methoxyethyl 3-amino-2-methyl-6-methylthiobenzoate: Oily substance
(4) 2-Methoxyethyl 3-iodo-2-methyl-6-methylthiobenzoate: Oily substance
(5) 3-[(2-methoxyethyl)oxycarbonyl]-2-methyl-4-methylthiobenzoic acid: Melting point: 90.degree.-93.degree. C.
REFERENCE EXAMPLE 8
Preparation of 2-methyl-4-methylthio-3-n-propoxycarbonylbenzoic acid and 4-methanesulfonyl-2-methyl-3-n-propoxy-carbonylbenzoic acid
(1) Methyl 3-bromo-2-methyl-6-methylthiobenzoate
16.1 g of the compound of Reference Example 2(3) was stirred in 150 ml of hydrobromic acid (48%) to convert it into a hydrobromide. While maintaining the solution at a temperature of not higher than 0.degree. C., a solution comprising 7.2 g of sodium nitrite and 20 ml of water was dropwise added to obtain a diazonium salt solution. The diazonium salt solution was dropwise added to a solution comprising 6.0 g of cuprous bromide and 7.7 g of hydrobromic acid (48%) while refluxing the solution under heating. After completion of the dropwise addition, the mixture was further refluxed for 1 hour under heating and then left to cool. Ice water was added thereto, and the mixture was extracted with chloroform. The extract was washed with an aqueous sodium hydrogensulfite solution and water and then dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 19.2 g of the desired product as a crude product. The crude product was purified by silica gel column chromatography (eluted with benzene) to obtain 17.1 g of a purified product as an oily substance.
(2) 3-Bromo-2-2-methyl-6-methylthiobenzoic acid
To 100 ml of an ethanol solution containing 17.0 g of methyl 3-bromo-2-methyl-6-methylthiobenzoate, 16 g of a 50% sodium hydroxide aqueous solution was added, and the mixture was refluxed for 3 hours under heating. The reaction mixture was concentrated under reduced pressure. Then, water was added thereto, and the mixture was washed with chloroform. The aqueous layer was acidified with concentrated hydrochloric acid and extracted with chloroform. The extract was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 15.9 g of the desired product. Melting point: 98.degree.-103.degree. C.
(3) n-Propyl 3-bromo-2-methyl-6-methylthiobenzoate
Thionyl chloride was added to 15.8 g of 3-bromo-2-methyl-6-methylthiobenzoic acid, and the mixture was refluxed for 4 hours under heating. Thionyl chloride was distilled off, and 70 ml of n-propanol was added to the residue under cooling with ice. Then, a solution comprising 7.3 g of pyridine and 20 ml of n-propanol was dropwise added thereto. The mixture was stirred at room temperature overnight and then concentrated under reduced pressure. Then, ethyl acetate was added thereto, and the mixture was washed sequentially with a 5% sodium carbonate aqueous solution, 10% hydrochloric acid and water and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 18 g of the desired product as a crude product. The crude product was purified by silica gel column chromatography (eluted with benzene) to obtain 16.6 g of a purified product as an oily substance.
(4) 3-Bromo-2-methyl-6-methylthiobenzoic acid
This product was prepared in the same manner as in Reference Example 2(5). Melting point: 138.degree.-142.degree. C.
(5) 3-Bromo-6-methanesulfonyl-2-methylbenzoic acid
This compound was prepared in the same manner as in Reference Example 2(6). Melting point: 142.degree.-146.degree. C.
REFERENCE EXAMPLE 9
Preparation of 2-chloro-3-isopropoxycarbonyl-4-methanesulfonylbenzoic acid
This compound was prepared from the compound of Reference Example 6(4) in the same manner as in Reference Example 8(2)-(5). Melting point: 146.degree.-148.degree. C.
The physical properties of the intermediates were as follows:
(1) 2-Chloro-3-iodo-6-methylthiobenzoic acid: Melting point: 155.degree.-159.degree. C.
(2) Isopropyl 2-chloro-3-iodo-6-methylthiobenzoate: Oily substance
(3) 2-Chloro-3-isopropoxycarbonyl-4-methylthiobenzoic acid: Melting point: 114.degree.-118.degree. C.
REFERENCE EXAMPLE 10
Preparation of 3-(1-methoxyethyl)-2-methyl-4-methylthiobenzoic acid and 4-methanesulfonyl-3-(1-methoxyethyl)-2-methylbenzoic acid
(1) 2'-Methyl-3'-nitroacetophenone
To 5.4 g of metal magnesium, 5 ml of absolute ethanol and 0.5 ml of carbon tetrachloride were dropwise added under a dry nitrogen stream. Further, 130 ml of dried diethyl ether was added under refluxing, and then a solution comprising 25 ml of a diethyl ether, 35.2 g of diethyl malonate and 20 ml of ethanol was dropwise added at a rate to maintain the refluxing. After completion of the dropwise addition, refluxing was continued for 3 hours to prepare diethyl ethoxymagnesiomalonate. To the solution of diethyl ethoxymagnesiomalonate thus obtained, 150 ml of a diethyl ether solution of 40.0 g of 2-methyl-3-nitrobenzoic acid chloride prepared from 2-methyl-3-nitrobenzoic acid and thionyl chloride, was dropwise added over a period of 20 minutes under refluxing, and the reaction was continued for 2 hours. After cooling, dilute sulfuric acid was added thereto for hydrolysis. The diethyl ether layer was washed sequentially with water and a saturated sodium chloride aqueous solution. Then, the solvent was distilled off under reduced pressure, and the residue was dried to obtain a crude product of diethyl 2-(2-methyl-3-nitrobenzoyl)malonate. To this crude product, a mixture comprising 7.5 ml of concentrated sulfuric acid, 60 ml of acetic acid and 40 ml of water was added, and the mixture was refluxed for 6 hours under heating. Then, the mixture was adjusted to pH 10 with a 20% sodium hydroxide aqueous solution. Precipitated oil component was extracted with chloroform. This chloroform layer was washed sequentially with water and a sodium chloride aqueous solution. Then, the solvent was distilled off under reduced pressure to obtain 34.0 g of the desired product. (Yield: 95%) Melting point: 53.0.degree.-54.0.degree. C.
(2) Preparation of 1-methyl-2'-methyl-3'-nitrobenzyl alcohol
To 50 ml of a methanol solution of 0.5 g of sodium hydroxide, 0.9 g of sodium borohydride was added at 0.degree. C., and then 100 ml of a methanol solution of 14.3 g of 2'-methyl-3'-nitroacetophenone was dropwise added thereto. The temperature of the mixture was returned to room temperature and reacted for 1 hour. After the reaction, the reaction mixture was poured into water and extracted with benzene. The subsequent operation was conducted in a usual manner to obtain 14.3 g of the desired product as an oily substance. (Yield: 99%)
Subsequently, the synthesis was conducted in the same manner as in Reference Example 1 to obtain intermediates (3) to (9).
(3) 1-Methyl-2'-methyl-3'-nitrobenzyl methyl ether: Oily substance
(4) 1-Methyl-3'-amino-2'-methylbenzyl methyl ether: Oily substance
(5) 1-Methyl-3'-amino-2'-methyl-6'-thiocyanobenzyl methyl ether: Solid
(6) 1-Methyl-3'-amino-2'-methyl-6'-methylthiobenzyl methyl ether: Oily substance
(7) 1-Methyl-3'-iodo-2'-methyl-6'-methylthiobenzyl: Oily substance
(8) 3-(1-Methoxyethyl)-2-methyl-4-methylthiobenzoic acid: Oily substance
(9) 4-Methanesulfonyl-3-(1-methoxyethyl)-2-methylbenzoic acid: Melting point: 106.degree.-109.degree. C.
REFERENCE EXAMPLE 11
Preparation of 2,4-dichloro-3-methoxycarbonylbenzoic acid
(1) 2,4-dichloro-3-nitrobenzoic acid
To a solution of 25 ml of fuming nitric acid and 20 ml of sulfuric acid, 25 g of 2,4-dichlorobenzoic acid was gradually added. After completion of the heat generation, the reaction mixture was poured into ice water. Precipitated solid was washed with water and dried to obtain 23.0 g of the desired product.
(2) Methyl 2,4-dichloro-3-nitrobenzoate
23.0 g of 2,4-dichloro-3-nitrobenzoic acid and 150 ml of thionyl chloride were refluxed for 6 hours under heating. Then, thionyl chloride was distilled off to obtain crude 2,4-dichloro-3-nitrobenzoyl chloride. 200 ml of methanol was added to the crude compound and refluxed under heating. Methanol was distilled off, and then ethyl acetate was added thereto to obtain an ethyl acetate solution. The solution was washed sequentially with a 5% sodium hydroxide aqueous solution, diluted hydrochloric acid and water. After drying, the solvent was distilled off to obtain 21.8 g of the desired product. Melting point: 72.degree.-74.degree. C.
Subsequently, the synthesis was conducted in the same manner as in Reference Example 1 to obtain intermediates (3) and (4), and the desired product (5).
(3) 3-amino-2,4-dichlorobenzoate: Oily substance
(4) Methyl 2,4-dichloro-3-iodobenzoate: Oily substance
(5) 2,4-dichloro-3-methoxycarbonylbenzoic acid: Melting point: 183.degree.-185.degree. C.
REFERENCE EXAMPLE 12
Preparation of 2-chloro-3-cyanomethyl-4-methanesulfonyl benzoic acid
(1) Methyl 2-chloro-3-cyanomethyl-4-methanesulfonylbenzoate
5.0 g of methyl 3-bromomethyl-2-chloro-4-methanesulfonylbenzoate was added to a solution of 0.4 g of 18-crown-6 and 1.9 g of potassium cyanide in 50 ml of acetonitrile. The mixture was stirred for 72 hours at room temperature. After filtering off the solid, water was added to the filtrate, and the mixture was extracted with chloroform. After washing the extract with water and drying it, the solvent was distilled off to obtain a crude product. The crude product was purified by short silica gel column chlomatography (eluent: chloroform) to obtain 4.1 g of the desired product. Melting point: 151.degree.-155.degree. C.
(2) 2-chloro-3-cyanomethyl-4-methanesulfonylbenzoic acid
To 4.0 g of methyl 2-chloro-3-cyanomethyl-4-methanesulfonylbenzoate and 50 ml of methanol, 5 ml of an aqueous solution containing 0.72 g of sodium hydroxide (93%) was gradually added. The mixture was stirred for 15 minutes at room temperature. Then, the reaction mixture was neutralized with diluted hydrochloric acid, methanol was distilled off under reduced pressure and the concentrated solution was extracted with chloroform. After washing the extract with water and drying it, chloroform was distilled off to obtain 0.9 g of the desired product. Melting point: 169.degree.-172.degree. C.
REFERENCE EXAMPLE 13
Preparation of 3-acetoxymethyl-2-chloro-4-methanesulfonyl benzoic acid
(1) Methyl 3-acetoxymethyl-2-chloro-4-methanesulfonylbenzoate
50 ml of a DMF solution containing 5.0 g of methyl 3-bromomethyl-2-chloro-4-methanesulfonylbenzoate and 1.2 g of sodium acetate, was stirred for 2 hours at 100.degree. C. After cooling, the reaction mixture was poured into ice water and extracted with chloroform. After washing the extract with water and drying it, the solvent was distilled off to obtain 4.2 g of the desired product. Melting point: 165.degree.-168.degree. C.
(2) 2-chloro-3-hydroxymethyl-4-methanesulfonylbenzoic acid
6 ml of an aqueous solution containing 1.3 g of sodium hydroxide (93%), was added to 3.9 g of methyl 3-acetoxymethyl-2-chloro-4-methanesulfonylbenzoate and 100 ml of methanol. The mixture was stirred for 30 minutes at room temperature. 50 ml of water was added thereto, and methanol was distilled off under reduced pressure. Then, the reaction mixture was acidified with hydrochloric acid and extracted with chloroform. The extract was concentrated to dryness to obtain 1.3 g of the desired product. Melting point: 240.degree.-245.degree. C.
(3) 3-acetoxymethyl-2-chloro-4-methanesulfonylbenzoic acid
1.3 g of 2-chloro-3-hydroxymethyl-4-methanesulfonyl benzoic acid and 30 ml of acetic anhydride, was refluxed for 3 hours under heating. The reaction mixture was concentrated under reduced pressure. Then, 50 ml of water was added thereto and warmed for 1 hour. Precipitated solid was collected by filtration, washed with water and dried to obtain 1.35 g of the desired product. Melting point: 219.degree.-223.degree. C.
REFERENCE EXAMPLE 14
Preparation of 2,4-dichloro-3-methoxymethylbenzoic acid
This compound was prepared in the same manner as in Reference Examples 3(1) and 4. Melting point: 13.degree.-136.degree. C.
The physical properties of the intermediates were as follows:
(1) Methyl 3-bromomethyl-2,4-dichlorobenzoate: Melting point: 55.degree.-58.degree. C.
(2) Methyl 2,4-dichloro-3-methoxymethylbenzoate: Oily substance
The physical properties of benzoic acids prepared in accordance with the preceding Reference Examples will be given in Tables 1 and 2 including those of the preceding Reference Examples.
TABLE 1______________________________________ ##STR29##X Y Z Melting point (.degree.C.)______________________________________Me CH.sub.2 OMe SMe 192.about.194Me CH.sub.2 OMe SO.sub.2 Me 129.about.131Me CO.sub.2 Me SMe 178.about.178.5Me CO.sub.2 Me SO.sub.2 Me 151.about.152Me CH.sub.2 OEt SMe 172.about.175Me CH.sub.2 OEt SO.sub.2 Me 160.about.162Cl CO.sub.2 Me Cl 183-185Me CHMeOMe SMe Oily substanceMe CHMeOMe SO.sub.2 Me 106.about.109Me CO.sub.2 Pr-i SMe 151-153Me CO.sub.2 Pr-i SO.sub.2 Me 153.about.155Cl CH.sub.2 OMe SO.sub.2 Me 137.about.141Me CH.sub.2 OPr-i SMe 134.about.138Me CH.sub.2 OPr-i SO.sub.2 Me 159.about.161Me CO.sub.2 CH.sub.2 CH.sub.2 OMe SMe 90.about.93Me CO.sub.2 CH.sub.2 CH.sub.2 OMe SO.sub.2 Me 118.about.121Cl CH.sub.2 SEt SO.sub.2 Me 172.about.174Me CO.sub.2 Et SMe 114.about.120Me CO.sub.2 Et SO.sub.2 Me 119.7.about.127.9Cl CH.sub.2 OCH.sub.2 CH.sub.2 OMe SO.sub.2 Me 93.about.95Cl ##STR30## SO.sub.2 Me Oily substanceMe ##STR31## SMe 169.about.172Me ##STR32## SO.sub.2 Me 129.about.134Me CO.sub.2 Pr-n SMe 138.about.142Me CO.sub.2 Pr-n SO.sub.2 Me 142.about.146Cl CH.sub.2 OH SO.sub.2 Me 240.about.245Cl CO.sub.2 Me SMe 176.about.179Cl CO.sub.2 Me SO.sub.2 Me 160.about.162Cl CO.sub.2 Pr-i SMe 114.about.118Cl CO.sub.2 Pr-I SO.sub.2 Me 146.about.148OMe CO.sub.2 Me SMe 107.about.109OMe CO.sub.2 Me SO.sub.2 Me 113.about.119Me CHEtOMe SMe Oily substanceMe CHEtOMe SO.sub.2 Me Oily substanceMe CHMeOEt SMe Oily substanceMe CHMeOEt SO.sub.2 Me Oily substanceCl CH.sub.2 OCH.sub.2 CCH SO.sub.2 Me 166.about.169Cl CH.sub.2 OCH.sub.2 CHCH.sub.2 SO.sub.2 Me 118.about.119Cl CH.sub.2 OAm-n SO.sub.2 Me Oily substanceMe CO.sub.2 Am-i SMe 98.about.105Me CO.sub.2 Am-i SO.sub.2 Me 107.about.113Cl CH.sub.2 OCH.sub.2 CF.sub.3 SO.sub.2 Me 155.about.157OMe CH.sub.2 OMe SMe 157.about.161OMe CH.sub.2 OMe SO.sub.2 Me Oily substanceMe CO.sub.2 CH.sub.2 CH.sub.2 Cl SMe 138.about.144Me CO.sub.2 CH.sub.2 CH.sub.2 Cl SO.sub.2 Me 121.about.126Cl CH.sub.2 CN SO.sub.2 Me 169.about.172Cl CH.sub.2 OAc SO.sub.2 Me 219.about.223Cl CH.sub.2 OMe Cl 130.about.136Cl CO.sub.2 Et SO.sub.2 Me 156.about.159Cl CHCHOMe SO.sub.2 Me 146.about.149 (trans)Cl CON(Et).sub.2 SO.sub.2 Me 196.about.201______________________________________
TABLE 2______________________________________X Y Z .sup.1 H--NMR (.delta., ppm) [Solvent]______________________________________Me CHEtOMe SO.sub.2 Me 1.19(3H, t), 1.63(3H, d), 2.78(3H, s), 3.18(3H, s), 3.35(2H, q), 5.63(1H, q), 7.81(2H, A-B q), 10.20(1H, s) [CDCl.sub.3 ]Me CHMeOEt SMe 1.00(3H, t), 1.67.about.2.26(2H, m), 2.46(3H, s), 2.69(3H, s), 3.21(3H, s), 4.91(1H, d-d) 7.48(2H, A-Bq), 10.2(1H, s) [CDCl.sub.3 ]Me CHMeOEt SO.sub.2 Me 1.04(3H, t), 1.60.about.2.20(2H, m), 2.66(3H, s), 3.23(6H, s), 5.26(1H, d-d), 7.79(2H, A-B q) 9.0(1H, Broad s) [CDCl.sub.3 + DMSO-d.sub.6 ]OMe CH.sub.2 OMe SO.sub.2 Me 3.04(3H, s), 3.24(3H, s), 3.71(3H, s), 4.71(2H, s), 7.71(2H, s), 8.88(1H, Broad s) [CDCl.sub.3 + DMSO-d.sub.6 ]______________________________________
These benzoic acids can readily be led to benzoyl chlorides by chlorinating agents such as phosphorus pentachloride, thionyl chloride and sulfuryl chloride.
By using such benzoic acids or benzoyl chlorides, compounds of the present invention can be readily prepared in accordance with reaction schemes (1) to (4).
The present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples.





EXAMPLE 1
Preparation of 1-ethyl-5-hydroxy-4-(4-methanesulfonyl-3-methoxymethyl-2-methylbenzoyl)pyrazole
1.12 g (0.01 mol) of 1-ethyl-5-hydroxypyrazole is dissolved in 30 ml of t-amyl alcohol, and then 2.59 g (0.01 mol) of 4-methanesulfonyl-3-methoxymethyl-2-methylbenzoic acid, 2.06 g (0.01 mol) of N,N'-dicyclohexylcarbodiimide and 0.69 g (0.005 mol) of anhydrous potassium carbonate were sequentially added thereto. The mixture was reacted at a temperature of from 80.degree. to 90.degree. C. for 8 hours under stirring. After completion of the reaction, t-amyl alcohol was distilled off under reduced pressure, and 30 ml of water was added to the residue to dissolve the soluble components. The mixture was subjected to filtration to separate out the insolubles. The aqueous solution thus obtained was washed with chloroform, and concentrated hydrochloric acid was added to adjust pH<1. The precipitated oil component was extracted with chloroform. The solvent was distilled off under reduced pressure, and the residue was purified with silica gel column chromatography (eluent: ethyl acetate/ethanol=9/1) to obtain 2.3 g of the desired product. (Yield: 66%, melting point: 116.degree.-118.degree. C.)
EXAMPLE 2
Preparation of 1-ethyl-5-hydroxy-4-(4-methanesulfonyl-3-methoxycarbonyl-2-methylbenzoyl)pyrazole
1.12 g (0.01 mol) of 1-ethyl-5-hydroxypyrazole was dissolved in 30 ml of t-amyl alcohol, and 2.72 g (0.01 mol) of 4-methanesulfonyl-3-methoxycarbonyl-2-methylbenzoic acid, 2.27 g (0.011 mol) of N,N'-dicyclohexylcarbodiimide and 0.76 g (0.0055 mol) of anhydrous potassium carbonate were sequentially added thereto. The mixture was reacted at 80.degree. C. for 6 hours under stirring. After completion of the reaction, t-amyl alcohol was distilled off under reduced pressure, and then water was added to the residue to dissolve the soluble component. The mixture was subjected to filtration to separate out the insolubles. The aqueous solution thus obtained was washed twice with chloroform, and then concentrated hydrochloric acid was added to adjust pH<1. The precipitated oil component was extracted with chloroform. The chloroform layer was washed sequentially with water and a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate Then, the solvent was distilled off under reduced pressure, and the residue thus obtained was recrystallized from water/ethanol to obtain 2.26 g of the desired product. (Yield: 62%, melting point: 150.degree.-152.degree. C.)
EXAMPLE 3
Preparation of 5-hydroxy-(3-isopropoxycarbonyl-4-methanesulfonyl-2-methylbenzoyl)-1-methylpyrazole
The operation and treatment were conducted in the same manner as in Example 1 except that 1.12 g of 1-ethyl-5-hydroxypyrazole was changed to 0.98 g of 5-hydroxy-1-methylpyrazole, and 2.72 g of 4-methanesulfonyl-3-methoxycarbonyl-2-methylbenzoic acid was changed to 3.00 g of 3-isopropoxycarbonyl-4-methanesulfonyl-2-methylbenzoic acid, to obtain 1.71 g of the desired product. (Yield: 45%, melting point: 192.degree.-194.degree. C.)
EXAMPLE 4
Preparation of 4-(2-chloro-3-ethylthiomethyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole
3 g of 2-chloro-3-ethylthiomethyl-4-methanesulfonylbenzoic acid, 0.72 g of potassium carbonate, 50 ml of t-amyl alcohol, 1.95 g of N,N'-dicyclohexylcarbodiimide and 4.5 g of a 25% t-amyl alcohol solution of 1-ethyl-5-pyrazolone were mixed and heated under stirring for 4 hours at a temperature of from 70.degree. to 80.degree. C. After cooling, the mixture was distilled under reduced pressure, and 200 ml of water was added to the residue. After filtering off the insolubles, the filtrate was washed with chloroform. Hydrochloric acid was added to the aqueous layer, and the mixture was extracted with chloroform. The extract was dried, and the solvent was distilled off to obtain the desired product as a crude product. The crude product was recrystallized from ethanol to obtain 1.88 g of the purified product. (Melting point: 142.degree.-145.degree. C.)
EXAMPLE 5
Preparation of 4-(2-chloro-5-ethanesulfonylmethyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole
0.5 g of the compound obtained in Example 4 was dissolved in a solution comprising 30 ml of CHCl.sub.3 and 30 ml of THF at room temperature, and 2.2 equivalent of m-chloroperbenzoic acid was added thereto under cooling in ice bath. The mixture was gradually returned to room temperature and stirred for 1 day. The solvent was distilled off, and crystals thus obtained were collected by filtration and washed with ethyl ether to obtain 2.2 g of the desired product. (Melting point: 133.degree.-135.degree. C.)
EXAMPLE 6
Preparation Of 4-(2-chloro-3-ethanesulfinyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole
0.45 g of the compound obtained in Example 4 was dissolved in 30 ml of dioxane, and 0.21 g of sodium bromite trihydrate was added thereto. The mixture was stirred at room temperature for 30 minutes, and then water was added thereto. The mixture was extracted with chloroform. The extract was dried, and the solvent was distilled off to obtain a crude product. The crude product was purified by column chromatography (eluted with chloroform/ethanol) to obtain 0.2 g of the desired product as an oily substance.
EXAMPLE 7
Preparation of 4-(2,4-dichloro-3-methoxycarbonylbenzoyl)-3-1-ethyl-5-hydroxypyrazole
This compound was prepared in the same manner as in Example 2. Melting point: 167.degree.-170.degree. C.
EXAMPLE 8
Preparation of 5-benzyloxy-4-(2,4-dichloro-3-methoxycarbonylbenzoyl)-1-ethylpyrazole
A solution prepared by dissolving 0.3 g of the compound prepared in Example 7 and 0.1 g of triethylamine in 13 ml of benzene, was stirred at room temperature for 30 minutes, and then at 50.degree. C. for 3 hours. Insoluble substances were filtered off, and then the filtrate was concentrated under reduced pressure The concentrated product was purified by silica gel column chromatography (eluent: benzene/ethyl acetate) to obtain 0.15 g of the desired product as an oily substance.
EXAMPLE 9
Preparation of 5-hydroxy-4-(4-methanesulfonyl-3-methoxymethyl-2-methylbenzoyl)-3-methoxymethyl-1-methylpyrazole
(1) 5-(4-methanesulfonyl-3-methoxymethyl-2-methylbenzoyl)oxy- 3-methoxymethyl-1-methylpyrazole
1.9 g of 5-hydroxy-3-methoxymethyl was added to a mixture consisting of 8 ml of an aqueous solution containing 0.5 g of potassium hydroxide (85%) and 12 ml of chloroform, and then 4-methanesulfonyl-3-methoxymethyl-2-methylbenzoyl chloride was added thereto. The mixture was stirred for 3 hours at room temperature. Then, the reaction mixture was extracted with chloroform. The chloroform solution was washed with water and dried to obtain the desired product substantially quantitatively as an oily substance.
(2) 5-hydroxy-4-(4methanesulfonyl-3-methoxymethyl-2-methylbenzoyl)-3-methoxymethyl-1-methylpyrazole
3.0 g of the compound obtained in step (1), 2.7 g of potassium carbonate and 8 ml of dioxane, were stirred at 120.degree. C. for 3.5 hours. 20 ml of water was added thereto and then the mixture was left to cool. The reaction solution was washed with chloroform and acidified with hydrochloric acid. The reaction solution was extracted with chloroform, washed with water and dried to obtain 1.8 g of a crude product. The crude product was recrystallized from ethanol to obtain 1.2 g of the desired product Melting point: 100.degree.-104.degree. C.
EXAMPLE 10
Preparation of 4-(3-acetoxymethyl-2-chloro-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole
This compound was prepared in the same manner as in Example 2. Melting point: 140.degree.-144.degree. C.,
EXAMPLE 11
Preparation of 4-(2-chloro-3-hydroxymethyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole
To 30 ml of a methanol solution containing 0.3 g of the compound prepared in Example 10, 5 ml of an aqueous solution containing 0.1 g of sodium hydroxide (93%) was added, and the mixture was stirred for 2 hours at room temperature. Methanol was distilled off under reduced pressure. Then, hydrochloric acid was added to the residue. The precipitated product was collected by filtration to obtain 0.2 g of the desired product. Melting point: 70.degree.-76.degree. C.
The physical properties of the compounds prepared in the same manner as the preceding Examples will be given in Tables 3 and 4 including those of the preceding Examples.
TABLE 3__________________________________________________________________________ ##STR33##CompoundNo. A B X Y Z Q Melting point (.degree.C.)__________________________________________________________________________1 Me H Me CH.sub.2 OMe SO.sub.2 Me H Oily substance2 Me H Me CH.sub.2 OMe SO.sub.2 Me CH.sub.2 Ph Oily substance3 Et H Me CH.sub.2 OMe SO.sub.2 Me H 116.about.1184 i-Pr H Me CH.sub.2 OMe SO.sub.2 Me H Oily substance5 Me H Me CO.sub.2 H SO.sub.2 Me H 274.about.274.56 Me H Me CO.sub.2 Me SO.sub.2 Me H 199.about.2017 Et H Me CO.sub.2 Me SO.sub.2 Me H 150.about.1528 Me H Me CO.sub.2 Et SO.sub.2 Me H 174.about.174.59 Et H Me CO.sub.2 Et SO.sub.2 Me H 78.about.8110 Me H Me CO.sub.2 Pr-i SO.sub.2 Me H 192.about.19411 Et H Me CO.sub.2 Pr-i SO.sub.2 Me H 125.about.12812 Me H Cl CO.sub.2 Me Cl H 123.about.12613 Me H Cl CO.sub.2 Me Cl p-Ts Oily substance14 Me H Me CH.sub.2 OEt SO.sub.2 Me H 178.about.17915 Et H Me CH.sub.2 OEt SO.sub.2 Me H Oily substance16 i-Pr H Me CH.sub.2 OEt SO.sub.2 Me H Oily substance17 Me Me Me CH.sub.2 OEt SO.sub.2 Me H Oily substance18 Me H Me CHMeOMe SO.sub.2 Me H 238.about.24019 Et H Me CHMeOMe SO.sub.2 Me H 138.about.14120 Me H Cl CH.sub.2 OMe SO.sub.2 Me H 189.about.19021 Et H Cl CH.sub.2 OMe SO.sub.2 Me H 151.about.15422 i-Pr H Cl CH.sub.2 OMe SO.sub.2 Me H 142.about.14423 Et H Me CH.sub.2 OPr-i SO.sub.2 Me H 125.about.12724 Me H Me CO.sub.2 CH.sub.2 CH.sub.2 OMe SO.sub.2 Me H 114.about.11725 Et H Me CO.sub.2 CH.sub.2 CH.sub.2 OMe SO.sub.2 Me H 122.about.12426 Me H Cl CH.sub.2 OCH.sub.2 CH.sub.2 OMe SO.sub.2 Me H 157.about.16127 Et H Cl CH.sub.2 SEt SO.sub.2 Me H 142.about.14528 Et H Cl CH.sub.2 SOEt SO.sub.2 Me H Oily substance29 Et H Cl CH.sub.2 SO.sub.2 Et SO.sub.2 Me H 133.about.13530 Et H Me CO.sub.2 Pr-n SO.sub.2 Me H Oily substance31 Me H Cl ##STR34## SO.sub.2 Me H Oily substance32 Me H Me ##STR35## SO.sub.2 Me H 220.about.22233 Et H Me ##STR36## SO.sub.2 Me H 179.about.18334 Me H Cl CO.sub.2 Me SO.sub.2 Me H 183.about.18535 Et H Cl CO.sub.2 Me SO.sub.2 Me H 174.about.17636 Pr-i H Cl CO.sub.2 Me SO.sub.2 Me H 138.about.14037 Et H Cl CH.sub.2 OCH.sub.2 C CH SO.sub.2 Me H 161.about.16438 Me H Cl CH.sub.2 OAm-n SO.sub.2 Me H Oily substance39 Et H Me CH.sub.2 OMe SO.sub.2 Me K 180.about.19040 Et H Me CH.sub.2 OMe SO.sub.2 Me Na 210.about.21641 Et H Me CH.sub.2 OMe SO.sub.2 Me NH.sub.3.sup.+ Pr-i 95.about.10242 Me H OMe CO.sub.2 Me SO.sub.2 Me H 195.about.19843 Me H Cl CO.sub.2 Pr-i SO.sub.2 Me H 117.about.11944 Et H Cl CO.sub.2 Pr-i SO.sub.2 Me H 141.about.14345 Me H Cl CH.sub.2 OCH.sub.2 CF.sub.3 SO.sub.2 Me H 167.about.17046 Et H Me CH.sub.2 OMe SO.sub.2 Me 1/2 Ca 232.about.24247 Pr-i H Me CO.sub.2 Me SO.sub.2 Me H 116.about.12148 Me H OMe CH.sub.2 OMe SO.sub.2 Me H 154.about.15749 Et H Me CO.sub.2 CH.sub.2 CH.sub.2 Cl SO.sub.2 Me H 149.about.15250 Et H OMe CO.sub.2 Me SO.sub.2 Me H 172.about.17551 Et H Cl CO.sub.2 Me Cl H 167.about.17052 Et H Cl CO.sub.2 Me Cl CH.sub.2Ph Oily substance53 Pr-i H Cl CO.sub.2 Me Cl H 144.about.15154 Pr-i H Cl CO.sub.2 Me Cl CH.sub.2Ph 104.about.11055 Me CH.sub.2 OMe Me CH.sub.2 OMe SO.sub.2 Me H 100.about.10456 Et H Cl CH.sub.2 CN SO.sub.2 Me H 235.about.23957 Et H Cl CH.sub.2 OAc SO.sub.2 Me H 140.about.14458 Et H Cl CH.sub.2 OH SO.sub.2 Me H 70.about.7659 Et H Me CO.sub.2 Me SMe H 142.about.14660 Et H Cl CH.sub.2 Me Cl H 102.about.10461 Et H Cl CO.sub.2 Et SO.sub.2 Me H 100.about.10462 Et H Me CH.sub.2 OMe SMe H Oily substance63 Me H Cl CH.sub.2 OMe Cl H 141.about.14464 Et H Cl CHCHOMe SO.sub.2 Me H 165.about.171 (trans)65 Pr-i H Cl CO.sub.2 Et SO.sub.2 Me H 123.about.12666 Et H OMe CH.sub.2 OMe SO.sub.2 Me H Oily substance67 Et H Me CHMeOEt SO.sub.2 Me H Oily substance68 Et H Me CHEtOMe SO.sub.2 Me H Oily substance69 Et H Cl CON(Et).sub.2 SO.sub.2 Me H 94.about.97__________________________________________________________________________
The compounds represented by the Compound Nos. in the following Table are the same as represented by the corresponding Compound Nos. in Table 3.
TABLE 4______________________________________CompoundNo. .sup.1 H--NMR (.delta., ppm) [Solvent]______________________________________ 1 2.47(3H,s), 3.22(3H,s), 3.50 (3H,s), 3.69(3H,s), 4.96(2H,s), 7.30(1H,s), 7.78(2H,A-Bq), 10.9(1H) [CDCl.sub.3 ] 2 2.41(3H,s), 3.17(3H,s), 3.50 (3H,s), 4.94(2H,s), 5.53(2H,s), 7.30.about.8.12 (8H,m) [CDCl.sub.3 ] 3 1.44(3H,t), 2.48(3H,s), 3.23 (3H,s), 3.51(3H,s), 4.07(2H,q), 4.98(2H,s), 7.36(1H,s), 7.82(2H,A-Bq) [CDCl.sub.3 ] 4 1.48(6H,d), 2.47(3H,s), 3.19 (3H,s), 3.48(3H,s), 4.53(1H,m), 4.92(2H,s), 7.18(1H,s), 7.69(2H,A-Bq), 9.57(1H) [CDCl.sub.3 ]13 2.43(3H,s), 3.78(3H,s), 3.94 (3H,s), 7.24.about.7.81(7H,m) [CDCl.sub.3 ]15 1.07(3H,t), 2.27(3H,s), 3.01 (3H,s), 3.30.about.3.65(5H,m), 4.77(2H,s), 6.99(1H,s), 7.48(2H, A-B q), 8.22(1H,s) [CDCl.sub.3 ]28 1.45(3H,t), 3.04(2H,q), 4.05 (2H,q), 4.91(2H,q), 7.29(1H,s), 7.70 (1H,s), 7.85(2H,q) [CDCl.sub.3 ]30 0.91.about.2.03(8H,m), 2.41(3H,s), 3.20(3H,s), 3.91.about.4.47(4H,m), 7.36.about.8.08 (4H,m), [CDCl.sub.3 ]16 1.26(3H,t), 1.49(3H,d), 2.49 (3H,s), 3.24(3H,s), 3.69(2H,q), 4.59 (1H,m), 5.00(2H,s), 7.28.about.8.14(4H,m), [CDCl.sub.3 ]17 1.27(3H,t), 1.67(3H,s), 2.42 (3H,s), 3.23(3H,s), 3.63(3H,s), 3.68 (2H,q), 5.02(2H,s), 7.7 (1H,s), 7.75 (2H,A-B q) [CDCl.sub.3 ]62 1.45(3H,t), 2.49(6H,Broad s), 3.44(3H,s), 4.03(2H,q), 4.66 (2H,s), 7.29(2H,q), 7.39(1H,s),66 1.47(3H,t), 3.29(3H, s), 3.51(3H,s), 3.82(3H,s), 4.09(2H,q), 5.00 (2H,s), 7.50(1H,s), 7.84(2H,A-Bq), 7.96(1H,s), [CDCl.sub.3 ]67 1.07-1.67 (9H, m), 2.59(3H,s), 3.17(3H,s), 3.42(2H,t), 3.96 (2H,t), 5.61(1H,q), 7.27(1H,s), 7.61(2H,A-Bq) 9.66 (1H, Broad s) [CDCl.sub.3 ]68 1.09(3H,t), 1.45(3H, t), 2.55(3H,s) 3.16(3H,s), 3.27(3H,s), 3.70-4.20(4H,m), 5.13-5.36(1H,m), 7.14(1H,s), 7.60(2H, A-Bq), 9.46(1H, Broad s) [CDCl.sub.3 ]______________________________________
Compounds which can be prepared in the same manner as the preceding Examples will be given in Table 5 including those of the preceding Examples. However, the present invention is not restricted to such compounds.
Various symbols used in Table 5 has the following meanings. ##STR37##
TABLE 5__________________________________________________________________________A B X Y Z Q__________________________________________________________________________Me H Cl COOMe MeS HMe H Cl COOMe MeSO HMe H Cl COOMe Ms HMe H Cl COOMe Ms Q1Me H Cl COOMe Ms Q2Me H Cl COOMe Ms Q3Me H Cl COOMe Ms Q4Me H Cl COOMe Ms Q5Me H Cl COOMe Ms Q6Me H Cl COOMe Ms Q20Me Me Cl COOMe Ms HMe Cl Cl COOMe Ms HMe CF.sub.3 Cl COOMe Ms HMe OMe Cl COOMe Ms HMe SMe Cl COOMe Ms HMe H Cl COOEt MeS HMe H Cl COOEt MeSO HMe H Cl COOEt Ms HMe H Cl COOEt Ms Q1Me H Cl COOEt Ms Q18Me H Cl COOEt Ms Q13Me H Cl COOEt Ms Q4Me H Cl COOEt Ms Q5Me H Cl COOEt Ms Q6Me H Cl COOEt Ms Q22Me Me Cl COOEt Ms HMe Cl Cl COOEt Ms HMe CF.sub.3 Cl COOEt Ms HMe OMe Cl COOEt Ms HMe SMe Cl COOEt Ms HMe H Cl COOCH(CH.sub.3).sub.2 MeS HMe H Cl COOCH(CH.sub.3).sub.2 MeSO HMe H Cl COOCH(CH.sub.3).sub.2 Ms HMe H Cl COOCH(CH.sub.3).sub.2 Ms Q7Me H Cl COOCH(CH.sub.3).sub.2 Ms Q12Me H Cl COOCH(CH.sub.3).sub.2 Ms Q9Me H Cl COOCH(CH.sub.3).sub.2 Ms Q4Me H Cl COOCH(CH.sub.3).sub.2 Ms Q5Me H Cl COOCH(CH.sub.3).sub.2 Ms Q6Me H Cl COOCH(CH.sub.3).sub.2 Ms Q17Me Me Cl COOCH(CH.sub.3).sub.2 Ms HMe Cl Cl COOCH(CH.sub.3).sub.2 Ms HMe CF.sub.3 Cl COOCH(CH.sub.3).sub.2 Ms HMe OMe Cl COOCH(CH.sub.3).sub.2 Ms HMe SMe Cl COOCH(CH.sub.3).sub.2 Ms HMe H Cl COOMe Cl HMe H Cl COOMe Cl Q1Me H Cl COOMe Cl Q2Me H Cl COOMe Cl Q3Me H Cl COOEt Cl HMe H Cl COOEt Cl Q1Me H Cl COOEt Cl Q2Me H Cl COOEt Cl Q3Me H Cl COOCH(CH.sub.3).sub.2 Cl HMe H Cl COOCH(CH.sub.3).sub.2 Cl Q1Me H Cl COOCH(CH.sub.3).sub.2 Cl Q2Me H Cl COOCH(CH.sub.3).sub.2 Cl Q3Me H Cl CON(CH.sub.3).sub.2 MeS HMe H Cl CON(CH.sub.3).sub.2 MeSO HMe H Cl CON(CH.sub.3).sub.2 Ms HMe H Cl CON(CH.sub.3).sub.2 Ms Q1Me H Cl CON(CH.sub.3).sub.2 Ms Q18Me H Cl CON(CH.sub.3).sub.2 Ms Q13Me H Cl CON(CH.sub.3).sub.2 Ms Q4Me H Cl CON(CH.sub.3).sub.2 Ms Q5Me H Cl CON(CH.sub.3).sub.2 Ms Q6Me H Cl CON(CH.sub.3).sub.2 Ms Q22Me Me Cl CON(CH.sub.3).sub.2 Ms HMe Cl Cl CON(CH.sub.3).sub.2 Ms HMe CF.sub.3 Cl CON(CH.sub.3).sub.2 Ms HMe OMe Cl CON(CH.sub.3).sub.2 Ms HMe SMe Cl CON(CH.sub.3).sub.2 Ms HMe H Cl CON(CH.sub.3).sub.2 Cl HMe H Cl CON(CH.sub.3).sub.2 Cl Q1Me H Cl CON(CH.sub.3).sub.2 Cl Q2Me H Cl CON(CH.sub.3).sub.2 Cl Q3Me H Cl COOC.sub.4 H.sub.9 Ms HMe H Cl COOC.sub.4 H.sub.9 Cl HMe H Cl COOCH.sub.2 CH(CH.sub.3).sub.2 Ms HMe H Cl COOCH.sub.2 CH(CH.sub.3).sub.2 Cl HMe H Cl COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms HMe H Cl COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl HMe H Cl COOC(CH.sub.3).sub.3 Ms HMe H Cl COOC(CH.sub.3).sub.3 Cl HMe H Cl CONHMe Ms HMe H Cl CONHMe Cl HMe H Cl CONHEt Ms HMe H Cl CONHEt Cl HMe H Cl CONHCH(CH.sub.3).sub.2 Ms HMe H Cl CONHCH(CH.sub.3).sub.2 Cl HMe H Cl CONHC(CH.sub.3).sub.3 Ms HMe H Cl CONHC(CH.sub.3).sub.3 Cl HMe H Cl CONHC.sub.4 H.sub.9 Ms HMe H Cl CONHC.sub.4 H.sub.9 Cl HMe H Cl CONHCH.sub.2 CH(CH.sub. 3).sub.2 Ms HMe H Cl CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl HMe H Cl CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms HMe H Cl CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl HMe H Cl CONEt.sub.2 Ms HMe H Cl CONEt.sub.2 Cl HMe H Cl CON(CH(CH.sub.3).sub.2).sub.2 Ms HMe H Cl CON(CH(CH.sub.3).sub.2).sub.2 Cl HMe H Cl Y1 Ms HMe H Cl Y1 Cl HMe H Cl Y2 Ms HMe H Cl Y2 Cl HMe H Cl Y3 Ms HMe H Cl Y3 Cl HMe H Cl COOPh Ms HMe H Cl COOPh Cl HMe H Cl COOCH.sub.2 Ph Ms HMe H Cl COOCH.sub.2 Ph Cl HMe H Cl COOCH.sub.2 CHCH.sub.2 Ms HMe H Cl COOCH.sub.2 CHCH.sub.2 Cl HMe H Cl COOCH.sub.2 C CH.sub.2 Ms HMe H Cl COOCH.sub.2 C CH.sub.2 Cl HMe H Cl C(O)SMe Ms HMe H Cl C(O)SMe Cl HMe H Cl C(O)SEt Ms HMe H Cl C(O)SEt Cl HMe H Cl C(O)SCH(CH.sub.3).sub.2 Ms HMe H Cl C(O)SCH(CH.sub.3).sub.2 Cl HMe H Cl C(O)SC.sub.3 H.sub.7 Ms HMe H Cl C(O)SC.sub.3 H.sub.7 Cl HMe H Cl C(S)OMe Ms HMe H Cl C(S)OMe Cl HMe H Cl C(S)OEt Ms HMe H Cl C(S)OEt Cl HMe H Cl C(S)OCH(CH.sub.3).sub.2 Ms HMe H Cl C(S)OCH(CH.sub.3).sub.2 Cl HMe H Cl C(S)SC.sub.3 H.sub.7 Ms HMe H Cl C(S)SC.sub.3 H.sub.7 Cl HMe H Cl C(S)SMe Ms HMe H Cl C(S)SMe Cl HMe H Cl C(S)SEt Ms HMe H Cl C(S)SEt Cl HMe H Cl C(S)SCH(CH.sub.3).sub.2 Ms HMe H Cl C(S)SCH(CH.sub.3).sub.2 Cl HMe H Cl C(S)SC.sub.3 H.sub.7 Ms HMe H Cl C(S)SC.sub.3 H.sub.7 Cl HMe H Me COOMe MeS HMe H Me COOMe MeSO HMe H Me COOMe Ms HMe H Me COOMe Ms Q1Me H Me COOMe Ms Q2Me H Me COOMe Ms Q3Me H Me COOMe Ms Q4Me H Me COOMe Ms Q5Me H Me COOMe Ms Q6Me H Me COOMe Ms Q20Me Me Me COOMe Ms HMe Cl Me COOMe Ms HMe CF.sub.3 Me COOMe Ms HMe OMe Me COOMe Ms HMe SMe Me COOMe Ms HMe H Me COOEt MeS HMe H Me COOEt MeSO HMe H Me COOEt Ms HMe H Me COOEt Ms Q1Me H Me COOEt Ms Q18Me H Me COOEt Ms Q13Me H Me COOEt Ms Q4Me H Me COOEt Ms Q5Me H Me COOEt Ms Q6Me H Me COOEt Ms Q22Me Me Me COOEt Ms HMe Cl Me COOEt Ms HMe CF.sub.3 Me COOEt Ms HMe OMe Me COOEt Ms HMe SMe Me COOEt Ms HMe H Me COOCH(CH.sub.3).sub.2 MeS HMe H Me COOCH(CH.sub.3).sub.2 MeSO HMe H Me COOCH(CH.sub.3).sub.2 Ms HMe H Me COOCH(CH.sub.3).sub.2 Ms Q7Me H Me COOCH(CH.sub.3).sub. 2 Ms Q12Me H Me COOCH(CH.sub.3).sub.2 Ms Q9Me H Me COOCH(CH.sub.3).sub.2 Ms Q4Me H Me COOCH(CH.sub.3).sub.2 Ms Q5Me H Me COOCH(CH.sub.3).sub.2 Ms Q6Me H Me COOCH(CH.sub.3).sub.2 Ms Q17Me Me Me COOCH(CH.sub.3).sub.2 Ms HMe Cl Me COOCH(CH.sub.3).sub.2 Ms HMe CF.sub.3 Me COOCH(CH.sub.3).sub.2 Ms HMe OMe Me COOCH(CH.sub.3).sub.2 Ms HMe SMe Me COOCH(CH.sub.3).sub.2 Ms HMe H Me COOMe Cl HMe H Me COOMe Cl Q1Me H Me COOMe Cl Q2Me H Me COOMe Cl Q3Me H Me COOEt Cl HMe H Me COOEt Cl Q1Me H Me COOEt Cl Q2Me H Me COOEt Cl Q3Me H Me COOCH(CH.sub.3).sub.2 Cl HMe H Me COOCH(CH.sub.3).sub.2 Cl Q1Me H Me COOCH(CH.sub.3).sub.2 Cl Q2Me H Me COOCH(CH.sub.3).sub.2 Cl Q3Me H Me CON(CH.sub.3).sub.2 MeS HMe H Me CON(CH.sub.3).sub.2 MeSO HMe H Me CON(CH.sub. 3).sub.2 Ms HMe H Me CON(CH.sub.3).sub.2 Ms Q1Me H Me CON(CH.sub.3).sub.2 Ms Q18Me H Me CON(CH.sub.3).sub.2 Ms Q13Me H Me CON(CH.sub.3).sub.2 Ms Q4Me H Me CON(CH.sub.3).sub.2 Ms Q5Me H Me CON(CH.sub.3).sub.2 Ms Q6Me H Me CON(CH.sub.3).sub.2 Ms Q22Me Me Me CON(CH.sub.3).sub.2 Ms HMe Cl Me CON(CH.sub.3).sub.2 Ms HMe CF.sub.3 Me CON(CH.sub.3).sub.2 Ms HMe OMe Me CON(CH.sub.3).sub.2 Ms HMe SMe Me CON(CH.sub.3).sub.2 Ms HMe H Me CON(CH.sub.3).sub.2 Cl HMe H Me CON(CH.sub.3).sub.2 Cl Q1Me H Me CON(CH.sub.3).sub.2 Cl Q2Me H Me CON(CH.sub.3).sub.2 Cl Q3Me H Me COOC.sub.4 H.sub.9 Ms HMe H Me COOC.sub.4 H.sub.9 Cl HMe H Me COOCH.sub.2 CH(CH.sub.3).sub.2 Ms HMe H Me COOCH.sub.2 CH(CH.sub.3).sub.2 Cl HMe H Me COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms HMe H Me COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl HMe H Me COOC(CH.sub.3).sub.3 Ms HMe H Me COOC(CH.sub.3).sub.2 Cl HMe H Me CONHMe Ms HMe H Me CONHMe Cl HMe H Me CONHEt Ms HMe H Me CONHEt Cl HMe H Me CONHCH(CH.sub.3).sub.2 Ms HMe H Me CONHCH(CH.sub.3).sub.2 Cl HMe H Me CONHC(CH.sub.3).sub.3 Ms HMe H Me CONHC(CH.sub.3).sub.3 Cl HMe H Me CONHC.sub.4 H.sub.9 Ms HMe H Me CONHC.sub.4 H.sub.9 Cl HMe H Me CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms HMe H Me CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl HMe H Me CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms HMe H Me CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl HMe H Me CONEt.sub.2 Ms HMe H Me CONEt.sub.2 Cl HMe H Me CON(CH(CH.sub.3).sub.2).sub.2 Ms HMe H Me CON(CH(CH.sub.3).sub.2).sub.2 Cl HMe H Me Y1 Ms HMe H Me Y1 Cl HMe H Me Y2 Ms HMe H Me Y2 Cl HMe H Me Y3 Ms HMe H Me Y3 Cl HMe H Me COOPh Ms HMe H Me COOPh Cl HMe H Me COOCH.sub.2 Ph Ms HMe H Me COOCH.sub.2 Ph Cl HMe H Me COOCH.sub.2 CHCH.sub.2 Ms HMe H Me COOCH.sub.2 CHCH.sub.2 Cl HMe H Me COOCH.sub.2 C CH Ms HMe H Me COOCH.sub.2 C CH Cl HMe H Me C(O)SMe Ms HMe H Me C(O)SMe Cl HMe H Me C(O)SEt Ms HMe H Me C(O)SEt Cl HMe H Me C(O)SCH(CH.sub.3).sub.2 Ms HMe H Me C(O)SCH(CH.sub.3).sub.2 Cl HMe H Me C(O)SC.sub.3 H.sub.7 Ms HMe H Me C(O)SC.sub.3 H.sub.7 Cl HMe H Me C(S)OMe Ms HMe H Me C(S)OMe Cl HMe H Me C(S)OEt Ms HMe H Me C(S)OEt Cl HMe H Me C(S)OCH(CH.sub.3).sub.2 Ms HMe H Me C(S)OCH(CH.sub.3).sub.2 Cl HMe H Me C(S)SC.sub.3 H.sub.7 Ms HMe H Me C(S)SC.sub.3 H.sub.7 Cl HMe H Me C(S)SMe Ms HMe H Me C(S)SMe Cl HMe H Me C(S)SEt Ms HMe H Me C(S)SEt Cl HMe H Me C(S)SCH(CH.sub.3).sub.2 Ms HMe H Me C(S)SCH(CH.sub.3).sub.2 Cl HMe H Me C(S)SC.sub.3 H.sub.7 Ms HMe H Me C(S)SC.sub.3 H.sub.7 Cl HMe H OMe COOMe MeS HMe H OMe COOMe MeSO HMe H OMe COOMe Ms HMe H OMe COOMe Ms Q1Me H OMe COOMe Ms Q2Me H OMe COOMe Ms Q3Me H OMe COOMe Ms Q4Me H OMe COOMe Ms Q5Me H OMe COOMe Ms Q6Me H OMe COOMe Ms Q20Me Me OMe COOMe Ms HMe Cl OMe COOMe Ms HMe CF.sub.3 OMe COOMe Ms HMe OMe OMe COOMe Ms HMe SMe OMe COOMe Ms HMe H OMe COOEt MeS HMe H OMe COOEt MeSO HMe H OMe COOEt Ms HMe H OMe COOEt Ms Q1Me H OMe COOEt Ms Q18Me H OMe COOEt Ms Q13Me H OMe COOEt Ms Q4Me H OMe COOEt Ms Q5Me H OMe COOEt Ms Q6Me H OMe COOEt Ms Q22Me Me OMe COOEt Ms HMe Cl OMe COOEt Ms HMe CF.sub.3 OMe COOEt Ms HMe OMe OMe COOEt Ms HMe SMe OMe COOEt Ms HMe H OMe COOCH(CH.sub.3).sub.2 MeS HMe H OMe COOCH(CH.sub.3).sub.2 MeSO HMe H OMe COOCH(CH.sub.3).sub.2 Ms HMe H OMe COOCH(CH.sub.3).sub.2 Ms Q7Me H OMe COOCH(CH.sub.3).sub.2 Ms Q12Me H OMe COOCH(CH.sub.3).sub.2 Ms Q9Me H OMe COOCH(CH.sub.3).sub.2 Ms Q4Me H OMe COOCH(CH.sub.3).sub.2 Ms Q5Me H OMe COOCH(CH.sub.3).sub.2 Ms Q6Me H OMe COOCH(CH.sub.3).sub.2 Ms Q17Me Me OMe COOCH(CH.sub.3).sub.2 Ms HMe Cl OMe COOCH(CH.sub.3).sub.2 Ms HMe CF.sub.3 OMe COOCH(CH.sub.3).sub.2 Ms HMe OMe OMe COOCH(CH.sub.3).sub.2 Ms HMe SMe OMe COOCH(CH.sub.3).sub.2 Ms HMe H OMe COOMe Cl HMe H OMe COOMe Cl Q1Me H OMe COOMe Cl Q2Me H OMe COOMe Cl Q3Me H OMe COOEt Cl HMe H OMe COOEt Cl Q1Me H OMe COOEt Cl Q2Me H OMe COOEt Cl Q3Me H OMe COOCH(CH.sub.3).sub.2 Cl HMe H OMe COOCH(CH.sub.3).sub.2 Cl Q1Me H OMe COOCH(CH.sub.3).sub.2 Cl Q2Me H OMe COOCH(CH.sub.3).sub.2 Cl Q3Me H OMe CON(CH.sub.3).sub.2 MeS HMe H OMe CON(CH.sub.3).sub.2 MeSO HMe H OMe CON(CH.sub.3).sub.2 Ms HMe H OMe CON(CH.sub.3).sub.2 Ms Q1Me H OMe CON(CH.sub.3).sub.2 Ms Q18Me H OMe CON(CH.sub.3).sub.2 Ms Q13Me H OMe CON(CH.sub.3).sub.2 Ms Q4Me H OMe CON(CH.sub.3).sub.2 Ms Q5Me H OMe CON(CH.sub.3).sub.2 Ms Q6Me H OMe CON(CH.sub.3).sub.2 Ms Q22Me Me OMe CON(CH.sub.3).sub.2 Ms HMe Cl OMe CON(CH.sub.3).sub.2 Ms HMe CF.sub. 3 OMe CON(CH.sub.3).sub.2 Ms HMe OMe OMe CON(CH.sub.3).sub.2 Ms HMe SMe OMe CON(CH.sub.3).sub.2 Ms HMe H OMe CON(CH.sub.3).sub.2 Cl HMe H OMe CON(CH.sub.3).sub.2 Cl Q1Me H OMe CON(CH.sub.3).sub.2 Cl Q2Me H OMe CON(CH.sub.3).sub.2 Cl Q3Me H OMe COOC.sub.4 H.sub.9 Ms HMe H OMe COOC.sub.4 H.sub.9 Cl HMe H OMe COOCH.sub.2 CH(CH.sub.3).sub.2 Ms HMe H OMe COOCH.sub.2 CH(CH.sub.3).sub.2 Cl HMe H OMe COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms HMe H OMe COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl HMe H OMe COOC(CH.sub.3).sub.3 Ms HMe H OMe COOC(CH.sub.3).sub.3 Cl HMe H OMe CONHMe Ms HMe H OMe CONHMe Cl HMe H OMe CONHEt Ms HMe H OMe CONHEt Cl HMe H OMe CONHCH(CH.sub.3).sub.2 Ms HMe H OMe CONHCH(CH.sub.3).sub.2 Cl HMe H OMe CONHC(CH.sub.3).sub.3 Ms HMe H OMe CONHC(CH.sub.3).sub.3 Cl HMe H OMe CONHC.sub.4 H.sub.9 Ms HMe H OMe CONHC.sub.4 H.sub.9 Cl HMe H OMe CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms HMe H OMe CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl HMe H OMe CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms HMe H OMe CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl HMe H OMe CONEt.sub.2 Ms HMe H OMe CONEt.sub.2 Cl HMe H OMe CON(CH(CH.sub.3).sub.2).sub.2 Ms HMe H OMe CON(CH(CH.sub.3).sub.2).sub.2 Cl HMe H OMe Y1 Ms HMe H OMe Y1 Cl HMe H OMe Y2 Ms HMe H OMe Y2 Cl HMe H OMe Y3 Ms HMe H OMe Y3 Cl HMe H OMe COOPh Ms HMe H OMe COOPh Cl HMe H OMe COOCH.sub.2 Ph Ms HMe H OMe COOCH.sub.2 Ph Cl HMe H OMe COOCH.sub.2 CHCH.sub.2 Ms HMe H OMe COOCH.sub.2 CHCH.sub.2 Cl HMe H OMe COOCH.sub.2 C CH Ms HMe H OMe COOCH.sub.2 C CH Cl HMe H OMe C(O)SMe Ms HMe H OMe C(O)SMe Cl HMe H OMe C(O)SEt Ms HMe H OMe C(O)SEt Cl HMe H OMe C(O)SCH(CH.sub.3).sub.2 Ms HMe H OMe C(O)SCH(CH.sub.3).sub.2 Cl HMe H OMe C(O)SC.sub.3 H.sub.7 Ms HMe H OMe C(O)SC.sub.3 H.sub.7 Cl HMe H OMe C(S)OMe Ms HMe H OMe C(S)OMe Cl HMe H OMe C(S)OEt Ms HMe H OMe C(S)OEt Cl HMe H OMe C(S)OCH(CH.sub.3).sub.2 Ms HMe H OMe C(S)OCH(CH.sub.3).sub.2 Cl HMe H OMe C(S)SC.sub.3 H.sub.7 Ms HMe H OMe C(S)SC.sub.3 H.sub.7 Cl HMe H OMe C(S)SMe Ms HMe H OMe C(S)SMe Cl HMe H OMe C(S)SEt Ms HMe H OMe C(S)SEt Cl HMe H OMe C(S)SCH(CH.sub.3).sub.2 Ms HMe H OMe C(S)SCH(CH.sub.3).sub.2 Cl HMe H OMe C(S)SC.sub.3 H.sub.7 Ms HMe H OMe C(S)SC.sub.3 H.sub.7 Cl HMe H Br COOMe Ms HMe H Br COOMe Cl HMe H Br COOEt Ms HMe H Br COOEt Cl HMe H Br COOCH(CH.sub.3).sub.2 Ms HMe H Br COOCH(CH.sub.3).sub.2 Cl HMe H Br CON(CH.sub.3).sub.2 Ms HMe H Br CON(CH.sub.3).sub.2 Cl HMe H Br CONHMe Ms HMe H Br CONHEt Ms HMe H Br CONHC.sub.3 H.sub.7 Ms HMe H Br CONHCH(CH.sub.3).sub.2 Ms HMe H Br CONHC(CH.sub.3).sub.3 Ms HMe H Br CONEt.sub.2 Ms HMe H Br CONHC(CH.sub.3).sub.3 Ms HMe H Br CONHC.sub.4 H.sub.9 Ms HMe H Br CONHC.sub.4 H.sub.9 Ms HMe H Br CON(CH(CH.sub.3).sub.2).sub.2 Ms HMe H Br Y1 Ms HMe H Br Y2 Ms HMe H Br COOPh Ms HMe H Br COOCH.sub.2 Ph Ms HMe H Br COOCH.sub.2 CHCH.sub.2 Ms HMe H Br COOCH.sub.2 C CH Ms HMe H OEt COOMe Ms HMe H OEt COOMe Cl HMe H OEt COOEt Ms HMe H OEt COOEt Cl HMe H OEt COOCH(CH.sub.3).sub.2 Ms HMe H OEt COOCH(CH.sub.3).sub.2 Cl HMe H OEt CON(CH.sub.3).sub.2 Ms HMe H OEt CON(CH.sub.3).sub.2 Cl HMe H OEt CONHMe Ms HMe H OEt CONHEt Ms HMe H OEt CONHC.sub.3 H.sub.7 Ms HMe H OEt CONHCH(CH.sub.3).sub.2 Ms HMe H OEt CONHC(CH.sub.3).sub.3 Ms HMe H OEt CONEt.sub.2 Ms HMe H OEt CONHC(CH.sub.3).sub.3 Ms HMe H OEt CONHC.sub.4 H.sub.9 Ms HMe H OEt CONHC.sub.4 H.sub.9 Ms HMe H OEt CON(CH(CH.sub.3).sub.2).sub.2 Ms HMe H OEt Y1 Ms HMe H OEt Y2 Ms HMe H OEt COOPh Ms HMe H OEt COOCH.sub.2 Ph Ms HMe H OEt COOCH.sub.2 CHCH.sub.2 Ms HMe H OEt COOCH.sub.2 C CH Ms HMe H OCH(CH.sub.3 ).sub.2 COOMe Ms HMe H OCH(CH.sub.3).sub.2 COOMe Cl HMe H OCH(CH.sub.3).sub.2 COOEt Ms HMe H OCH(CH.sub.3).sub.2 COOEt Cl HMe H OCH(CH.sub.3).sub.2 COOCH(CH.sub.3).sub.2 Ms HMe H OCH(CH.sub.3).sub.2 COOCH(CH.sub.3).sub.2 Cl HMe H OCH(CH.sub.3).sub.2 CON(CH.sub.3).sub.2 Ms HMe H OCH(CH.sub.3).sub.2 CON(CH.sub.3).sub.2 Cl HMe H OCH(CH.sub.3).sub.2 CONHMe Ms HMe H OCH(CH.sub.3).sub.2 CONHEt Ms HMe H OCH(CH.sub.3).sub.2 CONHC.sub.3 H.sub.7 Ms HMe H OCH(CH.sub.3).sub.2 CONHCH(CH.sub.3).sub.2 Ms HMe H OCH(CH.sub.3).sub.2 CONHC(CH.sub.3).sub.3 Ms HMe H OCH(CH.sub.3).sub.2 CONEt.sub.2 Ms HMe H OCH(CH.sub.3).sub.2 CONHC(CH.sub.3).sub.3 Ms HMe H OCH(CH.sub.3).sub.2 CONHC.sub.4 H.sub.9 Ms HMe H OCH(CH.sub.3).sub.2 CONHC.sub.4 H.sub.9 Ms HMe H OCH(CH.sub.3).sub.2 CON(CH(CH.sub.3).sub.2).sub.2 Ms HMe H OCH(CH.sub.3).sub.2 Y1 Ms HMe H OCH(CH.sub.3).sub.2 Y2 Ms HMe H OCH(CH.sub.3).sub.2 COOPh Ms HMe H OCH(CH.sub.3).sub.2 COOCH.sub.2 Ph Ms HMe H OCH(CH.sub.3).sub.2 COOCH.sub.2 CHCH.sub.2 Ms HMe H OCH(CH.sub.3).sub.2 COOCH.sub.2 C CH Ms HMe H CH.sub.2 OCH.sub.3 COOMe Ms HMe H CH.sub.2 OCH.sub.3 COOMe Cl HMe H CH.sub.2 OCH.sub.3 COOEt Ms HMe H CH.sub.2 OCH.sub.3 COOEt Cl HMe H CH.sub.2 OCH.sub.3 COOCH(CH.sub.3).sub.2 Ms HMe H CH.sub.2 OCH.sub.3 COOCH(CH.sub.3).sub.2 Cl HMe H CH.sub.2 OCH.sub.3 CON(CH.sub.3).sub.2 Ms HMe H CH.sub.2 OCH.sub.3 CON(CH.sub.3).sub.2 Cl HMe H CH.sub.2 OCH.sub.3 CONHMe Ms HMe H CH.sub.2 OCH.sub.3 CONHEt Ms HMe H CH.sub.2 OCH.sub.3 CONHC.sub.3 H.sub.7 Ms HMe H CH.sub.2 OCH.sub.3 CONHCH(CH.sub.3).sub.2 Ms HMe H CH.sub.2 OCH.sub.3 CONHC(CH.sub.3 ).sub.3 Ms HMe H CH.sub.2 OCH.sub.3 CONEt.sub.2 Ms HMe H CH.sub.2 OCH.sub.3 CONHC(CH.sub.3).sub.2 Ms HMe H CH.sub.2 OCH.sub.3 CONHC.sub.4 H.sub.9 Ms HMe H CH.sub.2 OCH.sub.3 CONHC.sub.4 H.sub.9 Ms HMe H CH.sub.2 OCH.sub.3 CON(CH(CH.sub.3).sub.2).sub.2 Ms HMe H CH.sub.2 OCH.sub.3 Y1 Ms HMe H CH.sub.2 OCH.sub.3 Y2 Ms HMe H CH.sub.2 OCH.sub.3 COOPh Ms HMe H CH.sub.2 OCH.sub.3 COOCH.sub.2 Ph Ms HMe H CH.sub.2 OCH.sub.3 COOCH.sub.2 CHCH.sub.2 Ms HMe H CH.sub.2 OCH.sub.3 COOCH.sub.2 C CH Ms HEt H Cl COOMe MeS HEt H Cl COOMe MeSO HEt H Cl COOMe Ms HEt H Cl COOMe Ms Q1Et H Cl COOMe Ms Q2Et H Cl COOMe Ms Q3Et H Cl COOMe Ms Q4Et H Cl COOMe Ms Q5Et H Cl COOMe Ms Q6Et H Cl COOMe Ms Q20Et Me Cl COOMe Ms HEt Cl Cl COOMe Ms HEt CF.sub.3 Cl COOMe Ms HEt OMe Cl COOMe Ms HEt SMe Cl COOMe Ms HEt H Cl COOEt MeS HEt H Cl COOEt MeSO HEt H Cl COOEt Ms HEt H Cl COOEt Ms Q1Et H Cl COOEt Ms Q18Et H Cl COOEt Ms Q13Et H Cl COOEt Ms Q4Et H Cl COOEt Ms Q5Et H Cl COOEt Ms Q6Et H Cl COOEt Ms Q22Et Me Cl COOEt Ms HEt Cl Cl COOEt Ms HEt CF.sub.3 Cl COOEt Ms HEt OMe Cl COOEt Ms HEt SMe Cl COOEt Ms HEt H Cl COOCH(CH.sub.3).sub.2 MeS HEt H Cl COOCH(CH.sub.3).sub.2 MeSO HEt H Cl COOCH(CH.sub.3).sub.2 Ms HEt H Cl COOCH(CH.sub.3).sub.2 Ms Q7Et H Cl COOCH(CH.sub.3).sub.2 Ms Q12Et H Cl COOCH(CH.sub.3).sub.2 Ms Q9Et H Cl COOCH(CH.sub.3).sub.2 Ms Q4Et H Cl COOCH(CH.sub.3).sub.2 Ms Q5Et H Cl COOCH(CH.sub.3).sub.2 Ms Q6Et H Cl COOCH(CH.sub.3).sub.2 Ms Q17Et Me Cl COOCH(CH.sub.3).sub.2 Ms HEt Cl Cl COOCH(CH.sub.3).sub.2 Ms HEt CF.sub.3 Cl COOCH(CH.sub.3).sub.2 Ms HEt OMe Cl COOCH(CH.sub.3).sub.2 Ms HEt SMe Cl COOCH(CH.sub.3).sub.2 Ms HEt H Cl COOMe Cl HEt H Cl COOMe Cl Q1Et H Cl COOMe Cl Q2Et H Cl COOMe Cl Q3Et H Cl COOEt Cl HEt H Cl COOEt Cl Q1Et H Cl COOEt Cl Q2Et H Cl COOEt Cl Q3Et H Cl COOCH(CH.sub.3).sub.2 Cl HEt H Cl COOCH(CH.sub.3).sub.2 Cl Q1Et H Cl COOCH(CH.sub.3).sub.2 Cl Q2Et H Cl COOCH(CH.sub.3).sub.2 Cl Q3Et H Cl CON(CH.sub.3).sub.2 MeS HEt H Cl CON(CH.sub.3).sub.2 MeSO HEt H Cl CON(CH.sub.3).sub.2 Ms HEt H Cl CON(CH.sub.3).sub.2 Ms Q1Et H Cl CON(CH.sub.3).sub.2 Ms Q18Et H Cl CON(CH.sub.3).sub.2 Ms Q13Et H Cl CON(CH.sub.3).sub.2 Ms Q4Et H Cl CON(CH.sub.3).sub.2 Ms Q5Et H Cl CON(CH.sub.3).sub.2 Ms Q6Et H Cl CON(CH.sub.3).sub.2 Ms Q22Et Me Cl CON(CH.sub.3).sub.2 Ms HEt Cl Cl CON(CH.sub.3).sub.2 Ms HEt CF.sub.3 Cl CON(CH.sub.3).sub.2 Ms HEt OMe Cl CON(CH.sub.3).sub.2 Ms HEt SMe Cl CON(CH.sub.3).sub.2 Ms HEt H Cl CON(CH.sub.3).sub.2 Cl HEt H Cl CON(CH.sub.3).sub.2 Cl Q1Et H Cl CON(CH.sub.3).sub.2 Cl Q2Et H Cl CON(CH.sub.3).sub.2 Cl Q3Et H Cl COOC.sub.4 H.sub.9 Ms HEt H Cl COOC.sub.4 H.sub.9 Cl HEt H Cl COOCH.sub.2 CH(CH.sub.3).sub.2 Ms HEt H Cl COOCH.sub.2 CH(CH.sub.3).sub.2 Cl HEt H Cl COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms HEt H Cl COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl HEt H Cl COOC(CH.sub.3).sub.3 Ms HEt H Cl COOC(CH.sub.3).sub.3 Cl HEt H Cl CONHMe Ms HEt H Cl CONHMe Cl HEt H Cl CONHEt Ms HEt H Cl CONHEt Cl HEt H Cl CONHCH(CH.sub.3).sub.2 Ms HEt H Cl CONHCH(CH.sub.3).sub.2 Cl HEt H Cl CONHC(CH.sub.3).sub.3 Ms HEt H Cl CONHC(CH.sub.3).sub.3 Cl HEt H Cl CONHC.sub.4 H.sub.9 Ms HEt H Cl CONHC.sub.4 H.sub.9 Cl HEt H Cl CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms HEt H Cl CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl HEt H Cl CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms HEt H Cl CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl HEt H Cl CONEt.sub.2 Ms HEt H Cl CONEt.sub.2 Cl HEt H Cl CON(CH(CH.sub.3).sub.2).sub.2 Ms HEt H Cl CON(CH(CH.sub.3).sub.2).sub.2 Cl HEt H Cl Y1 Ms HEt H Cl Y1 Cl HEt H Cl Y2 Ms HEt H Cl Y2 Cl HEt H Cl Y3 Ms HEt H Cl Y3 Cl HEt H Cl COOPh Ms HEt H Cl COOPh Cl HEt H Cl COOCH.sub. 2 Ph Ms HEt H Cl COOCH.sub.2 Ph Cl HEt H Cl COOCH.sub.2 CHCH.sub.2 Ms HEt H Cl COOCH.sub.2 CHCH.sub.2 Cl HEt H Cl COOCH.sub.2 C CH Ms HEt H Cl COOCH.sub.2 C CH Cl HEt H Cl C(O)SMe Ms HEt H Cl C(O)SMe Cl HEt H Cl C(O)SEt Ms HEt H Cl C(O)SEt Cl HEt H Cl C(O)SCH(CH.sub.3).sub.2 Ms HEt H Cl C(O)SCH(CH.sub.3).sub.2 Cl HEt H Cl C(O)SC.sub.3 H.sub.7 Ms HEt H Cl C(O)SC.sub.3 H.sub.7 Cl HEt H Cl C(S)OMe Ms HEt H Cl C(S)OMe Cl HEt H Cl C(S)OEt Ms HEt H Cl C(S)OEt Cl HEt H Cl C(S)OCH(CH.sub.3).sub.2 Ms HEt H Cl C(S)OCH(CH.sub.3).sub.2 Cl HEt H Cl C(S)SC.sub.3 H.sub.7 Ms HEt H Cl C(S)SC.sub.3 H.sub.7 Cl HEt H Cl C(S)SMe Ms HEt H Cl C(S)SMe Cl HEt H Cl C(S)SEt Ms HEt H Cl C(S)SEt Cl HEt H Cl C(S)SCH(CH.sub.3).sub.2 Ms HEt H Cl C(S)SCH(CH.sub.3).sub.2 Cl HEt H Cl C(S)SC.sub.3 H.sub.7 Ms HEt H Cl C(S)SC.sub.3 H.sub.7 Cl HEt H Me COOMe MeS HEt H Me COOMe MeSO HEt H Me COOMe Ms HEt H Me COOMe Ms Q1Et H Me COOMe Ms Q2Et H Me COOMe Ms Q3Et H Me COOMe Ms Q4Et H Me COOMe Ms Q5Et H Me COOMe Ms Q6Et H Me COOMe Ms Q20Et Me Me COOMe Ms HEt Cl Me COOMe Ms HEt CF.sub.3 Me COOMe Ms HEt OMe Me COOMe Ms HEt SMe Me COOMe Ms HEt H Me COOEt MeS HEt H Me COOEt MeSO HEt H Me COOEt Ms HEt H Me COOEt Ms Q1Et H Me COOEt Ms Q18Et H Me COOEt Ms Q13Et H Me COOEt Ms Q4Et H Me COOEt Ms Q5Et H Me COOEt Ms Q6Et H Me COOEt Ms Q22Et Me Me COOEt Ms HEt Cl Me COOEt Ms HEt CF.sub.3 Me COOEt Ms HEt OMe Me COOEt Ms HEt SMe Me COOEt Ms HEt H Me COOCH(CH.sub.3).sub.2 MeS HEt H Me COOCH(CH.sub.3).sub.2 MeSO HEt H Me COOCH(CH.sub.3).sub.2 Ms HEt H Me COOCH(CH.sub.3).sub.2 Ms Q7Et H Me COOCH(CH.sub.3).sub.2 Ms Q12Et H Me COOCH(CH.sub.3).sub.2 Ms Q9Et H Me COOCH(CH.sub.3).sub.2 Ms Q4Et H Me COOCH(CH.sub.3).sub.2 Ms Q5Et H Me COOCH(CH.sub.3).sub.2 Ms Q6Et H Me COOCH(CH.sub.3).sub.2 Ms Q17Et Me Me COOCH(CH.sub.3).sub.2 Ms HEt Cl Me COOCH(CH.sub.3).sub.2 Ms HEt CF.sub.3 Me COOCH(CH.sub.3).sub.2 Ms HEt OMe Me COOCH(CH.sub.3).sub.2 Ms HEt SMe Me COOCH(CH.sub.3).sub.2 Ms HEt H Me COOMe Cl HEt H Me COOMe Cl Q1Et H Me COOMe Cl Q2Et H Me COOMe Cl Q3Et H Me COOEt Cl HEt H Me COOEt Cl Q1Et H Me COOEt Cl Q2Et H Me COOEt Cl Q3Et H Me COOCH(CH.sub.3).sub.2 Cl HEt H Me COOCH(CH.sub.3).sub.2 Cl Q1Et H Me COOCH(CH.sub.3).sub.2 Cl Q2Et H Me COOCH(CH.sub.3).sub.2 Cl Q3Et H Me CON(CH.sub.3).sub.2 MeS HEt H Me CON(CH.sub.3).sub.2 MeSO HEt H Me CON(CH.sub.3).sub.2 Ms HEt H Me CON(CH.sub.3).sub.2 Ms Q1Et H Me CON(CH.sub.3).sub.2 Ms Q18Et H Me CON(CH.sub.3).sub.2 Ms Q13Et H Me CON(CH.sub.3).sub.2 Ms Q4Et H Me CON(CH.sub.3).sub.2 Ms Q5Et H Me CON(CH.sub.3).sub.2 Ms Q6Et H Me CON(CH.sub.3).sub.2 Ms Q22Et Me Me CON(CH.sub.3).sub.2 Ms HEt Cl Me CON(CH.sub.3).sub.2 Ms HEt CF.sub.3 Me CON(CH.sub.3).sub.2 Ms HEt OMe Me CON(CH.sub.3).sub.2 Ms HEt SMe Me CON(CH.sub.3).sub.2 Ms HEt H Me CON(CH.sub.3).sub.2 Cl HEt H Me CON(CH.sub.3 ).sub.2 Cl Q1Et H Me CON(CH.sub.3).sub.2 Cl Q2Et H Me CON(CH.sub.3).sub.2 Cl Q3Et H Me COOC.sub.4 H.sub.9 Ms HEt H Me COOC.sub.4 H.sub.9 Cl HEt H Me COOCH.sub.2 CH(CH.sub.3).sub.2 Ms HEt H Me COOCH.sub.2 CH(CH.sub.3).sub.2 Cl HEt H Me COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms HEt H Me COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl HEt H Me COOC(CH.sub.3).sub.3 Ms HEt H Me COOC(CH.sub.3).sub.3 Cl HEt H Me CONHMe Ms HEt H Me CONHMe Cl HEt H Me CONHEt Ms HEt H Me CONHEt Cl HEt H Me CONHCH(CH.sub.3).sub.2 Ms HEt H Me CONHCH(CH.sub.3).sub.2 Cl HEt H Me CONHC(CH.sub.3).sub.3 Ms HEt H Me CONHC(CH.sub.3).sub.3 Cl HEt H Me CONHC.sub.4 H.sub.9 Ms HEt H Me CONHC.sub.4 H.sub.9 Cl HEt H Me CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms HEt H Me CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl HEt H Me CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms HEt H Me CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl HEt H Me CONEt.sub.2 Ms HEt H Me CONEt.sub.2 Cl HEt H Me CON(CH(CH.sub.3).sub.2).sub.2 Ms HEt H Me CON(CH(CH.sub.3).sub.2).sub.2 Cl HEt H Me Y1 Ms HEt H Me Y1 Cl HEt H Me Y2 Ms HEt H Me Y2 Cl HEt H Me Y3 Ms HEt H Me Y3 Cl HEt H Me COOPh Ms HEt H Me COOPh Cl HEt H Me COOCH.sub.2 Ph Ms HEt H Me COOCH.sub.2 Ph Cl HEt H Me COOCH.sub.2 CHCH.sub.2 Ms HEt H Me COOCH.sub.2 CHCH.sub.2 Cl HEt H Me COOCH.sub.2 C CH Ms HEt H Me COOCH.sub.2 C CH Cl HEt H Me C(O)SMe Ms HEt H Me C(O)SMe Cl HEt H Me C(O)SEt Ms HEt H Me C(O)SEt Cl HEt H Me C(O)SCH(CH.sub.3).sub.2 Ms HEt H Me C(O)SCH(CH.sub.3).sub.2 Cl HEt H Me C(O)SC.sub.3 H.sub.7 Ms HEt H Me C(O)SC.sub.3 H.sub.7 Cl HEt H Me C(S)OMe Ms HEt H Me C(S)OMe Cl HEt H Me C(S)OEt Ms HEt H Me C(S)OEt Cl HEt H Me C(S)OCH(CH.sub.3).sub.2 Ms HEt H Me C(S)OCH(CH.sub.3).sub.2 Cl HEt H Me C(S)SC.sub.3 H.sub.7 Ms HEt H Me C(S)SC.sub.3 H.sub.7 Cl HEt H Me C(S)SMe Ms HEt H Me C(S)SMe Cl HEt H Me C(S)SEt Ms HEt H Me C(S)SEt Cl HEt H Me C(S)SCH(CH.sub.3).sub.2 Ms HEt H Me C(S)SCH(CH.sub.3).sub.2 Cl HEt H Me C(S)SC.sub.3 H.sub.7 Ms HEt H Me C(S)SC.sub.3 H.sub.7 Cl HEt H OMe COOMe MeS HEt H OMe COOMe MeSO HEt H OMe COOMe Ms HEt H OMe COOMe Ms Q1Et H OMe COOMe Ms Q2Et H OMe COOMe Ms Q3Et H OMe COOMe Ms Q4Et H OMe COOMe Ms Q5Et H OMe COOMe Ms Q6Et H OMe COOMe Ms Q20Et Me OMe COOMe Ms HEt Cl OMe COOMe Ms HEt CF.sub.3 OMe COOMe Ms HEt OMe OMe COOMe Ms HEt SMe OMe COOMe Ms HEt H OMe COOEt MeS HEt H OMe COOEt MeSO HEt H OMe COOEt Ms HEt H OMe COOEt Ms Q1Et H OMe COOEt Ms Q18Et H OMe COOEt Ms Q13Et H OMe COOEt Ms Q4Et H OMe COOEt Ms Q5Et H OMe COOEt Ms Q6Et H OMe COOEt Ms Q22Et Me OMe COOEt Ms HEt Cl OMe COOEt Ms HEt CF.sub.3 OMe COOEt Ms HEt OMe OMe COOEt Ms HEt SMe OMe COOEt Ms HEt H OMe COOCH(CH.sub.3).sub.2 MeS HEt H OMe COOCH(CH.sub.3).sub.2 MeSO HEt H OMe COOCH(CH.sub.3).sub.2 Ms HEt H OMe COOCH(CH.sub.3).sub.2 Ms Q7Et H OMe COOCH(CH.sub.3).sub.2 Ms Q12Et H OMe COOCH(CH.sub.3).sub.2 Ms Q9Et H OMe COOCH(CH.sub. 3).sub.2 Ms Q4Et H OMe COOCH(CH.sub.3).sub.2 Ms Q5Et H OMe COOCH(CH.sub.3).sub.2 Ms Q6Et H OMe COOCH(CH.sub.3).sub.2 Ms Q17Et Me OMe COOCH(CH.sub.3).sub.2 Ms HEt Cl OMe COOCH(CH.sub.3).sub.2 Ms HEt CF.sub.3 OMe COOCH(CH.sub.3).sub.2 Ms HEt OMe OMe COOCH(CH.sub.3).sub.2 Ms HEt SMe OME COOCH(CH.sub.3).sub.2 Ms HEt H OMe COOMe Cl HEt H OMe COOMe Cl Q1Et H OMe COOMe Cl Q2Et H OMe COOMe Cl Q3Et H OMe COOEt Cl HEt H OMe COOEt Cl Q1Et H OMe COOEt Cl Q2Et H OMe COOEt Cl Q3Et H OMe COOCH(CH.sub.3).sub.2 Cl HEt H OMe COOCH(CH.sub.3).sub.2 Cl Q1Et H OMe COOCH(CH.sub.3).sub.2 Cl Q2Et H OMe COOCH(CH.sub.3).sub.2 Cl Q3Et H OMe CON(CH.sub.3).sub.2 MeS HEt H OMe CON(CH.sub.3).sub.2 MeSO HEt H OMe CON(CH.sub.3).sub.2 Ms HEt H OMe CON(CH.sub.3).sub.2 Ms Q1Et H OMe CON(CH.sub.3).sub.2 Ms Q18Et H OMe CON(CH.sub.3).sub.2 Ms Q13Et H OMe CON(CH.sub.3).sub.2 Ms Q4Et H OMe CON(CH.sub.3).sub.2 Ms Q5Et H OMe CON(CH.sub.3).sub.2 Ms Q6Et H OMe CON(CH.sub.3).sub.2 Ms Q22Et Me OMe CON(CH.sub.3).sub.2 Ms HEt Cl OMe CON(CH.sub.3).sub.2 Ms HEt CF.sub.3 OMe CON(CH.sub.3).sub.2 Ms HEt OMe OMe CON(CH.sub.3).sub.2 Ms HEt SMe OMe CON(CH.sub.3).sub.2 Ms HEt H OMe CON(CH.sub.3).sub.2 Cl HEt H OMe CON(CH.sub.3).sub.2 Cl Q1Et H OMe CON(CH.sub.3).sub.2 Cl Q2Et H OMe CON(CH.sub.3).sub.2 Cl Q3Et H OMe COOC.sub.4 H.sub.9 Ms HEt H OMe COOC.sub.4 H.sub.9 Cl HEt H OMe COOCH.sub.2 CH(HC.sub.3).sub.2 Ms HEt H OMe COOCH.sub.2 CH(HC.sub.3).sub.2 Cl HEt H OMe COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms HEt H OMe COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl HEt H OMe COOC(CH.sub. 3).sub.3 Ms HEt H OMe COOC(CH.sub.3).sub.3 Cl HEt H OMe CONHMe Ms HEt H OMe CONHMe Cl HEt H OMe CONHEt Ms HEt H OMe CONHEt Cl HEt H OMe CONHCH(CH.sub.3).sub.2 Ms HEt H OMe CONHCH(CH.sub.3).sub.2 Cl HEt H OMe CONHC(CH.sub.3).sub.3 Ms HEt H OMe CONHC(CH.sub.3).sub.3 Cl HEt H OMe CONHC.sub.4 H.sub.9 Ms HEt H OMe CONHC.sub.4 H.sub.9 Cl HEt H OMe CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms HEt H OMe CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl HEt H OMe CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms HEt H OMe CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl HEt H OMe CONEt.sub.2 Ms HEt H OMe CONEt.sub.2 Cl HEt H OMe CON(CH(CH.sub.3).sub.2).sub.2 Ms HEt H OMe CON(CH(CH.sub.3).sub.2).sub.2 Cl HEt H OMe Y1 Ms HEt H OMe Y1 Cl HEt H OMe Y2 Ms HEt H OMe Y2 Cl HEt H OMe Y3 Ms HEt H OMe Y3 Cl HEt H OMe COOPh Ms HEt H OMe COOPh Cl HEt H OMe COOCH.sub.2 Ph Ms HEt H OMe COOCH.sub.2 Ph Cl HEt H OMe COOCH.sub.2 CHCH.sub.2 Ms HEt H OMe COOCH.sub.2 CHCH.sub.2 Cl HEt H OMe COOCH.sub.2 C CH Ms HEt H OMe COOCH.sub.2 C CH Cl HEt H OMe C(O)SMe Ms HEt H OMe C(O)SMe Cl HEt H OMe C(O)SEt Ms HEt H OMe C(O)SEt Cl HEt H OMe C(O)SCH(CH.sub.3).sub.2 Ms HEt H OMe C(O)SCH(CH.sub.3).sub.2 Cl HEt H OMe C(O)SC.sub.3 H.sub.7 Cl HEt H OMe C(S)OMe Ms HEt H OMe C(S)OMe Cl HEt H OMe C(S)OEt Ms HEt H OMe C(S)OEt Cl HEt H OMe C(S)OCH(CH.sub.3).sub.2 Ms HEt H OMe C(S)OCH(CH.sub.3).sub.2 Cl HEt H OMe C(S)SC.sub.3 H.sub.7 Ms HEt H OMe C(S)SC.sub.3 H.sub. 7 Cl HEt H OMe C(S)SMe Ms HEt H OMe C(S)SMe Cl HEt H OMe C(S)SEt Ms HEt H OMe C(S)SEt Cl HEt H OMe C(S)SCH(CH.sub.3).sub.2 Ms HEt H OMe C(S)SCH(CH.sub.3).sub.2 Cl HEt H OMe C(S)SC.sub.3 H.sub.7 Ms HEt H OMe C(S)SC.sub.3 H.sub.7 Cl HEt H Br COOMe Ms HEt H Br COOMe Cl HEt H Br COOEt Ms HEt H Br COOEt Cl HEt H Br COOCH(CH.sub.3).sub.2 Ms HEt H Br COOCH(CH.sub.3).sub.2 Cl HEt H Br CON(CH.sub.3).sub.2 Ms HEt H Br CON(CH.sub.3).sub.2 Cl HEt H Br CONHMe Ms HEt H Br CONHEt Cl HEt H Br CONHC.sub.3 H.sub.7 Ms HEt H Br CONHCH(CH.sub.3).sub.2 Cl HEt H Br CONHC(CH.sub.3).sub.3 Ms HEt H Br CONEt.sub.2 Cl HEt H Br CONHC(CH.sub.3).sub.3 Ms HEt H Br CONHC.sub.4 H.sub.9 Cl HEt H Br CONHC.sub.4 H.sub.9 Ms HEt H Br CON(CH(CH.sub. 3).sub.2).sub.2 Cl HEt H Br Y1 Ms HEt H Br Y2 Cl HEt H Br COOPh Ms HEt H Br COOCH.sub.2 Ph Cl HEt H Br COOCH.sub.2 CHCH.sub.2 Ms HEt H Br COOCH.sub.2 C CH Cl HEt H OEt COOMe Ms HEt H OEt COOMe Cl HEt H OEt COOEt Ms HEt H OEt COOEt Cl HEt H OEt COOCH(CH.sub.3).sub.2 Ms HEt H OEt COOCH(CH.sub.3).sub.2 Cl HEt H OEt CON(CH.sub.3).sub.2 Ms HEt H OEt CON(CH.sub.3).sub.2 Cl HEt H OEt CONHMe Ms HEt H OEt CONHEt Ms HEt H OEt CONHC.sub.3 H.sub.7 Ms HEt H OEt CONHCH(CH.sub.3).sub.2 Ms HEt H OEt CONHC(CH.sub.3).sub.3 Ms HEt H OEt CONEt.sub.2 Ms HEt H OEt CONHC(CH.sub.3).sub.3 Ms HEt H OEt CONHC.sub.4 H.sub.9 Ms HEt H OEt CONHC.sub.4 H.sub.9 Ms HEt H OEt CON(CH(CH.sub.3).sub. 2).sub.2 Ms HEt H OEt Y1 Ms HEt H OEt Y2 Ms HEt H OEt COOPh Ms HEt H OEt COOCH.sub.2 Ph Ms HEt H OEt COOCH.sub.2 CHCH.sub.2 Ms HEt H OEt COOCH.sub.2 C Ms HEt H OCH(CH.sub.3).sub.2 COOMe Ms HEt H OCH(CH.sub.3).sub.2 COOMe Cl HEt H OCH(CH.sub.3).sub.2 COOEt Ms HEt H OCH(CH.sub.3).sub.2 COOEt Cl HEt H OCH(CH.sub.3).sub.2 COOCH(CH.sub.3).sub.2 Ms HEt H OCH(CH.sub.3).sub.2 COOCH(CH.sub.3).sub.2 Cl HEt H OCH(CH.sub.3).sub.2 CON(CH.sub.3).sub.2 Ms HEt H OCH(CH.sub.3).sub.2 CON(CH.sub.3).sub.2 Cl HEt H OCH(CH.sub.3).sub.2 CONHMe Ms HEt H OCH(CH.sub.3).sub.2 CONHEt Ms HEt H OCH(CH.sub.3).sub.2 CONHC.sub.3 H.sub.7 Ms HEt H OCH(CH.sub.3).sub.2 CONHCH(CH.sub.3).sub.2 Ms HEt H OCH(CH.sub.3).sub.2 CONHC(CH.sub.3).sub.3 Ms HEt H OCH(CH.sub.3 ).sub.2 CONEt.sub.2 Ms HEt H OCH(CH.sub.3).sub.2 CONHC(CH.sub.3).sub.3 Ms HEt H OCH(CH.sub.3).sub.2 CONHC.sub.4 H.sub.9 Ms HEt H OCH(CH.sub.3).sub.2 CONHC.sub.4 H.sub.9 Ms HEt H OCH(CH.sub.3).sub.2 CON(CH(CH.sub.3).sub.2).sub.2 Ms HEt H OCH(CH.sub.3).sub.2 Y1 Ms HEt H OCH(CH.sub.3).sub.2 Y2 Ms HEt H OCH(CH.sub.3).sub.2 COOPh Ms HEt H OCH(CH.sub.3).sub.2 COOCH.sub.2 Ph Ms HEt H OCH(CH.sub.3).sub.2 COOCH.sub.2 CHCH.sub.2 Ms HEt H OCH(CH.sub.3).sub.2 COOCH.sub.2 C CH Ms HEt H CH.sub.2 OCH.sub.3 COOMe Ms HEt H CH.sub.2 OCH.sub.3 COOMe Cl HEt H CH.sub.2 OCH.sub.3 COOEt Ms HEt H CH.sub.2 OCH.sub.3 COOEt Cl HEt H CH.sub.2 OCH.sub.3 COOCH(CH.sub.3).sub.2 Ms HEt H CH.sub.2 OCH.sub.3 COOCH(CH.sub.3).sub.2 Cl HEt H CH.sub.2 OCH.sub.3 CON(CH.sub.3).sub.2 Ms HEt H CH.sub.2 OCH.sub.3 CON(CH.sub.3).sub.2 Cl HEt H CH.sub.2 OCH.sub.3 CONHMe Ms HEt H CH.sub.2 OCH.sub.3 CONHEt Ms HEt H CH.sub.2 OCH.sub.3 CONHC.sub.3 H.sub.7 Ms HEt H CH.sub.2 OCH.sub.3 CONHCH(CH.sub.3).sub.2 Ms HEt H CH.sub.2 OCH.sub.3 CONHC(CH.sub.3).sub.3 Ms HEt H CH.sub.2 OCH.sub.3 CONEt.sub.2 Ms HEt H CH.sub.2 OCH.sub.3 CONHC(CH.sub.3).sub.3 Ms HEt H CH.sub.2 OCH.sub.3 CONHC.sub.4 H.sub.9 Ms HEt H CH.sub.2 OCH.sub.3 CONHC.sub.4 H.sub.9 Ms HEt H CH.sub.2 OCH.sub.3 CON(CH(CH.sub.3).sub.2).sub.2 Ms HEt H CH.sub.2 OCH.sub.3 Y1 Ms HEt H CH.sub.2 OCH.sub.3 Y2 Ms HEt H CH.sub.2 OCH.sub.3 COOPh Ms HEt H CH.sub.2 OCH.sub.3 COOCH.sub.2 Ph Ms HEt H CH.sub.2 OCH.sub.3 COOCH.sub.2 CHCH.sub.2 Ms HEt H CH.sub.2 OCH.sub.3 COOCH.sub.2 C CH Ms Hi-Pr H Cl COOMe MeS Hi-Pr H Cl COOMe MeSO Hi-Pr H Cl COOMe Ms Hi-Pr H Cl COOMe Ms Q1i-Pr H Cl COOMe Ms Q2i-Pr H Cl COOMe Ms Q3i-Pr H Cl COOMe Ms Q4i-Pr H Cl COOMe Ms Q5i-Pr H Cl COOMe Ms Q6i-Pr H Cl COOMe Ms Q20i-Pr Me Cl COOMe Ms Hi-Pr Cl Cl COOMe Ms Hi-Pr CF.sub.3 Cl COOMe Ms Hi-Pr OMe Cl COOMe Ms Hi-Pr SMe Cl COOMe Ms Hi-Pr H Cl COOEt MeS Hi-Pr H Cl COOEt MeSO Hi-Pr H Cl COOEt Ms Hi-Pr H Cl COOEt Ms Q1i-Pr H Cl COOEt Ms Q18i-Pr H Cl COOEt Ms Q13i-Pr H Cl COOEt Ms Q4i-Pr H Cl COOEt Ms Q5i-Pr H Cl COOEt Ms Q6i-Pr H Cl COOEt Ms Q22i-Pr Me Cl COOEt Ms Hi-Pr Cl Cl COOEt Ms Hi-Pr CF.sub.3 Cl COOEt Ms Hi-Pr OMe Cl COOEt Ms Hi-Pr SMe Cl COOEt Ms Hi-Pr H Cl COOCH(CH.sub.3).sub.2 MeS Hi-Pr H Cl COOCH(CH.sub.3).sub.2 MeSO Hi-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Hi-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Q7i-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Q12i-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Q9i-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Q4i-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Q5i-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Q6i-Pr H Cl COOCH(CH.sub.3).sub.2 Ms Q17i-Pr Me Cl COOCH(CH.sub.3).sub.2 Ms Hi-Pr Cl Cl COOCH(CH.sub.3).sub.2 Ms Hi-Pr CF.sub.3 Cl COOCH(CH.sub.3).sub.2 Ms Hi-Pr OMe Cl COOCH(CH.sub.3).sub.2 Ms Hi-Pr SMe Cl COOCH(CH.sub.3).sub.2 Ms Hi-Pr H Cl COOMe Cl Hi-Pr H Cl COOMe Cl Q1i-Pr H Cl COOMe Cl Q2i-Pr H Cl COOMe Cl Q3i-Pr H Cl COOEt Cl Hi-Pr H Cl COOEt Cl Q1i-Pr H Cl COOEt Cl Q2i-Pr H Cl COOEt Cl Q3i-Pr H Cl COOCH(CH.sub.3).sub.2 Cl Hi-Pr H Cl COOCH(CH.sub.3).sub.2 Cl Q1i-Pr H Cl COOCH(CH.sub.3).sub.2 Cl Q2i-Pr H Cl COOCH(CH.sub.3).sub.2 Cl Q3i-Pr H Cl CON(CH.sub.3).sub.2 MeS Hi-Pr H Cl CON(CH.sub.3).sub.2 MeSO Hi-Pr H Cl CON(CH.sub.3).sub.2 Ms Hi-Pr H Cl CON(CH.sub.3).sub.2 Ms Q1i-Pr H Cl CON(CH.sub.3).sub.2 Ms Q18i-Pr H Cl CON(CH.sub.3).sub.2 Ms Q13i-Pr H Cl CON(CH.sub.3).sub.2 Ms Q4i-Pr H Cl CON(CH.sub.3).sub.2 Ms Q5i-Pr H Cl CON(CH.sub.3).sub.2 Ms Q6i-Pr H Cl CON(CH.sub.3).sub.2 Ms Q22i-Pr Me Cl CON(CH.sub.3).sub.2 Ms Hi-Pr Cl Cl CON(CH.sub.3).sub.2 Ms Hi-Pr CF.sub.3 Cl CON(CH.sub.3).sub.2 Ms Hi-Pr OMe Cl CON(CH.sub.3).sub.2 Ms Hi-Pr SMe Cl CON(CH.sub.3).sub.2 Ms Hi-Pr H Cl CON(CH.sub.3).sub.2 Cl Hi-Pr H Cl CON(CH.sub.3).sub.2 Cl Q1i-Pr H Cl CON(CH.sub.3).sub.2 Cl Q2i-Pr H Cl CON(CH.sub.3).sub.2 Cl Q3i-Pr H Cl COOC.sub.4 H.sub.9 Ms Hi-Pr H Cl COOC.sub.4 H.sub.9 Cl Hi-Pr H Cl COOCH.sub.2 CH(CH.sub.3).sub.2 Ms Hi-Pr H Cl COOCH.sub.2 CH(CH.sub.3).sub.2 Cl Hi-Pr H Cl COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms Hi-Pr H Cl COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl Hi-Pr H Cl COOC(CH.sub.3).sub.3 Ms Hi-Pr H Cl COOC(CH.sub.3).sub.3 Cl Hi-Pr H Cl CONHMe Ms Hi-Pr H Cl CONHMe Cl Hi-Pr H Cl CONHEt Ms Hi-Pr H Cl CONHEt Cl Hi-Pr H Cl CONHCH(CH.sub.3).sub.2 Ms Hi-Pr H Cl CONHCH(CH.sub.3).sub.2 Cl Hi-Pr H Cl CONHC(CH.sub.3).sub.3 Ms Hi-Pr H Cl CONHC(CH.sub.3).sub.3 Cl Hi-Pr H Cl CONHC.sub.4 H.sub.9 Ms Hi-Pr H Cl CONHC.sub.4 H.sub.9 Cl Hi-Pr H Cl CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms Hi-Pr H Cl CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl Hi-Pr H Cl CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms Hi-Pr H Cl CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl Hi-Pr H Cl CONEt.sub.2 Ms Hi-Pr H Cl CONEt.sub.2 Cl Hi-Pr H Cl CON(CH(CH.sub.3).sub.2).sub.2 Ms Hi-Pr H Cl CON(CH(CH.sub.3).sub.2).sub.2 Cl Hi-Pr H Cl Y1 Ms Hi-Pr H Cl Y1 Cl Hi-Pr H Cl Y2 Ms Hi-Pr H Cl Y2 Cl Hi-Pr H Cl Y3 Ms Hi-Pr H Cl Y3 Cl Hi-Pr H Cl COOPh Ms Hi-Pr H Cl COOPh Cl Hi-Pr H Cl COOCH.sub.2 Ph Ms Hi-Pr H Cl COOCH.sub.2 Ph Cl Hi-Pr H Cl COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H Cl COOCH.sub.2 CHCH.sub.2 Cl Hi-Pr H Cl COOCH.sub.2 C CH Ms Hi-Pr H Cl COOCH.sub.2 C CH Cl Hi-Pr H Cl C(O)SMe Ms Hi-Pr H Cl C(O)SMe Cl Hi-Pr H Cl C(O)SEt Ms Hi-Pr H Cl C(O)SEt Cl Hi-Pr H Cl C(O)SCH(CH.sub.3).sub.2 Ms Hi-Pr H Cl C(O)SCH(CH.sub.3).sub.2 Cl Hi-Pr H Cl C(O)SC.sub.3 H.sub.7 Ms Hi-Pr H Cl C(O)SC.sub.3 H.sub.7 Cl Hi-Pr H Cl C(S)OMe Ms Hi-Pr H Cl C(S)OMe Cl Hi-Pr H Cl C(S)OEt Ms Hi-Pr H Cl C(S)OEt Cl Hi-Pr H Cl C(S)OCH(CH.sub.3).sub.2 Ms Hi-Pr H Cl C(S)OCH(CH.sub.3).sub.2 Cl Hi-Pr H Cl C(S)SC.sub.3 H.sub.7 Ms Hi-Pr H Cl C(S)SC.sub.3 H.sub.7 Cl Hi-Pr H Cl C(S)SMe Ms Hi-Pr H Cl C(S)SMe Cl Hi-Pr H Cl C(S)SEt Ms Hi-Pr H Cl C(S)SEt Cl Hi-Pr H Cl C(S)SCH(CH.sub.3).sub.2 Ms Hi-Pr H Cl C(S)SCH(CH.sub.3).sub.2 Cl Hi-Pr H Cl C(S)SC.sub.3 H.sub.7 Ms Hi-Pr H Cl C(S)SC.sub.3 H.sub.7 Cl Hi-Pr H Me COOMe MeS Hi-Pr H Me COOMe MeSO Hi-Pr H Me COOMe Ms Hi-Pr H Me COOMe Ms Q1i-Pr H Me COOMe Ms Q2i-Pr H Me COOMe Ms Q3i-Pr H Me COOMe Ms Q4i-Pr H Me COOMe Ms Q5i-Pr H Me COOMe Ms Q6i-Pr H Me COOMe Ms Q20i-Pr Me Me COOMe Ms Hi-Pr Cl Me COOMe Ms Hi-Pr CF.sub.3 Me COOMe Ms Hi-Pr OMe Me COOMe Ms Hi-Pr SMe Me COOMe Ms Hi-Pr H Me COOEt MeS Hi-Pr H Me COOEt MeSO Hi-Pr H Me COOEt Ms Hi-Pr H Me COOEt Ms Q1i-Pr H Me COOEt Ms Q18i-Pr H Me COOEt Ms Q13i-Pr H Me COOEt Ms Q4i-Pr H Me COOEt Ms Q5i-Pr H Me COOEt Ms Q6i-Pr H Me COOEt Ms Q22i-Pr Me Me COOEt Ms Hi-Pr Cl Me COOEt Ms Hi-Pr CF.sub.3 Me COOEt Ms Hi-Pr OMe Me COOEt Ms Hi-Pr SMe Me COOEt Ms Hi-Pr H Me COOCH(CH.sub.3).sub.2 MeS Hi-Pr H Me COOCH(CH.sub.3).sub.2 MeSO Hi-Pr H Me COOCH(CH.sub.3).sub.2 Ms Hi-Pr H Me COOCH(CH.sub.3).sub.2 Ms Q7i-Pr H Me COOCH(CH.sub.3).sub.2 Ms Q12i-Pr H Me COOCH(CH.sub.3).sub.2 Ms Q9i-Pr H Me COOCH(CH.sub.3).sub.2 Ms Q4i-Pr H Me COOCH(CH.sub.3).sub.2 Ms Q5i-Pr H Me COOCH(CH.sub.3).sub.2 Ms Q6i-Pr H Me COOCH(CH.sub.3).sub.2 Ms Q17i-Pr Me Me COOCH(CH.sub.3).sub.2 Ms Hi-Pr Cl Me COOCH(CH.sub.3).sub.2 Ms Hi-Pr CF.sub.3 Me COOCH(CH.sub.3).sub.2 Ms Hi-Pr OMe Me COOCH(CH.sub.3).sub.2 Ms Hi-Pr SMe Me COOCH(CH.sub.3).sub.2 Ms Hi-Pr H Me COOMe Cl Hi-Pr H Me COOMe Cl Q1i-Pr H Me COOMe Cl Q2i-Pr H Me COOMe Cl Q3i-Pr H Me COOEt Cl Hi-Pr H Me COOEt Cl Q1i-Pr H Me COOEt Cl Q2i-Pr H Me COOEt Cl Q3i-Pr H Me COOCH(CH.sub.3).sub.2 Cl Hi-Pr H Me COOCH(CH.sub.3).sub.2 Cl Q1i-Pr H Me COOCH(CH.sub.3).sub.2 Cl Q2i-Pr H Me COOCH(CH.sub.3).sub.2 Cl Q3i-Pr H Me CON(CH.sub.3).sub.2 MeS Hi-Pr H Me CON(CH.sub.3).sub.2 MeSO Hi-Pr H Me CON(CH.sub.3).sub.2 Ms Hi-Pr H Me CON(CH.sub.3).sub.2 Ms Q1i-Pr H Me CON(CH.sub.3).sub.2 Ms Q18i-Pr H Me CON(CH.sub.3).sub.2 Ms Q13i-Pr H Me CON(CH.sub.3).sub.2 Ms Q4i-Pr H Me CON(CH.sub.3).sub.2 Ms Q5i-Pr H Me CON(CH.sub.3).sub.2 Ms Q6i-Pr H Me CON(CH.sub.3).sub.2 Ms Q22i-Pr Me Me CON(CH.sub.3).sub.2 Ms Hi-Pr CF.sub.3 Me CON(CH.sub.3).sub.2 Ms Hi-Pr OMe Me CON(CH.sub.3).sub.2 Ms Hi-Pr SMe Me CON(CH.sub.3).sub.2 Ms Hi-Pr H Me CON(CH.sub.3).sub.2 Cl Hi-Pr H Me CON(CH.sub.3).sub.2 Cl Q1i-Pr H Me CON(CH.sub.3).sub.2 Cl Q2i-Pr H Me CON(CH.sub.3).sub.2 Cl Q3i-Pr H Me COOC.sub.4 H.sub.9 Ms Hi-Pr H Me COOC.sub.4 H.sub.9 Cl Hi-Pr H Me COOCH.sub.2 CH(CH.sub.3).sub.2 Ms Hi-Pr H Me COOCH.sub.2 CH(CH.sub.3).sub.2 Cl Hi-Pr H Me COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms Hi-Pr H Me COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl Hi-Pr H Me COOC(CH.sub.3).sub.3 Ms Hi-Pr H Me COOC(CH.sub.3).sub.3 Cl Hi-Pr H Me CONHMe Ms Hi-Pr H Me CONHMe Cl Hi-Pr H Me CONHEt Ms Hi-Pr H Me CONHEt Cl Hi-Pr H Me CONHCH(CH.sub.3).sub.2 Ms Hi-Pr H Me CONHCH(CH.sub.3).sub.2 Cl Hi-Pr H Me CONHC(CH.sub.3).sub.3 Ms Hi-Pr H Me CONHC(CH.sub.3).sub.3 Cl Hi-Pr H Me CONHC.sub.4 H.sub.9 Ms Hi-Pr H Me CONHC.sub.4 H.sub.9 Cl Hi-Pr H Me CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms Hi-Pr H Me CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl Hi-Pr H Me CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms Hi-Pr H Me CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl Hi-Pr H Me CONEt.sub.2 Ms Hi-Pr H Me CONEt.sub.2 Cl Hi-Pr H Me CON(CH(CH.sub.3).sub.2).sub.2 Ms Hi-Pr H Me CON(CH(CH.sub.3).sub.2).sub.2 Cl Hi-Pr H Me Y1 Ms Hi-Pr H Me Y1 Cl Hi-Pr H Me Y2 Ms Hi-Pr H Me Y2 Cl Hi-Pr H Me Y3 Ms Hi-Pr H Me Y3 Cl Hi-Pr H Me COOPh Ms Hi-Pr H Me COOPh Cl Hi-Pr H Me COOCH.sub.2 Ph Ms Hi-Pr H Me COOCH.sub.2 Ph Cl Hi-Pr H Me COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H Me COOCH.sub.2 CHCH.sub.2 Cl Hi-Pr H Me COOCH.sub.2 C CH Ms Hi-Pr H Me COOCH.sub.2 C CH Cl Hi-Pr H Me C(O)SMe Ms Hi-Pr H Me C(O)SMe Cl Hi-Pr H Me C(O)SEt Ms Hi-Pr H Me C(O)SEt Cl Hi-Pr H Me C(O)SCH(CH.sub.3).sub.2 Ms Hi-Pr H Me C(O)SCH(CH.sub.3).sub.2 Cl Hi-Pr H Me C(O)SC.sub.3 H.sub.7 Ms Hi-Pr H Me C(O)SC.sub.3 H.sub.7 Cl Hi-Pr H Me C(S)OMe Ms Hi-Pr H Me C(S)OMe Cl Hi-Pr H Me C(S)OEt Ms Hi-Pr H Me C(S)OEt Cl Hi-Pr H Me C(S)OCH(CH.sub.3).sub.2 Ms Hi-Pr H Me C(S)OCH(CH.sub.3).sub.2 Cl Hi-Pr H Me C(S)SC.sub.3 H.sub.7 Ms Hi-Pr H Me C(S)SC.sub.3 H.sub.7 Cl Hi-Pr H Me C(S)SMe Ms Hi-Pr H Me C(S)SMe Cl Hi-Pr H Me C(S)SEt Ms Hi-Pr H Me C(S)SEt Cl Hi-Pr H Me C(S)SCH(CH.sub.3).sub.2 Ms Hi-Pr H Me C(S)SCH(CH.sub.3).sub.2 Cl Hi-Pr H Me C(S)SC.sub.3 H.sub.7 Ms Hi-Pr H Me C(S)SC.sub.3 H.sub.7 Cl Hi-Pr H OMe COOMe MeS Hi-Pr H OMe COOMe MeSO Hi-Pr H OMe COOMe Ms Hi-Pr H OMe COOMe Ms Q1i-Pr H OMe COOMe Ms Q2i-Pr H OMe COOMe Ms Q3i-Pr H OMe COOMe Ms Q4i-Pr H OMe COOMe Ms Q5i-Pr H OMe COOMe Ms Q6i-Pr H OMe COOMe Ms Q20i-Pr Me OMe COOMe Ms Hi-Pr Cl OMe COOMe Ms Hi-Pr CF.sub.3 OMe COOMe Ms Hi-Pr OMe OMe COOMe Ms Hi-Pr SMe OMe COOMe Ms Hi-Pr H OMe COOEt MeS Hi-Pr H OMe COOEt MeSO Hi-Pr H OMe COOEt Ms Hi-Pr H OMe COOEt Ms Q1i-Pr H OMe COOEt Ms Q18i-Pr H OMe COOEt Ms Q13i-Pr H OMe COOEt Ms Q4i-Pr H OMe COOEt Ms Q5i-Pr H OMe COOEt Ms Q6i-Pr H OMe COOEt Ms Q22i-Pr Me OMe COOEt Ms Hi-Pr Cl OMe COOEt Ms Hi-Pr CF.sub.3 OMe COOEt Ms Hi-Pr OMe OMe COOEt Ms Hi-Pr SMe OMe COOEt Ms Hi-Pr H OMe COOCH(CH.sub.3 ).sub.2 MeS Hi-Pr H OMe COOCH(CH.sub.3).sub.2 MeSO Hi-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Hi-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Q7i-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Q12i-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Q9i-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Q4i-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Q5i-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Q6i-Pr H OMe COOCH(CH.sub.3).sub.2 Ms Q17i-Pr Me OMe COOCH(CH.sub.3).sub.2 Ms Hi-Pr Cl OMe COOCH(CH.sub.3).sub.2 Ms Hi-Pr CF.sub.3 OMe COOCH(CH.sub.3).sub.2 Ms Hi-Pr OMe OMe COOCH(CH.sub.3).sub.2 Ms Hi-Pr SMe OMe COOCH(CH.sub.3).sub.2 Ms Hi-Pr H OMe COOMe Cl Hi-Pr H OMe COOMe Cl Q1i-Pr H OMe COOMe Cl Q2i-Pr H OMe COOMe Cl Q3i-Pr H OMe COOEt Cl Hi-Pr H OMe COOEt Cl Q1i-Pr H OMe COOEt Cl Q2i-Pr H OMe COOEt Cl Q3i-Pr H OMe COOCH(CH.sub.3).sub.2 Cl Hi-Pr H OMe COOCH(CH.sub.3).sub.2 Cl Q1i-Pr H OMe COOCH(CH.sub.3).sub.2 Cl Q2i-Pr H OMe COOCH(CH.sub.3).sub.2 Cl Q3i-Pr H OMe CON(CH.sub.3).sub.2 MeS Hi-Pr H OMe CON(CH.sub.3).sub.2 MeSO Hi-Pr H OMe CON(CH.sub.3).sub.2 Ms Hi-Pr H OMe CON(CH.sub.3).sub.2 Ms Q1i-Pr H OMe CON(CH.sub.3).sub.2 Ms Q18i-Pr H OMe CON(CH.sub.3).sub.2 Ms Q13i-Pr H OMe CON(CH.sub.3).sub.2 Ms Q4i-Pr H OMe CON(CH.sub.3).sub.2 Ms Q5i-Pr H OMe CON(CH.sub.3).sub.2 Ms Q6i-Pr H OMe CON(CH.sub.3).sub.2 Ms Q22i-Pr Me OMe CON(CH.sub.3).sub.2 Ms Hi-Pr Cl OMe CON(CH.sub.3).sub.2 Ms Hi-Pr CF.sub.3 OMe CON(CH.sub.3).sub.2 Ms Hi-Pr OMe OMe CON(CH.sub.3).sub.2 Ms Hi-Pr SMe OMe CON(CH.sub.3).sub.2 Ms Hi-Pr H OMe CON(CH.sub.3).sub.2 Cl Hi-Pr H OMe CON(CH.sub.3).sub.2 Cl Q1i-Pr H OMe CON(CH.sub.3).sub.2 Cl Q2i-Pr H OMe CON(CH.sub.3).sub.2 Cl Q3i-Pr H OMe COOC.sub.4 H.sub.9 Ms Hi-Pr H OMe COOC.sub. 4 H.sub.9 Cl Hi-Pr H OMe COOCH.sub.2 CH(CH.sub.3).sub.2 Ms Hi-Pr H OMe COOCH.sub.2 CH(CH.sub.3).sub.2 Cl Hi-Pr H OMe COOCH(CH.sub.3)C.sub.2 H.sub.5 Ms Hi-Pr H OMe COOCH(CH.sub.3)C.sub.2 H.sub.5 Cl Hi-Pr H OMe COOC(CH.sub.3).sub.3 Ms Hi-Pr H OMe COOC(CH.sub.3).sub.3 Cl Hi-Pr H OMe CONHMe Ms Hi-Pr H OMe CONHMe Cl Hi-Pr H OMe CONHEt Ms Hi-Pr H OMe CONHEt Cl Hi-Pr H OMe CONHCH(CH.sub.3).sub.2 Ms Hi-Pr H OMe CONHCH(CH.sub.3).sub.2 Cl Hi-Pr H OMe CONHC(CH.sub.3).sub.3 Ms Hi-Pr H OMe CONHC(CH.sub.3).sub.3 Cl Hi-Pr H OMe CONHC.sub.4 H.sub.9 Ms Hi-Pr H OMe CONHC.sub.4 H.sub.9 Cl Hi-Pr H OMe CONHCH.sub.2 CH(CH.sub.3).sub.2 Ms Hi-Pr H OMe CONHCH.sub.2 CH(CH.sub.3).sub.2 Cl Hi-Pr H OMe CONHCH(CH.sub.3)C.sub.2 H.sub.5 Ms Hi-Pr H OMe CONHCH(CH.sub.3)C.sub.2 H.sub.5 Cl Hi-Pr H OMe CONEt.sub.2 Ms Hi-Pr H OMe CONEt.sub. 2 Cl Hi-Pr H OMe CON(CH(CH.sub.3).sub.2).sub.2 Ms Hi-Pr H OMe CON(CH(CH.sub.3).sub.2).sub.2 Cl Hi-Pr H OMe Y1 Ms Hi-Pr H OMe Y1 Cl Hi-Pr H OMe Y2 Ms Hi-Pr H OMe Y2 Cl Hi-Pr H OMe Y3 Ms Hi-Pr H OMe Y3 Cl Hi-Pr H OMe COOPh Ms Hi-Pr H OMe COOPh Cl Hi-Pr H OMe COOCH.sub.2 Ph Ms Hi-Pr H OMe COOCH.sub.2 Ph Cl Hi-Pr H OMe COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H OMe COOCH.sub.2 CHCH.sub.2 Cl Hi-Pr H OMe COOCH.sub.2 C CH Ms Hi-Pr H OMe COOCH.sub.2 C CH Cl Hi-Pr H OMe C(O)SMe Ms Hi-Pr H OMe C(O)SMe Cl Hi-Pr H OMe C(O)SEt Ms Hi-Pr H OMe C(O)SEt Cl Hi-Pr H OMe C(O)SCH(CH.sub.3).sub.2 Ms Hi-Pr H OMe C(O)SCH(CH.sub.3).sub.2 Cl Hi-Pr H OMe C(O)SC.sub.3 H.sub.7 Ms Hi-Pr H OMe C(O)SC.sub. 3 H.sub.7 Cl Hi-Pr H OMe C(S)OMe Ms Hi-Pr H OMe C(S)OMe Cl Hi-Pr H OMe C(S)OEt Ms Hi-Pr H OMe C(S)OEt Cl Hi-Pr H OMe C(S)OCH(CH.sub.3).sub.2 Ms Hi-Pr H OMe C(S)OCH(CH.sub.3).sub.2 Cl Hi-Pr H OMe C(S)SC.sub.3 H.sub.7 Ms Hi-Pr H OMe C(S)SC.sub.3 H.sub.7 Cl Hi-Pr H OMe C(S)SMe Ms Hi-Pr H OMe C(S)SMe Cl Hi-Pr H OMe C(S)SEt Ms Hi-Pr H OMe C(S)SEt Cl Hi-Pr H OMe C(S)SCH(CH.sub.3).sub.2 Ms Hi-Pr H OMe C(S)SCH(CH.sub.3).sub.2 Cl Hi-Pr H OMe C(S)SC.sub.3 H.sub.7 Ms Hi-Pr H OMe C(S)SC.sub.3 H.sub.7 Cl Hi-Pr H Br COOMe Ms Hi-Pr H Br COOMe Cl Hi-Pr H Br COOEt Ms Hi-Pr H Br COOEt Cl Hi-Pr H Br COOCH(CH.sub.3).sub.2 Ms Hi-Pr H Br COOCH(CH.sub.3).sub.2 Cl Hi-Pr H Br CON(CH.sub.3).sub.2 Ms Hi-Pr H Br CON(CH.sub.3).sub.2 Cl Hi-Pr H Br CONHMe Ms Hi-Pr H Br CONHEt Ms Hi-Pr H Br CONHC.sub.3 H.sub.7 Ms Hi-Pr H Br CONHCH(CH.sub.3).sub.2 Ms Hi-Pr H Br CONHC(CH.sub.3).sub.3 Ms Hi-Pr H Br CONEt.sub.2 Ms Hi-Pr H Br CONHC(CH.sub.3).sub.3 Ms Hi-Pr H Br CONHC.sub.4 H.sub.9 Ms Hi-Pr H Br CONHC.sub.4 H.sub.9 Ms Hi-Pr H Br CON(CH(CH.sub.3).sub.2).sub.2 Ms Hi-Pr H Br Y1 Ms Hi-Pr H Br Y2 Ms Hi-Pr H Br COOPh Ms Hi-Pr H Br COOCH.sub.2 Ph Ms Hi-Pr H Br COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H Br COOCH.sub.2 C CH Ms Hi-Pr H OEt COOMe Ms Hi-Pr H OEt COOMe Cl Hi-Pr H OEt COOEt Ms Hi-Pr H OEt COOEt Cl Hi-Pr H OEt COOCH(CH.sub.3).sub.2 Ms Hi-Pr H OEt COOCH(CH.sub.3).sub.2 Cl Hi-Pr H OEt CON(CH.sub.3).sub.2 Ms Hi-Pr H OEt CON(CH.sub.3).sub.2 Cl Hi-Pr H OEt CONHMe Ms Hi-Pr H OEt CONHEt Ms Hi-Pr H OEt CONHC.sub.3 H.sub.7 Ms Hi-Pr H OEt CONHCH(CH.sub.3).sub.2 Ms Hi-Pr H OEt CONHC(CH.sub.3).sub.3 Ms Hi-Pr H OEt CONEt.sub.2 Ms Hi-Pr H OEt CONHC(CH.sub.3).sub.3 Ms Hi-Pr H OEt CONHC.sub.4 H.sub.9 Ms Hi-Pr H OEt CONHC.sub.4 H.sub.9 Ms Hi-Pr H OEt CON(CH(CH.sub.3).sub.2).sub.2 Ms Hi-Pr H OEt Y1 Ms Hi-Pr H OEt Y2 Ms Hi-Pr H OEt COOPh Ms Hi-Pr H OEt COOCH.sub.2 Ph Ms Hi-Pr H OEt COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H OEt COOCH.sub.2 C CH Ms Hi-Pr H OCH(CH.sub.3).sub.2 COOMe Ms Hi-Pr H OCH(CH.sub.3).sub.2 COOMe Cl Hi-Pr H OCH(CH.sub.3).sub.2 COOEt Ms Hi-Pr H OCH(CH.sub.3).sub.2 COOEt Cl Hi-Pr H OCH(CH.sub.3).sub.2 COOCH(CH.sub.3).sub.2 Ms Hi-Pr H OCH(CH.sub.3).sub.2 COOCH(CH.sub.3).sub.2 Cl Hi-Pr H OCH(CH.sub.3).sub.2 CON(CH.sub.3).sub.2 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CON(CH.sub. 3).sub.2 Cl Hi-Pr H OCH(CH.sub.3).sub.2 CONHMe Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONHEt Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONHC.sub.3 H.sub.7 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONHCH(CH.sub.3).sub.2 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONHC(CH.sub.3).sub.3 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONEt.sub.2 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONHC(CH.sub.3).sub.3 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONHC.sub.4 H.sub.9 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CONHC.sub.4 H.sub.9 Ms Hi-Pr H OCH(CH.sub.3).sub.2 CON(CH(CH.sub.3).sub.2).sub.2 Ms Hi-Pr H OCH(CH.sub.3).sub.2 Y1 Ms Hi-Pr H OCH(CH.sub.3).sub.2 Y2 Ms HMe H CF.sub.3 COOMe Ms HMe H CF.sub.3 COOEt Ms HMe H CF.sub.3 COOCH(CH.sub.3).sub.2 Ms HMe H CF.sub.3 CONMe.sub.2 Ms HMe H CF.sub.3 CONEt.sub.2 Ms HMe H CF.sub.3 COOC.sub.3 H.sub.7 Ms HMe H CF.sub.3 Y1 Ms HMe H CF.sub.3 Y2 Ms HMe H CF.sub.3 Y3 Ms HMe H CF.sub.3 COOPh Ms HMe H CF.sub.3 COOCH.sub.2 Ph Ms HMe H CF.sub.3 COOCH.sub.2 CHCH.sub.2 Ms HMe H CN COOMe Ms HMe H CN COOEt Ms HMe H CN COOCH(CH.sub.3).sub.2 Ms HMe H CN CONMe.sub.2 Ms HMe H CN CONEt.sub.2 Ms HMe H CN COOC.sub.3 H.sub.7 Ms HMe H CN Y1 Ms HMe H CN Y2 Ms HMe H CN Y3 Ms HMe H CN COOPh Ms HMe H CN COOCH.sub.2 Ph Ms HMe H CN COOCH.sub.2 CHCH.sub.2 Ms HMe H CH.sub.2 OEt COOMe Ms HMe H CH.sub.2 OEt COOEt Ms HMe H CH.sub.2 OEt COOCH(CH.sub.3).sub.2 Ms HMe H CH.sub.2 OEt CONMe.sub.2 Ms HMe H CH.sub.2 OEt CONEt.sub.2 Ms HMe H CH.sub.2 OEt COOC.sub.3 H.sub.7 Ms HMe H CH.sub.2 OEt Y1 Ms HMe H CH.sub.2 OEt Y2 Ms HMe H CH.sub.2 OEt Y3 Ms HMe H CH.sub.2 OEt COOPh Ms HMe H CH.sub.2 OEt COOCH.sub.2 Ph Ms HMe H CH.sub.2 OEt COOCH.sub.2 CHCH.sub.2 Ms HMe H Et COOMe Ms HMe H Et COOEt Ms HMe H Et COOCH(CH.sub.3).sub.2 Ms HMe H Et CONMe.sub.2 Ms HMe H Et CONEt.sub.2 Ms HMe H Et COOC.sub.3 H.sub.7 Ms HMe H Et Y1 Ms HMe H Et Y2 Ms HMe H Et Y3 Ms HMe H Et COOPh Ms HMe H Et COOCH.sub.2 Ph Ms HMe H Et COOCH.sub.2 CHCH.sub.2 Ms HMe H i-Pr COOMe Ms HMe H i-Pr COOEt Ms HMe H i-Pr COOCH(CH.sub.3).sub.2 Ms HMe H i-Pr CONMe.sub.2 Ms HMe H i-Pr CONEt.sub.2 Ms HMe H i-Pr COOC.sub.3 H.sub.7 Ms HMe H i-Pr Y1 Ms HMe H i-Pr Y2 Ms HMe H i-Pr Y3 Ms HMe H i-Pr COOPh Ms HMe H i-Pr COOCH.sub.2 Ph Ms HMe H i-Pr COOCH.sub.2 CHCH.sub. 2 Ms HMe H n-Pr COOMe Ms HMe H n-Pr COOEt Ms HMe H n-Pr COOCH(CH.sub.3).sub.2 Ms HMe H n-Pr CONMe.sub.2 Ms HMe H n-Pr CONEt.sub.2 Ms HMe H n-Pr COOC.sub.3 H.sub.7 Ms HMe H n-Pr Y1 Ms HMe H n-Pr Y2 Ms HMe H n-Pr Y3 Ms HMe H n-Pr COOPh Ms HMe H n-Pr COOCH.sub.2 Ph Ms HMe H n-Pr COOCH.sub.2 CHCH.sub.2 Ms HMe H I COOMe Ms HMe H I COOEt Ms HMe H I COOCH(CH.sub.3).sub.2 Ms HMe H I CONMe.sub.2 Ms HMe H I CONEt.sub.2 Ms HMe H I COOC.sub.3 H.sub.7 Ms HMe H I Y1 Ms HMe H I Y2 Ms H__________________________________________________________________________
__________________________________________________________________________Me H I Y3 Ms HMe H I COOPh Ms HMe H I COOCH.sub.2 Ph Ms HMe H I COOCH.sub.2 CHCH.sub.2 Ms HEt H NO.sub.2 COOMe Ms HEt H NO.sub.2 COOEt Ms HEt H NO.sub.2 COOCH(CH.sub.3).sub.2 Ms HEt H NO.sub.2 CONMe.sub.2 Ms HEt H NO.sub.2 CONEt.sub.2 Ms HEt H NO.sub.2 COOC.sub.3 H.sub.7 Ms HEt H NO.sub.2 Y1 Ms HEt H NO.sub.2 Y2 Ms HEt H NO.sub.2 Y3 Ms HEt H NO.sub.2 COOPh Ms HEt H NO.sub.2 Y2 Ms HEt H NO.sub.2 Y3 Ms HEt H NO.sub.2 COOPh Ms HEt H NO.sub.2 COOCH.sub.2 Ph Ms HEt H NO.sub.2 COOCH.sub.2 CHCH.sub.2 Ms HEt H CF.sub.3 COOMe Ms HEt H CF.sub.3 COOEt Ms HEt H CF.sub.3 COOCH(CH.sub.3).sub.2 Ms HEt H CF.sub.3 CONMe.sub.2 Ms HEt H CF.sub.3 CONEt.sub.2 Ms HEt H CF.sub.3 COOC.sub.3 H.sub.7 Ms HEt H CF.sub.3 Y1 Ms HEt H CF.sub.3 Y2 Ms HEt H NO.sub.2 Y3 Ms HEt H NO.sub.2 COOPh Ms HEt H NO.sub.2 COOCH.sub.2 Ph Ms HEt H NO.sub.2 COOCH.sub.2 CHCH.sub.2 Ms HEt H CF.sub.3 COOMe Ms HEt H CF.sub.3 COOEt Ms HEt H CF.sub.3 COOCH(CH.sub.3).sub.2 Ms HEt H CF.sub.3 CONMe.sub.2 Ms HEt H CF.sub.3 CONEt.sub.2 Ms HEt H CF.sub.3 COOC.sub.3 H.sub.7 Ms HEt H CF.sub.3 Y1 Ms HEt H CF.sub.3 Y2 Ms HEt H CF.sub.3 Y3 Ms HEt H CF.sub.3 COOPh Ms HEt H CF.sub.3 COOCH.sub.2 Ph Ms HEt H CF.sub.3 COOCH.sub.2 CHCH.sub.2 Ms HEt H CN COOMe Ms HEt H CN COOEt Ms HEt H CN COOCH(CH.sub.3).sub.2 Ms HEt H CN CONMe.sub.2 Ms HEt H CN CONEt.sub.2 Ms HEt H CN COOC.sub.3 H.sub.7 Ms HEt H CN Y1 Ms HEt H CN Y2 Ms HEt H CN Y3 Ms HEt H CN COOPh Ms HEt H CN COOCH.sub.2 Ph Ms HEt H CN COOCH.sub.2 CHCH.sub.2 Ms HEt H CH.sub.2 OEt COOMe Ms HEt H CH.sub.2 OEt COOEt Ms HEt H CH.sub.2 OEt COOCH(CH.sub.3).sub.2 Ms HEt H CH.sub.2 OEt CONMe.sub.2 Ms HEt H CH.sub.2 OEt CONEt.sub.2 Ms HEt H CH.sub.2 OEt COOC.sub.3 H.sub.7 Ms HEt H CH.sub.2 OEt Y1 Ms HEt H CH.sub.2 OEt Y2 Ms HEt H CH.sub.2 OEt Y3 Ms HEt H CH.sub.2 OEt COOPh Ms HEt H CH.sub.2 OEt COOCH.sub.2 Ph Ms HEt H CH.sub.2 OEt COOCH.sub.2 CHCH.sub.2 Ms HEt H Et COOMe Ms HEt H Et COOEt Ms HEt H Et COOCH(CH.sub.3).sub.2 Ms HEt H Et CONMe.sub.2 Ms HEt H Et CONEt.sub.2 Ms HEt H Et COOC.sub.3 H.sub.7 Ms HEt H Et Y1 Ms HEt H Et Y2 Ms HEt H Et Y3 Ms HEt H Et COOPh Ms HEt H Et COOCH.sub.2 Ph Ms HEt H Et COOCH.sub.2 CHCH.sub.2 Ms HEt H i-Pr COOMe Ms HEt H i-Pr COOEt Ms HEt H i-Pr COOCH(CH.sub.3).sub.2 Ms HEt H i-Pr CONMe.sub.2 Ms HEt H i-Pr CONEt.sub.2 Ms HEt H i-Pr COOC.sub.3 H.sub.7 Ms HEt H i-Pr Y1 Ms HEt H i-Pr Y2 Ms HEt H i-Pr Y3 Ms HEt H i-Pr COOPh Ms HEt H i-Pr COOCH.sub.2 Ph Ms HEt H i-Pr COOCH.sub.2 CHCH.sub.2 Ms HEt H n-Pr COOMe Ms HEt H n-Pr COOEt Ms HEt H n-Pr COOCH(CH.sub.3).sub.2 Ms HEt H n-Pr CONMe.sub.2 Ms HEt H n-Pr CONEt.sub.2 Ms HEt H n-Pr COOC.sub.3 H.sub.7 Ms HEt H n-Pr Y1 Ms HEt H n-Pr Y2 Ms HEt H n-Pr Y3 Ms HEt H n-Pr COOPh Ms HEt H n-Pr COOCH.sub.2 Ph Ms HEt H n-Pr COOCH.sub.2 CHCH.sub.2 Ms HEt H I COOMe Ms HEt H I COOEt Ms HEt H I COOCH(CH.sub.3).sub.2 Ms HEt H I CONMe.sub.2 Ms HEt H I CONEt.sub.2 Ms HEt H I COOC.sub.3 H.sub.7 Ms HEt H I Y1 Ms HEt H I Y2 Ms HEt H I Y3 Ms HEt H I COOPh Ms HEt H I COOCH.sub.2 Ph Ms HEt H I COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H NO.sub.2 COOMe Ms Hi-Pr H NO.sub.2 COOEt Ms Hi-Pr H NO.sub.2 COOCH(CH.sub.3).sub.2 Ms Hi-Pr H NO.sub.2 CONMe.sub.2 Ms Hi-Pr H NO.sub.2 CONEt.sub.2 Ms Hi-Pr H NO.sub.2 COOC.sub.3 H.sub.7 Ms Hi-Pr H NO.sub.2 Y1 Ms Hi-Pr H NO.sub.2 Y2 Ms Hi-Pr H NO.sub.2 Y3 Ms Hi-Pr H NO.sub.2 COOPh Ms Hi-Pr H NO.sub.2 COOCH.sub.2 Ph Ms Hi-Pr H CF.sub.3 COOMe Ms Hi-Pr H CF.sub.3 COOEt Ms Hi-Pr H CF.sub.3 COOCH(CH.sub. 3).sub.2 Ms Hi-Pr H CF.sub.3 CONMe.sub.2 Ms Hi-Pr H CF.sub.3 CONEt.sub.2 Ms Hi-Pr H CF.sub.3 COOC.sub.3 H.sub.7 Ms Hi-Pr H CF.sub.3 Y1 Ms Hi-Pr H CF.sub.3 Y2 Ms Hi-Pr H CF.sub.3 Y3 Ms Hi-Pr H CF.sub.3 COOPh Ms Hi-Pr H CF.sub.3 COOCH.sub.2 Ph Ms Hi-Pr H CF.sub.3 COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H CN COOMe Ms Hi-Pr H CN COOEt Ms Hi-Pr H CN COOCH(CH.sub.3).sub.2 Ms Hi-Pr H CN CONMe.sub.2 Ms Hi-Pr H CN CONEt.sub.2 Ms Hi-Pr H CN COOC.sub.3 H.sub.7 Ms Hi-Pr H CN Y1 Ms Hi-Pr H CN Y2 Ms Hi-Pr H CN Y3 Ms Hi-Pr H CN COOPh Ms Hi-Pr H CN COOCH.sub.2 Ph Ms Hi-Pr H CN COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H CH.sub.2 OEt COOMe Ms Hi-Pr H CH.sub.2 OEt COOEt Ms Hi-Pr H CH.sub.2 OEt COOCH(CH.sub.3).sub.2 Ms Hi-Pr H CH.sub.2 OEt CONMe.sub.2 Ms Hi-Pr H CH.sub.2 OEt CONEt.sub.2 Ms Hi-Pr H CH.sub.2 OEt COOC.sub.3 H.sub.7 Ms Hi-Pr H CH.sub.2 OEt Y1 Ms Hi-Pr H CH.sub.2 OEt Y2 Ms Hi-Pr H CH.sub.2 OEt Y3 Ms Hi-Pr H CH.sub.2 OEt COOPh Ms Hi-Pr H CH.sub.2 OEt COOCH.sub.2 Ph Ms Hi-Pr H CH.sub.2 OEt COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H Et COOMe Ms Hi-Pr H Et COOEt Ms Hi-Pr H Et COOCH(CH.sub.3).sub.2 Ms Hi-Pr H Et CONMe.sub.2 Ms Hi-Pr H Et CONEt.sub.2 Ms Hi-Pr H Et COOC.sub.3 H.sub.7 Ms Hi-Pr H Et Y1 Ms Hi-Pr H Et Y2 Ms Hi-Pr H Et Y3 Ms Hi-Pr H Et COOPh Ms Hi-Pr H Et COOCH.sub.2 Ph Ms Hi-Pr H Et COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H i-Pr COOMe Ms Hi-Pr H i-Pr COOEt Ms Hi-Pr H i-Pr COOCH(CH.sub.3).sub.2 Ms Hi-Pr H i-Pr CONMe.sub.2 Ms Hi-Pr H i-Pr CONEt.sub.2 Ms Hi-Pr H i-Pr COOC.sub. 3 H.sub.7 Ms Hi-Pr H i-Pr Y1 Ms Hi-Pr H i-Pr Y2 Ms Hi-Pr H i-Pr Y3 Ms Hi-Pr H i-Pr COOPh Ms Hi-Pr H i-Pr COOCH.sub.2 Ph Ms Hi-Pr H i-Pr COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H n-Pr COOMe Ms Hi-Pr H n-Pr COOEt Ms Hi-Pr H n-Pr COOCH(CH.sub.3).sub.2 Ms Hi-Pr H n-Pr CONMe.sub.2 Ms Hi-Pr H n-Pr CONEt.sub.2 Ms Hi-Pr H n-Pr COOC.sub.3 H.sub.7 Ms Hi-Pr H n-Pr Y1 Ms Hi-Pr H n-Pr Y2 Ms Hi-Pr H n-Pr Y3 Ms Hi-Pr H n-Pr COOPh Ms Hi-Pr H n-Pr COOCH.sub.2 Ph Ms Hi-Pr H n-Pr COOCH.sub.2 CHCH.sub.2 Ms Hi-Pr H I COOMe Ms Hi-Pr H I COOEt Ms Hi-Pr H I COOCH(CH.sub.3).sub.2 Ms Hi-Pr H I CONMe.sub.2 Ms Hi-Pr H I CONEt.sub.2 Ms Hi-Pr H I COOC.sub.3 H.sub.7 Ms Hi-Pr H I Y1 Ms Hi-Pr H I Y2 Ms Hi-Pr H I Y3 Ms Hi-Pr H I COOPh Msi-Pr H I COOCH.sub.2 Ph Ms Hi-Pr H I COOCH.sub.2 CHCH.sub.2 Ms Hallyl H NO.sub.2 COOMe Ms Hallyl H NO.sub.2 COOEt Ms Hallyl H NO.sub.2 COOCH(CH.sub.3).sub.2 Ms Hallyl H NO.sub.2 CONMe.sub.2 Ms Hallyl H NO.sub.2 CONEt.sub.2 Ms Hallyl H NO.sub.2 COOC.sub.3 H.sub.7 Ms Hallyl H NO.sub.2 Y1 Ms Hallyl H NO.sub.2 Y2 Ms Hallyl H NO.sub.2 Y3 Ms Hallyl H NO.sub.2 COOPh Ms Hallyl H NO.sub.2 COOCH.sub.2 Ph Ms Hallyl H NO.sub.2 COOCH.sub.2 CHCH.sub.2 Ms Hallyl H CF.sub.3 COOMe Ms Hallyl H CF.sub.3 COOEt Ms Hallyl H CF.sub.3 COOCH(CH.sub.3).sub.2 Ms Hallyl H CF.sub.3 CONMe.sub.2 Ms Hallyl H CF.sub.3 CONEt.sub.2 Ms Hallyl H CF.sub.3 COOC.sub.3 H.sub.7 Ms Hallyl H CF.sub.3 Y1 Ms Hallyl H CF.sub.3 Y2 Ms Hallyl H CF.sub.3 Y3 Ms Hallyl H CF.sub.3 COOPh Ms Hallyl H CF.sub.3 COOCH.sub. 2 Ph Ms Hallyl H CF.sub.3 COOCH.sub.2 CHCH.sub.2 Ms Hallyl H CN COOMe Ms Hallyl H CN COOEt Ms Hallyl H CN COOCH(CH.sub.3).sub.2 Ms Hallyl H CN CONMe.sub.2 Ms Hallyl H CN CONEt.sub.2 Ms Hallyl H CN COOC.sub.3 H.sub.7 Ms Hallyl H CN Y1 Ms Hallyl H CN Y2 Ms Hallyl H CN Y3 Ms Hallyl H CN COOPh Ms Hallyl H CN COOCH.sub.2 Ph Ms Hallyl H CN COOCH.sub.2 CHCH.sub.2 Ms Hallyl H CH.sub.2 OEt COOMe Ms Hallyl H CH.sub.2 OEt COOEt Ms Hallyl H CH.sub.2 OEt COOCH(CH.sub.3).sub.2 Ms Hallyl H CH.sub.2 OEt CONMe.sub.2 Ms Hallyl H CH.sub.2 OEt CONEt.sub.2 Ms Hallyl H CH.sub.2 OEt COOC.sub.3 H.sub.7 Ms Hallyl H CH.sub.2 OEt Y1 Ms Hallyl H CH.sub.2 OEt Y2 Ms Hallyl H CH.sub.2 OEt Y3 Ms Hallyl H CH.sub.2 OEt COOPh Ms Hallyl H CH.sub.2 OEt COOCH.sub.2 Ph Ms Hallyl H CH.sub.2 OEt COOCH.sub.2 CHCH.sub.2 Ms Hallyl H Et COOMe Ms Hallyl H Et COOEt Ms Hallyl H Et COOCH(CH.sub.3).sub.2 Ms Hallyl H Et CONMe.sub.2 Ms Hallyl H Et CONEt.sub.2 Ms Hallyl H Et COOC.sub.3 H.sub.7 Ms Hallyl H Et Y1 Ms Hallyl H Et Y2 Ms Hallyl H Et Y3 Ms Hallyl H Et COOPh Ms Hallyl H Et COOCH.sub.2 Ph Ms Hallyl H Et COOCH.sub.2 CHCH.sub.2 Ms Hallyl H i-Pr COOMe Ms Hallyl H i-Pr COOEt Ms Hallyl H i-Pr COOCH(CH.sub.3).sub.2 Ms Hallyl H i-Pr CONMe.sub.2 Ms Hallyl H i-Pr CONEt.sub.2 Ms Hallyl H i-Pr COOC.sub.3 H.sub.7 Ms Hallyl H i-Pr Y1 Ms Hallyl H i-Pr Y2 Ms Hallyl H i-Pr Y3 Ms Hallyl H i-Pr COOPh Ms Hallyl H i-Pr COOCH.sub.2 Ph Ms Hallyl H i-Pr COOCH.sub.2 CHCH.sub.2 Ms Hallyl H n-Pr COOMe Ms Hallyl H n-Pr COOEt Ms Hallyl H n-Pr COOCH(CH.sub.3 ).sub.2 Ms Hallyl H n-Pr CONMe.sub.2 Ms Hallyl H n-Pr CONEt.sub.2 Ms Hallyl H n-Pr COOC.sub.3 H.sub.7 Ms Hallyl H n-Pr Y1 Ms Hallyl H n-Pr Y2 Ms Hallyl H n-Pr Y3 Ms Hallyl H n-Pr COOPh Ms Hallyl H n-Pr COOCH.sub.2 Ph Ms Hallyl H n-Pr COOCH.sub.2 CHCH.sub.2 Ms Hallyl H I COOMe Ms Hallyl H I COOEt Ms Hallyl H I COOCH(CH.sub.3).sub.2 Ms Hallyl H I CONMe.sub.2 Ms Hallyl H I CONEt.sub.2 Ms Hallyl H I COOC.sub.3 H.sub.7 Ms Hallyl H I Y1 Ms Hallyl H I Y2 Ms Hallyl H I Y3 Ms Hallyl H I COOPh Ms Hallyl H I COOCH.sub.2 Ph Ms Hallyl H I COOCH.sub.2 CHCH.sub.2 Ms Hallyl H Me COOH Ms Hallyl H Cl COOH Ms HMe H Me COOH Ms HMe H Cl COOH Ms HEt H Me COOH Ms HEt H Cl COOH Ms Hi-Pr H Me COOH Ms HI-Pr H Cl COOH Ms HMe H COOMe CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HMe H COOMe CH.sub.2 OCH.sub.2 C CH Ms HMe H COOMe SCH.sub.3 Ms HMe H COOMe CH.sub.2 OH Ms HMe H COOMe CH.sub.2 SCH.sub.3 Ms HEt H COOMe CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HEt H COOMe CH.sub.2 OCH.sub.2 C CH Ms HEt H COOMe SCH.sub.3 Ms HEt H COOMe CH.sub.2 OH Ms HEt H COOMe CH.sub.2 SCH.sub.3 Ms Hi-Pr H COOMe CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms Hi-Pr H COOMe CH.sub.2 OCH.sub.2 C CH Ms Hi-Pr H COOMe SCH.sub.3 Ms Hi-Pr H COOMe CH.sub.2 OH Ms Hi-Pr H COOMe CH.sub.2 SCH.sub.3 Ms HMe H COOEt CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HMe H COOEt CH.sub.2 OCH.sub.2 C CH Ms HMe H COOEt SCH.sub.3 Ms HMe H COOEt CH.sub.2 OH Ms HMe H COOEt CH.sub.2 SCH.sub.3 Ms HEt H COOEt CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HEt H COOEt CH.sub.2 OCH.sub.2 C CH Ms HEt H COOEt SCH.sub.3 Ms HEt H COOEt CH.sub.2 OH Ms HEt H COOEt CH.sub.2 SCH.sub.3 Ms Hi-Pr H COOEt CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms Hi-Pr H COOEt CH.sub.2 OCH.sub.2 C CH Ms Hi-Pr H COOEt SCH.sub.3 Ms Hi-Pr H COOEt CH.sub.2 OH Ms Hi-Pr H COOEt CH.sub.2 SCH.sub.3 Ms HMe H Me COOY4 Ms HMe H Me COOY5 Ms HMe H Me COOY6 Ms HMe H Me COOCH.sub.2 CH.sub.2 Cl Ms HMe H Me COOCH.sub.2 CF.sub.3 Ms HMe H Me COOCH.sub.2 CClCH.sub.2 Ms HMe H Me COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms HMe H Me COOCH.sub.2 SCH.sub.3 Ms HMe H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HMe H Me COOCH.sub.2 CH.sub.2 OMs Ms HMe H Me COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms HMe H Me COOCH.sub.2 CH.sub.2 Ms Ms HMe H Me COOCH.sub.2 CH.sub.2 CN Ms HMe H Me COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms HMe H Me COOCH.sub.2 CH.sub.2 OH Ms HMe H Me COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms HMe H Me COOY7 Ms HMe H Me COOCH.sub.2 COCH.sub.3 Ms HMe H Me COOCH.sub.2 CO.sub.2 CH.sub.3 Ms HMe H Me COOCH(CH.sub.3)COOEt Ms HMe H Me COOCH.sub.2 CH.sub.2 OPh Ms HMe H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms HMe H Me COOPh-4-CH.sub.3 Ms HMe H Me COOPh-4-Cl Ms HMe H Me COOPh-4-NO.sub.2 Ms HMe H Me COOCH.sub.2 SiMe.sub.3 Ms HMe H Me COOY8 Ms HMe H Me COOCH.sub.2 Y8 Ms HMe H Me COOY9 Ms HMe H Me COOY10 Ms HMe H Me CONHSO.sub.2 CH.sub.3 Ms HMe H Me CONHSO.sub.2 CF.sub.3 Ms HMe H Cl COOY4 Ms HMe H Cl COOY5 Ms HMe H Cl COOY6 Ms HMe H Cl COOCH.sub.2 CH.sub.2 Cl Ms HMe H Cl COOCH.sub.2 CF.sub.3 Ms HMe H Cl COOCH.sub.2 CClCH.sub.2 Ms HMe H Cl COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms HMe H Cl COOCH.sub.2 SCH.sub.3 Ms HMe H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HMe H Cl COOCH.sub.2 CH.sub.2 OMs Ms HMe H Cl COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms HMe H Cl COOCH.sub.2 CH.sub.2 Ms Ms HMe H Cl COOCH.sub.2 CH.sub.2 CN Ms HMe H Cl COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms HMe H Cl COOCH.sub.2 CH.sub.2 OH Ms HMe H Cl COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms HMe H Cl COOY7 Ms HMe H Cl COOCH.sub.2 COCH.sub.3 Ms HMe H Cl COOCH.sub.2 CO.sub.2 CH.sub.3 Ms HMe H Cl COOCH(CH.sub.3)COOEt Ms HMe H Cl COOCH.sub.2 CH.sub.2 OPh Ms HMe H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms HMe H Cl COOPh-4-CH.sub.3 Ms HMe H Cl COOPh-4-Cl Ms HMe H Cl COOPh-4-NO.sub.2 Ms HMe H Cl COOCH.sub.2 SiMe.sub.3 Ms HMe H Cl COOY8 Ms HMe H Cl COOCH.sub.2 Y8 Ms HMe H Cl COOY9 Ms HMe H Cl COOY10 Ms HMe H Cl CONHSO.sub.2 CH.sub.3 Ms HMe H Cl CONHSO.sub.2 CF.sub.3 Ms HMe H OMe COOY4 Ms HMe H OMe COOY5 Ms HMe H OMe COOY6 Ms HMe H OMe COOCH.sub.2 CH.sub.2 Cl Ms HMe H OMe COOCH.sub.2 CF.sub.3 Ms HMe H OMe COOCH.sub.2 CClCH.sub.2 Ms HMe H OMe COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms HMe H OMe COOCH.sub.2 SCH.sub.3 Ms HMe H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HMe H OMe COOCH.sub.2 CH.sub. 2 OMs Ms HMe H OMe COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms HMe H OMe COOCH.sub.2 CH.sub.2 Ms Ms HMe H OMe COOCH.sub.2 CH.sub.2 CN Ms HMe H OMe COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms HMe H OMe COOCH.sub.2 CH.sub.2 OH Ms HMe H OMe COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms HMe H OMe COOY7 Ms HMe H OMe COOCH.sub.2 COCH.sub.3 Ms HMe H OMe COOCH.sub.2 CO.sub.2 CH.sub.3 Ms HMe H OMe COOCH(CH.sub.3)COOEt Ms HMe H OMe COOCH.sub.2 CH.sub.2 OPh Ms HMe H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms HMe H OMe COOPh-4-CH.sub.3 Ms HMe H OMe COOPh-4-Cl Ms HMe H OMe COOPh-4-NO.sub.2 Ms HMe H OMe COOCH.sub.2 SiMe.sub.3 Ms HMe H OMe COOY8 Ms HMe H OMe COOCH.sub.2 Y8 Ms HMe H OMe COOY9 Ms HMe H OMe COOY10 Ms HMe H OMe CONHSO.sub.2 CH.sub.3 Ms HMe H OMe CONHSO.sub.2 CF.sub.3 Ms HEt H Me COOY4 Ms HEt H Me COOY5 Ms HEt H Me COOY6 Ms HEt H Me COOCH.sub.2 CH.sub.2 Cl Ms HEt H Me COOCH.sub.2 CF.sub.3 Ms HEt H Me COOCH.sub.2 CClCH.sub.2 Ms HEt H Me COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms HEt H Me COOCH.sub.2 SCH.sub.3 Ms HEt H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HEt H Me COOCH.sub.2 CH.sub.2 OMs Ms HEt H Me COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms HEt H Me COOCH.sub.2 CH.sub.2 Ms Ms HEt H Me COOCH.sub.2 CH.sub.2 CN Ms HEt H Me COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms HEt H Me COOCH.sub.2 CH.sub.2 OH Ms HEt H Me COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms HEt H Me COOY7 Ms HEt H Me COOCH.sub.2 COCH.sub.3 Ms HEt H Me COOCH.sub.2 CO.sub.2 CH.sub.3 Ms HEt H Me COOCH(CH.sub.3)COOEt Ms HEt H Me COOCH.sub.2 CH.sub.2 OPh Ms HEt H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms HEt H Me COOPh-4-CH.sub.3 Ms HEt H Me COOPh-4-Cl Ms HEt H Me COOPh-4-NO.sub.2 Ms HEt H Me COOCH.sub.2 SiMe.sub.3 Ms HEt H Me COOY8 Ms HEt H Me COOCH.sub.2 Y8 Ms HEt H Me COOY9 Ms HEt H Me COOY10 Ms HEt H Me CONHSO.sub.2 CH.sub.3 Ms HEt H Me CONHSO.sub.2 CF.sub.3 Ms HEt H Cl COOY4 Ms HEt H Cl COOY5 Ms HEt H Cl COOY6 Ms HEt H Cl COOCH.sub.2 CH.sub.2 Cl Ms HEt H Cl COOCH.sub.2 CF.sub.3 Ms HEt H Cl COOCH.sub.2 CClCH.sub.2 Ms HEt H Cl COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms HEt H Cl COOCH.sub.2 SCH.sub.3 Ms HEt H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HEt H Cl COOCH.sub.2 CH.sub.2 OMs Ms HEt H Cl COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms HEt H Cl COOCH.sub.2 CH.sub.2 Ms Ms HEt H Cl COOCH.sub.2 CH.sub.2 CN Ms HEt H Cl COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms HEt H Cl COOCH.sub.2 CH.sub.2 OH Ms HEt H Cl COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms HEt H Cl COOY7 Ms HEt H Cl COOCH.sub.2 COCH.sub.3 Ms HEt H Cl COOCH.sub.2 CO.sub.2 CH.sub.3 Ms HEt H Cl COOCH(CH.sub.3)COOEt Ms HEt H Cl COOCH.sub.2 CH.sub.2 OPh Ms HEt H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms HEt H Cl COOPh-4-CH.sub.3 Ms HEt H Cl COOPh-4-Cl Ms HEt H Cl COOPh-4-NO.sub.2 Ms HEt H Cl COOCH.sub.2 SiMe.sub.3 Ms HEt H Cl COOY8 Ms HEt H Cl COOCH.sub.2 Y8 Ms HEt H Cl COOY9 Ms HEt H Cl COOY10 Ms HEt H Cl CONHSO.sub.2 CH.sub.3 Ms HEt H Cl CONHSO.sub.2 CF.sub.3 Ms HEt H OMe COOY4 Ms HEt H OMe COOY5 Ms HEt H OMe COOY6 Ms HEt H OMe COOCH.sub.2 CH.sub.2 Cl Ms HEt H OMe COOCH.sub.2 CF.sub.3 Ms HEt H OMe COOCH.sub.2 CClCH.sub.2 Ms HEt H OMe COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms HEt H OMe COOCH.sub.2 SCH.sub.3 Ms HEt H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HEt H OMe COOCH.sub.2 CH.sub.2 OMs Ms HEt H OMe COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms HEt H OMe COOCH.sub.2 CH.sub.2 Ms Ms HEt H OMe COOCH.sub.2 CH.sub.2 CN Ms HEt H OMe COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms HEt H OMe COOCH.sub.2 CH.sub.2 OH Ms HEt H OMe COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms HEt H OMe COOY7 Ms HEt H OMe COOCH.sub.2 COCH.sub.3 Ms HEt H OMe COOCH.sub.2 CO.sub.2 CH.sub.3 Ms HEt H OMe COOCH(CH.sub.3)COOEt Ms HEt H OMe COOCH.sub.2 CH.sub.2 OPh Ms HEt H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms HEt H OMe COOPh-4-CH.sub.3 Ms HEt H OMe COOPh-4-Cl Ms HEt H OMe COOPh-4-NO.sub.2 Ms HEt H OMe COOCH.sub.2 SiMe.sub.3 Ms HEt H OMe COOY8 Ms HEt H OMe COOCH.sub.2 Y8 Ms HEt H OMe COOY9 Ms HEt H OMe COOY10 Ms HEt H OMe CONHSO.sub.2 CH.sub.3 Ms HEt H OMe CONHSO.sub.2 CF.sub.3 Ms Hi-Pr H Me COOY4 Ms Hi-Pr H Me COOY5 Ms Hi-Pr H Me COOY6 Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 Cl Ms Hi-Pr H Me COOCH.sub.2 CF.sub.3 Ms Hi-Pr H Me COOCH.sub.2 CClCH.sub.2 Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms Hi-Pr H Me COOCH.sub.2 SCH.sub.3 Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 OMs Ms Hi-Pr H Me COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 Ms Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 CN Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms Hi-Pr H Me COOCH.sub. 2 CH.sub.2 OH Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms Hi-Pr H Me COOY7 Ms Hi-Pr H Me COOCH.sub.2 COCH.sub.3 Ms Hi-Pr H Me COOCH.sub.2 CO.sub.2 CH.sub.3 Ms Hi-Pr H Me COOCH(CH.sub.3)COOEt Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 OPh Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms Hi-Pr H Me COOPh-4-CH.sub.3 Ms Hi-Pr H Me COOPh-4-Cl Ms Hi-Pr H Me COOPh-4-NO.sub.2 Ms Hi-Pr H Me COOCH.sub.2 SiMe.sub.3 Ms Hi-Pr H Me COOY8 Ms Hi-Pr H Me COOCH.sub.2 Y8 Ms Hi-Pr H Me COOY9 Ms Hi-Pr H Me COOY10 Ms Hi-Pr H Me CONHSO.sub.2 CH.sub.3 Ms Hi-Pr H Me CONHSO.sub.2 CF.sub.3 Ms Hi-Pr H Cl COOY4 Ms Hi-Pr H Cl COOY5 Ms Hi-Pr H Cl COOY6 Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 Cl Ms Hi-Pr H Cl COOCH.sub.2 CF.sub.3 Ms Hi-Pr H Cl COOCH.sub.2 CClCH.sub.2 Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms Hi-Pr H Cl COOCH.sub.2 SCH.sub.3 Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OMs Ms Hi-Pr H Cl COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 Ms Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 CN Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OH Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms Hi-Pr H Cl COOY7 Ms Hi-Pr H Cl COOCH.sub.2 COCH.sub.3 Ms Hi-Pr H Cl COOCH.sub.2 CO.sub.2 CH.sub.3 Ms Hi-Pr H Cl COOCH(CH.sub.3)COOEt Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OPh Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms Hi-Pr H Cl COOPh-4-CH.sub.3 Ms Hi-Pr H Cl COOPh-4-Cl Ms Hi-Pr H Cl COOPh-4-NO.sub.2 Ms Hi-Pr H Cl COOCH.sub.2 SiMe.sub.3 Ms Hi-Pr H Cl COOY8 Ms Hi-Pr H Cl COOCH.sub.2 Y8 Ms Hi-Pr H Cl COOY9 Ms Hi-Pr H Cl COOY10 Ms Hi-Pr H Cl CONHSO.sub.2 CH.sub.3 Ms Hi-Pr H Cl CONHSO.sub.2 CF.sub.3 Ms Hi-Pr H OMe COOY4 Ms Hi-Pr H OMe COOY5 Ms Hi-Pr H OMe COOY6 Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 Cl Ms Hi-Pr H OMe COOCH.sub.2 CF.sub.3 Ms Hi-Pr H OMe COOCH.sub.2 CClCH.sub.2 Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OCH.sub.3 Ms Hi-Pr H OMe COOCH.sub.2 SCH.sub.3 Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OMs Ms Hi-Pr H OMe COOCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 Ms Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 CN Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 NHCH.sub.3 Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OH Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2 Ms Hi-Pr H OMe COOY7 Ms Hi-Pr H OMe COOCH.sub.2 COCH.sub.3 Ms Hi-Pr H OMe COOCH.sub.2 CO.sub.2 CH.sub.3 Ms Hi-Pr H OMe COOCH(CH.sub.3)COOEt Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OPh Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph Ms Hi-Pr H OMe COOPh-4-CH.sub.3 Ms Hi-Pr H OMe COOPh-4-Cl Ms Hi-Pr H OMe COOPh-4-NO.sub.2 Ms Hi-Pr H OMe COOCH.sub.2 SiMe.sub.3 Ms Hi-Pr H OMe COOY8 Ms Hi-Pr H OMe COOCH.sub.2 Y8 Ms Hi-Pr H OMe COOY9 Ms Hi-Pr H OMe COOY10 Ms Hi-Pr H OMe CONHSO.sub.2 CH.sub.3 Ms Hi-Pr H OMe CONHSO.sub.2 CF.sub.3 Ms HMe H Me CON(CH.sub.3)OCH.sub.3 Ms HMe H Me CONHPh Ms HMe H Me COOCH.sub.2 COC(CH.sub.3).sub.3Me H Me COOCH.sub.2 COPh Ms HMe H Me COOSi(CH.sub.3).sub.3 Ms HMe H Me COONC(CH.sub.3).sub.2 Ms HMe H Me COOY11 Ms HMe H Me COOY12 Ms HMe H Me COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms HMe H Me COOCH.sub. 2 OCOCH.sub.3 Ms HMe H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HMe H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms HMe H OMe CON(CH.sub.3)OCH.sub.3 Ms HMe H OMe CONHPh Ms HMe H OMe COOCH.sub.2 COC(CH.sub.3).sub.3Me H OMe COOCH.sub.2 COPh Ms HMe H OMe COOSi(CH.sub.3).sub.3 Ms HMe H OMe COONC(CH.sub.3).sub.2 Ms HMe H OMe COOY11 Ms HMe H OMe COOY12 Ms HMe H OMe COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms HMe H OMe COOCH.sub.2 OCOCH.sub.3 Ms HMe H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HMe H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms HMe H Cl CON(CH.sub.3)OCH.sub.3 Ms HMe H Cl CONHPh Ms HMe H Cl COOCH.sub.2 COC(CH.sub.3).sub.3Me H Cl COOCH.sub.2 COPh Ms HMe H Cl COOSi(CH.sub.3).sub.3 Ms HMe H Cl COONC(CH.sub.3).sub.2 Ms HMe H Cl COOY11 Ms HMe H Cl COOY12 Ms HMe H Cl COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms HMe H Cl COOCH.sub.2 OCOCH.sub.3 Ms HMe H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HMe H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms HEt H Me CON(CH.sub.3)OCH.sub.3 Ms HEt H Me CONHPh Ms HEt H Me COOCH.sub.2 COC(CH.sub.3).sub.3Et H Me COOCH.sub.2 COPh Ms HEt H Me COOSi(CH.sub.3).sub.3 Ms HEt H Me COONC(CH.sub.3).sub.2 Ms HEt H Me COOY11 Ms HEt H Me COOY12 Ms HEt H Me COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms HEt H Me COOCH.sub.2 OCOCH.sub.3 Ms HEt H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HEt H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms HEt H OMe CON(CH.sub.3)OCH.sub.3 Ms HEt H OMe CONHPh Ms HEt H OMe COOCH.sub.2 COC(CH.sub.3).sub.3Et H OMe COOCH.sub.2 COPh Ms HEt H OMe COOSi(CH.sub.3).sub.3 Ms HEt H OMe COONC(CH.sub.3).sub.2 Ms HEt H OMe COOY11 Ms HEt H OMe COOY12 Ms HEt H OMe COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms HEt H OMe COOCH.sub.2 OCOCH.sub.3 Ms HEt H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HEt H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms HEt H Cl CON(CH.sub.3)OCH.sub.3 Ms HEt H Cl CONHPh Ms HEt H Cl COOCH.sub.2 COC(CH.sub.3).sub.3Et H Cl COOCH.sub.2 COPh Ms HEt H Cl COOSi(CH.sub.3).sub.3 Ms HEt H Cl COONC(CH.sub.3).sub.2 Ms HEt H Cl COOY11 Ms HEt H Cl COOY12 Ms HEt H Cl COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms HEt H Cl COOCH.sub.2 OCOCH.sub.3 Ms HEt H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HEt H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms Hi-Pr H Me CON(CH.sub.3)OCH.sub.3 Ms Hi-Pr H Me CONHPh Ms Hi-Pr H Me COOCH.sub.2 COC(CH.sub.3).sub.3i-Pr H Me COOCH.sub.2 COPh Ms Hi-Pr H Me COOSi(CH.sub.3).sub.3 Ms Hi-Pr H Me COONC(CH.sub.3).sub.2 Ms Hi-Pr H Me COOY11 Ms Hi-Pr H Me COOY12 Ms Hi-Pr H Me COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms Hi-Pr H Me COOCH.sub.2 OCOCH.sub.3 Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms Hi-Pr H Me COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms Hi-Pr H OMe CON(CH.sub.3)OCH.sub.3 Ms Hi-Pr H OMe CONHPh Ms Hi-Pr H OMe COOCH.sub.2 COC(CH.sub.3).sub.3i-Pr H OMe COOCH.sub.2 COPh Ms Hi-Pr H OMe COOSi(CH.sub.3).sub.3 Ms Hi-Pr H OMe COON C(CH.sub.3).sub.2 Ms Hi-Pr H OMe COOY11 Ms Hi-Pr H OMe COOY12 Ms Hi-Pr H OMe COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms Hi-Pr H OMe COOCH.sub.2 OCOCH.sub.3 Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms Hi-Pr H OMe COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms Hi-Pr H Cl CON(CH.sub.3)OCH.sub.3 Ms Hi-Pr H Cl CONHPh Ms Hi-Pr H Cl COOCH.sub.2 COC(CH.sub.3).sub.3i-Pr H Cl COOCH.sub.2 COPh Ms Hi-Pr H Cl COOSi(CH.sub.3).sub.3 Ms Hi-Pr H Cl COONC(CH.sub.3).sub.2 Ms Hi-Pr H Cl COOY11 Ms Hi-Pr H Cl COOY12 Ms Hi-Pr H Cl COOCH.sub.2 OCOC(CH.sub.3).sub.3 Ms Hi-Pr H Cl COOCH.sub.2 OCOCH.sub.3 Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms Hi-Pr H Cl COOCH.sub.2 CH.sub.2 OCH.sub.2 C CH Ms HMe H Me CH.sub.2 OH Ms HMe H Me CH.sub.2 OMe Ms HMe H Me CH.sub.2 OMe Cl HMe H Me CH.sub.2 OMe MeS HMe H Me CH.sub.2 OMe MeSO HMe H Me CH.sub.2 OMe Ms Q1Me H Me CH.sub.2 OMe MeS Q1Me H Me CH.sub.2 OMe MeSO Q1Me H Me CH.sub.2 OMe Ms Q2Me H Me CH.sub.2 OMe MeS Q2Me H Me CH.sub.2 OMe MeSO Q2Me H Me CH.sub.2 OMe Ms Q3Me H Me CH.sub.2 OMe MeS Q3Me H Me CH.sub.2 OMe MeSO Q3Me H Me CH.sub.2 OMe Ms Q4Me H Me CH.sub.2 OMe Ms Q5Me H Me CH.sub.2 OMe Ms Q6Me H Me CH.sub.2 OMe Ms Q7Me H Me CH.sub.2 OMe Ms Q8Me H Me CH.sub.2 OMe Ms Q9Me H Me CH.sub.2 OEt Ms HMe H Me CH.sub.2 OEt Cl HMe H Me CH.sub.2 OEt MeS HMe H Me CH.sub.2 OEt MeSO HMe H Me CH.sub.2 OEt Ms Q1Me H Me CH.sub.2 OEt MeS Q1Me H Me CH.sub.2 OEt MeSO Q1Me H Me CH.sub.2 OEt Ms Q2Me H Me CH.sub.2 OEt MeS Q2Me H Me CH.sub.2 OEt MeSO Q2Me H Me CH.sub.2 OEt Ms Q3Me H Me CH.sub.2 OEt MeS Q3Me H Me CH.sub.2 OEt MeSO Q3Me H Me CH.sub.2 OEt Ms Q4Me H Me CH.sub.2 OEt Ms Q5Me H Me CH.sub.2 OEt Ms Q6Me H Me CH.sub.2 OEt Ms Q7Me H Me CH.sub.2 OEt Ms Q8Me H Me CH.sub.2 OEt Ms Q9Me H Me CH.sub.2 OPr-i Ms HMe H Me CH.sub.2 OPr-i Cl HMe H Me CH.sub.2 OPr-i MeS HMe H Me CH.sub.2 OPr-i MeSO HMe H Me CH.sub.2 OPr-i Ms Q1Me H Me CH.sub.2 OPr-i Ms Q2Me H Me CH.sub.2 OPr-i Ms Q3Me H Me CH.sub.2 OPr-n Ms HMe H Me CH.sub.2 OPr-n Cl HMe H Me CH.sub.2 OPr-n MeS HMe H Me CH.sub.2 OPr-n MeSO HMe H Me CH.sub.2 OCHCH.sub. 2 Ms HMe H Me CH.sub.2 OCHCH.sub.2 Cl HMe H Me CH.sub.2 OCHCH.sub.2 MeS HMe H Me CH.sub.2 OCHCH.sub.2 MeSO HMe H Me CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HMe H Me CH.sub.2 OCH.sub.2 CHCH.sub.2 Cl HMe H Me CH.sub.2 OCH.sub.2 CHCH.sub.2 MeS HMe H Me CH.sub.2 OCH.sub.2 CHCH.sub.2 MeSO HMe H Me CH.sub.2 OCH.sub.2 C CH Ms HMe H Me CH.sub.2 OCH.sub.2 C CH Cl HMe H Me CH.sub.2 OCH.sub.2 C CH MeS HMe H Me CH.sub.2 OCH.sub.2 C CH MeSO HMe H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HMe H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl Cl HMe H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl MeS HMe H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl MeSO HMe H Me CH.sub.2 OCH.sub.2 CH.sub.2 Br Ms HMe H Me CH.sub.2 OCH.sub.2 CH.sub.2 CN Ms HMe H Me CH.sub.2 OAm-n Ms HMe H Me CH.sub.2 O-Y5 Ms HMe H Me CHMeOH Ms HMe H Me CHMeOMe Ms HMe H Me CHMeOMe Cl HMe H Me CHMeOMe MeS HMe H Me CHMeOMe MeSO HMe H Me CHMeOMe Ms Q1Me H Me CHMeOMe Ms Q2Me H Me CHMeOMe Ms Q3Me H Me CHMeOEt Ms HMe H Me CHMeOEt Cl HMe H Me CHMeOEt MeS HMe H Me CHMeOEt MeSO HMe H Me CHMeOEt Ms Q1Me H Me CHMeOEt Ms Q2Me H Me CHMeOEt Ms Q3Me H Me CHMeOPr-i Ms HMe H Me CHMeOPr-i Cl HMe H Me CHMeOPr-i MeS HMe H Me CHMeOPr-i MeSO HMe H Me CHMeOPr-n Ms HMe H Me CHMeOCHCH.sub.2 Ms HMe H Me CHMeOCHCH.sub.2 Ms HMe H Me CHMeOCH.sub.2 CHCH.sub.2 Ms HMe H Me CHMeOCH.sub.2 C CH Ms HMe H Me CHMeOCH.sub.2 CH.sub.2 Cl Ms HMe H Me CHMeO-Y5 Ms HMe H Me CMe.sub.2 OH Ms HMe H Me CMe.sub.2 OMe Ms HMe H Me CMe.sub.2 OMe Cl HMe H Me CMe.sub.2 OMe MeS HMe H Me CMe.sub.2 OMe MeSO HMe H Me CMe.sub.2 OEt Ms HMe H Me CMe.sub.2 OEt Cl HMe H Me CMe.sub.2 OEt MeS HMe H Me CMe.sub.2 OEt MeSO HMe H Me CMe.sub.2 OPr-i Ms HMe H Me CH.sub.2 CH.sub.2 OMe Ms HMe H Me CH.sub.2 CH.sub.2 OMe Cl HMe H Me CH.sub.2 CH.sub.2 OMe MeS HMe H Me CH.sub.2 CH.sub.2 OMe MeSO HMe H Me CH.sub.2 CH.sub.2 OEt Ms HMe H Me CH.sub.2 CH.sub.2 OEt Cl HMe H Me CH.sub.2 CH.sub.2 OEt MeS HMe H Me CH.sub.2 CH.sub.2 OEt MeSO HMe H Me CH.sub.2 CH.sub.2 OPr-i Ms HMe H Me CH.sub.2 CH.sub.2 OPr-i Cl HMe H Me CH.sub.2 CH.sub.2 OPr-i MeS HMe H Me CH.sub.2 CH.sub.2 OPr-i MeSO HMe H Me CHEtOH Ms HMe H Me CHEtOMe Ms HMe H Me CHEtOMe Cl HMe H Me CHEtOMe MeS HMe H Me CHEtOMe MeSO HMe H Me CHEtOEt Ms HMe H Me CHEtOPr-i Ms HMe H Me CH.sub.2 OCH.sub.2 CH.sub.2 OMe Ms 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OCHCH.sub.2 Cl HEt H Me CH.sub.2 OCHCH.sub.2 MeS HEt H Me CH.sub.2 OCHCH.sub.2 MeSO HEt H Me CH.sub.2 OCH.sub.2 CHCH.sub. 2 Ms HEt H Me CH.sub.2 OCH.sub.2 CHCH.sub.2 Cl HEt H Me CH.sub.2 OCH.sub.2 CHCH.sub.2 MeS HEt H Me CH.sub.2 OCH.sub.2 CHCH.sub.2 MeSO HEt H Me CH.sub.2 OCH.sub.2 C CH Ms HEt H Me CH.sub.2 OCH.sub.2 C CH Cl HEt H Me CH.sub.2 OCH.sub.2 C CH MeS HEt H Me CH.sub.2 OCH.sub.2 C CH MeSO HEt H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl Ms HEt H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl Cl HEt H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl MeS HEt H Me CH.sub.2 OCH.sub.2 CH.sub.2 Cl MeSO HEt H Me CH.sub.2 OCH.sub.2 CH.sub.2 Br Ms HEt H Me CH.sub.2 OCH.sub.2 CH.sub.2 CN Ms HEt H Me CH.sub.2 OAm-n Ms HEt H Me CH.sub.2 O-Y5 Ms HEt H Me CHMeOH Ms HEt H Me CHMeOMe Ms HEt H Me CHMeOMe Cl HEt H Me CHMeOMe MeS HEt H Me CHMeOMe MeSO HEt H Me CHMeOMe Ms Q1Et H Me CHMeOMe Ms Q2Et H Me CHMeOMe Ms Q3Et H Me CHMeOEt Ms HEt H Me CHMeOEt Cl HEt H Me CHMeOEt MeS HEt H Me CHMeOEt MeSO HEt H Me CHMeOEt Ms Q1Et H Me 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OCHMeCO.sub.2 Me Ms HEt H Me CH.sub.2 CN Ms HEt H Me CHMeCN Ms HEt H Me CH.sub.2 SMe Ms HEt H Me CH.sub.2 SMe Cl HEt H Me CH.sub.2 SMe MeS HEt H Me CH.sub.2 SMe MeSO HEt H Me CH.sub.2 SEt Ms HEt H Me CH.sub.2 SEt Cl HEt H Me CH.sub.2 SEt MeS HEt H Me CH.sub.2 SEt MeSO HEt H Me CH.sub.2 SOMe Ms HEt H Me CH.sub.2 SOEt Ms HEt H Me CH.sub.2 SO.sub.2 Me Ms HEt H Me CH.sub.2 SO.sub.2 Me Cl HEt H Me CH.sub.2 SO.sub.2 Me MeS HEt H Me CH.sub.2 SO.sub.2 Me MeSO HEt H Me CH.sub.2 SO.sub.2 Et Ms HEt H Me CH.sub.2 SO.sub.2 Et Cl HEt H Me CH.sub.2 SO.sub.2 Et MeS HEt H Me CH.sub.2 SO.sub.2 Et MeSO HEt H Me CHMeSMe Ms HEt H Me CHMeSEt Ms HEt H Me CHMeSO.sub.2 Me Ms HEt H Me CHMeSO.sub.2 Et Ms HEt H Me CH.sub.2 SCH.sub.2 CH.sub.2 OMe Ms HEt H Me CH.sub.2 OCOMe Ms HEt H Me CH.sub.2 OCOEt Ms HEt H Me CHMeOCOMe Ms HEt H Me CH.sub.2 OSO.sub.2 Me Ms HEt H Me CH.sub.2 OSO.sub.2 Et Ms HEt H Me CHMeOSO.sub.2 Me Ms HPr-i H Me CH.sub.2 OH Ms HPr-i H Me CH.sub.2 OMe Ms HPr-i H Me CH.sub.2 OMe Cl HPr-i H Me 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MeSO HPr-i H Me CH.sub.2 OCH.sub.2 CH.sub.2 Br Ms HPr-i H Me CH.sub.2 OCH.sub.2 CH.sub.2 CN Ms HPr-i H Me CH.sub.2 OAm-n Ms HPr-i H Me CH.sub.2 O-Y5 Ms HPr-i H Me CHMeOH Ms HPr-i H Me CHMeOMe Ms HPr-i H Me CHMeOMe Cl HPr-i H Me CHMeOMe MeS HPr-i H Me CHMeOMe MeSO HPr-i H Me CHMeOMe Ms Q1Pr-i H Me CHMeOMe Ms Q2Pr-i H Me CHMeOMe Ms Q3Pr-i H Me CHMeOEt Ms HPr-i H Me CHMeOEt Cl HPr-i H Me CHMeOEt MeS HPr-i H Me CHMeOEt MeSO HPr-i H Me CHMeOEt Ms Q1Pr-i H Me CHMeOEt Ms Q2Pr-i H Me CHMeOEt Ms Q3Pr-i H Me CHMeOPr-i Ms HPr-i H Me CHMeOPr-i Cl HPr-i H Me CHMeOPr-i MeS HPr-i H Me CHMeOPr-i MeSO HPr-i H Me CHMeOPr-n Ms HPr-i H Me CHMeOCHCH.sub.2 Ms HPr-i H Me CHMeOCHCH.sub.2 Ms HPr-i H Me CHMeOCH.sub.2 CHCH.sub.2 Ms HPr-i H Me CHMeOCH.sub.2 C CH Ms HPr-i H Me CHMeOCH.sub.2 CH.sub.2 Cl Ms HPr-i H Me CHMeO-Y5 Ms HPr-i H Me CMe.sub.2 OH Ms HPr-i H Me CMe.sub.2 OMe Ms HPr-i H Me CMe.sub.2 OMe Cl HPr-i H Me CMe.sub.2 OMe MeS HPr-i H Me CMe.sub.2 OMe MeSO HPr-i H Me CMe.sub.2 OEt Ms HPr-i H Me 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OMe Ms HEt H Cl CH.sub.2 OMe Cl HEt H Cl CH.sub.2 OMe MeS HEt H Cl CH.sub.2 OMe MeSO HEt H Cl CH.sub.2 OMe Ms Q1Et H Cl CH.sub.2 OMe MeS Q1Et H Cl CH.sub.2 OMe MeSO Q1Et H Cl CH.sub.2 OMe Ms Q2Et H Cl CH.sub.2 OMe MeS Q2Et H Cl CH.sub.2 OMe MeSO Q2Et H Cl CH.sub.2 OMe Ms Q3Et H Cl CH.sub.2 OMe MeS Q3Et H Cl CH.sub.2 OMe MeSO Q3Et H Cl CH.sub.2 OMe Ms Q4Et H Cl CH.sub.2 OMe Ms Q5Et H Cl CH.sub.2 OMe Ms Q6Et H Cl CH.sub.2 OMe Ms Q7Et H Cl CH.sub.2 OMe Ms Q8Et H Cl CH.sub.2 OMe Ms Q9Et H Cl CH.sub.2 OEt Ms HEt H Cl CH.sub.2 OEt Cl HEt H Cl CH.sub.2 OEt MeS HEt H Cl CH.sub.2 OEt MeSO HEt H Cl CH.sub.2 OEt Ms Q1Et H Cl CH.sub.2 OEt MeS Q1Et H Cl CH.sub.2 OEt MeSO Q1Et H Cl CH.sub.2 OEt Ms Q2Et H Cl CH.sub.2 OEt MeS Q2Et H Cl CH.sub.2 OEt MeSO Q2Et H Cl CH.sub.2 OEt Ms Q3Et H Cl CH.sub.2 OEt MeS Q3Et H Cl CH.sub.2 OEt MeSO Q3Et H Cl CH.sub.2 OEt Ms Q4Et H Cl CH.sub.2 OEt Ms Q5Et H Cl CH.sub.2 OEt Ms Q6Et H Cl CH.sub.2 OEt Ms Q7Et H Cl CH.sub.2 OEt Ms Q8Et H Cl CH.sub.2 OEt Ms Q9Et H Cl 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OEt MeS Q2Pr-i H Cl CH.sub.2 OEt MeSO Q2Pr-i H Cl CH.sub.2 OEt Ms Q3Pr-i H Cl CH.sub.2 OEt MeS Q3Pr-i H Cl CH.sub.2 OEt MeSO Q3Pr-i H Cl CH.sub.2 OEt Ms Q4Pr-i H Cl CH.sub.2 OEt Ms Q5Pr-i H Cl CH.sub.2 OEt Ms Q6Pr-i H Cl CH.sub.2 OEt Ms Q7Pr-i H Cl CH.sub.2 OEt Ms Q8Pr-i H Cl CH.sub.2 OEt Ms Q9Pr-i H Cl CH.sub.2 OPr-i Ms HPr-i H Cl CH.sub.2 OPr-i Cl HPr-i H Cl CH.sub.2 OPr-i MeS HPr-i H Cl CH.sub.2 OPr-i MeSO HPr-i H Cl CH.sub.2 OPr-i Ms Q1Pr-i H Cl CH.sub.2 OPr-i Ms Q2Pr-i H Cl CH.sub.2 OPr-i Ms Q3Pr-i H Cl CH.sub.2 OPr-n Ms HPr-i H Cl CH.sub.2 OPr-n Cl HPr-i H Cl CH.sub.2 OPr-n MeS HPr-i H Cl CH.sub.2 OPr-n MeSO HPr-i H Cl CH.sub.2 OCHCH.sub.2 Ms HPr-i H Cl CH.sub.2 OCHCH.sub.2 Cl HPr-i H Cl CH.sub.2 OCHCH.sub.2 MeS HPr-i H Cl CH.sub.2 OCHCH.sub.2 MeSO HPr-i H Cl CH.sub.2 OCH.sub.2 CHCH.sub.2 Ms HPr-i H Cl CH.sub.2 OCH.sub.2 CHCH.sub.2 Cl HPr-i H Cl CH.sub.2 OCH.sub.2 CHCH.sub.2 MeS HPr-i H Cl CH.sub.2 OCH.sub.2 CHCH.sub.2 MeSO HPr-i H Cl CH.sub.2 OCH.sub.2 C CH Ms HPr-i H Cl 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HPr-i H Cl CHMeOCH.sub.2 C CH Ms HPr-i H Cl CHMeOCH.sub.2 CH.sub.2 Cl Ms HPr-i H Cl CHMeO-Y5 Ms HPr-i H Cl CMe.sub.2 OH Ms HPr-i H Cl CMe.sub.2 OMe Ms HPr-i H Cl CMe.sub.2 OMe Cl HPr-i H Cl CMe.sub.2 OMe MeS HPr-i H Cl CMe.sub.2 OMe MeSO HPr-i H Cl CMe.sub.2 OEt Ms HPr-i H Cl CMe.sub.2 OEt Cl HPr-i H Cl CMe.sub.2 OEt MeS HPr-i H Cl CMe.sub.2 OEt MeSO HPr-i H Cl CMe.sub.2 OPr-i Ms HPr-i H Cl CH.sub.2 CH.sub.2 OMe Ms HPr-i H Cl CH.sub.2 CH.sub.2 OMe Cl HPr-i H Cl CH.sub.2 CH.sub.2 OMe MeS HPr-i H Cl CH.sub.2 CH.sub.2 OMe MeSO HPr-i H Cl CH.sub.2 CH.sub.2 OEt Ms HPr-i H Cl CH.sub.2 CH.sub.2 OEt Cl HPr-i H Cl CH.sub.2 CH.sub.2 OEt MeS HPr-i H Cl CH.sub.2 CH.sub.2 OEt MeSO HPr-i H Cl CH.sub.2 CH.sub.2 OPr-i Ms HPr-i H Cl CH.sub.2 CH.sub.2 OPr-i Cl HPr-i H Cl CH.sub.2 CH.sub.2 OPr-i MeS HPr-i H Cl CH.sub.2 CH.sub.2 OPr-i MeSO HPr-i H Cl CHEtOH Ms HPr-i H Cl CHEtOMe Ms HPr-i H Cl CHEtOMe Cl HPr-i H Cl CHEtOMe MeS HPr-i H Cl CHEtOMe MeSO HPr-i H Cl CHEtOEt Ms HPr-i H Cl CHEtOPr-i Ms HPr-i H Cl 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CMe.sub.2 OEt MeSO HMe H MeO CMe.sub.2 OPr-i Ms HMe H MeO CH.sub.2 CH.sub.2 OMe Ms HMe H MeO CH.sub.2 CH.sub.2 OMe Cl HMe H MeO CH.sub.2 CH.sub.2 OMe MeS HMe H MeO CH.sub.2 CH.sub.2 OMe MeSO HMe H MeO CH.sub.2 CH.sub.2 OEt Ms HMe H MeO CH.sub.2 CH.sub.2 OEt Cl HMe H MeO CH.sub.2 CH.sub.2 OEt MeS HMe H MeO CH.sub.2 CH.sub.2 OEt MeSO HMe H MeO CH.sub.2 CH.sub.2 OPr-i Ms HMe H MeO CH.sub.2 CH.sub.2 OPr-i Cl HMe H MeO CH.sub.2 CH.sub.2 OPr-i MeS HMe H MeO CH.sub.2 CH.sub.2 OPr-i MeSO HMe H MeO CHEtOH Ms HMe H MeO CHEtOMe Ms HMe H MeO CHEtOMe Cl HMe H MeO CHEtOMe MeS HMe H MeO CHEtOMe MeSO HMe H MeO CHEtOEt Ms HMe H MeO CHEtOPr-i Ms HMe H MeO CH.sub.2 OCH.sub.2 CH.sub.2 OMe Ms HMe H MeO CH.sub.2 OCH.sub.2 CH.sub.2 OMe Cl HMe H MeO CH.sub.2 OCH.sub.2 CH.sub.2 OMe MeS HMe H MeO CH.sub.2 OCH.sub.2 CH.sub.2 OMe MeSO HMe H MeO CH.sub.2 OCH.sub.2 CH.sub.2 OEt Ms HMe H MeO CHMeOCH.sub.2 CH.sub.2 OMe Ms HMe H MeO CH.sub.2 O-Y8 Ms HMe H MeO CH.sub.2 O-Y9 Ms HMe H MeO CH.sub.2 O-Y10 Ms HMe H MeO CHMeO-Y8 Ms HMe H MeO CHMeO-Y9 Ms HMe H MeO CHMeO-Y10 Ms HMe H MeO CH.sub.2 O-Y13 Ms HMe H MeO CHMeO-Y13 Ms HMe H MeO CH.sub.2 NHMe Ms HMe H MeO CH.sub.2 NMe.sub.2 Ms HMe H MeO Ch.sub.2 NEtMe Ms HMe H MeO CH.sub.2 NEt.sub.2 Ms HMe H MeO CH.sub.2 -Y14 Ms HMe H MeO CHMeNMe.sub.2 Ms HMe H MeO CH.sub.2 CH.sub.2 NMe.sub.2 Ms HMe H MeO CH.sub.2 OCH.sub.2 Ph Ms HMe H MeO CHMeOCH.sub.2 Ph Ms HMe H MeO CH.sub.2 OCH.sub.2 CO.sub.2 Me Ms HMe H MeO CH.sub.2 OCH.sub.2 CO.sub.2 Et Ms HMe H MeO CH.sub.2 OCHMeCO.sub.2 Me Ms HMe H MeO CH.sub.2 CN Ms HMe H MeO CHMeCN Ms HMe H MeO CH.sub.2 SMe Ms HMe H MeO CH.sub.2 SMe Cl HMe H MeO CH.sub.2 SMe MeS HMe H MeO CH.sub.2 SMe MeSO HMe H MeO CH.sub.2 SEt Ms HMe H MeO CH.sub.2 SEt Cl HMe H MeO CH.sub.2 SEt MeS HMe H MeO CH.sub.2 SEt MeSO HMe H MeO CH.sub.2 SOMe Ms HMe H MeO CH.sub.2 SOEt Ms HMe H MeO CH.sub.2 SO.sub.2 Me Ms HMe H MeO CH.sub. 2 SO.sub.2 Me Cl HMe H MeO CH.sub.2 SO.sub.2 Me MeS HMe H MeO CH.sub.2 SO.sub.2 Me MeSO HMe H MeO CH.sub.2 SO.sub.2 Et Ms HMe H MeO CH.sub.2 SO.sub.2 Et Cl HMe H MeO CH.sub.2 SO.sub.2 Et MeS HMe H MeO CH.sub.2 SO.sub.2 Et MeSO HMe H MeO CHMeSMe Ms HMe H MeO CHMeSEt Ms HMe H MeO CHMeSO.sub.2 Me Ms HMe H MeO CHMeSO.sub.2 Et Ms HMe H MeO CH.sub.2 SCH.sub.2 CH.sub.2 OMe Ms HMe H MeO CH.sub.2 OCOMe Ms HMe H MeO CH.sub.2 OCOEt Ms HMe H MeO CHMeOCOMe Ms HMe H MeO CH.sub.2 OSO.sub.2 Me Ms HMe H MeO CH.sub.2 OSO.sub.2 Et Ms HMe H MeO CHMeOSO.sub.2 Me Ms HEt H MeO CH.sub.2 OH Ms HEt H MeO CH.sub.2 OMe Ms HEt H MeO CH.sub.2 OMe Cl HEt H MeO CH.sub.2 OMe MeS HEt H MeO CH.sub.2 OMe MeSO HEt H MeO CH.sub. 2 OMe Ms Q1Et H MeO CH.sub.2 OMe MeS Q1Et H MeO CH.sub.2 OMe MeSO Q1Et H MeO CH.sub.2 OMe Ms Q2Et H MeO CH.sub.2 OMe MeS Q2Et H MeO CH.sub.2 OMe MeSO Q2Et H MeO CH.sub.2 OMe Ms Q3Et H MeO CH.sub.2 OMe MeS Q3Et H MeO CH.sub.2 OMe MeSO Q3Et H MeO CH.sub.2 OMe Ms Q4Et H MeO CH.sub.2 OMe Ms Q5Et H MeO CH.sub.2 OMe Ms Q6Et H MeO CH.sub.2 OMe Ms Q7Et H MeO CH.sub.2 OMe Ms Q8Et H MeO CH.sub.2 OMe Ms Q9Et H MeO CH.sub.2 OEt Ms HEt H MeO CH.sub.2 OEt Cl HEt H MeO CH.sub.2 OEt MeS HEt H MeO CH.sub.2 OEt MeSO HEt H MeO CH.sub.2 OEt Ms Q1Et H MeO CH.sub.2 OEt MeS Q1Et H MeO CH.sub.2 OEt MeSO Q1Et H MeO CH.sub.2 OEt Ms Q2Et H MeO CH.sub.2 OEt MeS Q2Et H MeO CH.sub.2 OEt MeSO Q2Et H MeO CH.sub. 2 OEt Ms Q3Et H MeO CH.sub.2 OEt MeS Q3Et H MeO CH.sub.2 OEt MeSO Q3Et H MeO CH.sub.2 OEt Ms Q4Et H MeO CH.sub.2 OEt Ms Q5Et H MeO CH.sub.2 OEt Ms Q6Et H MeO CH.sub.2 OEt Ms Q7Et H MeO CH.sub.2 OEt Ms Q8Et H MeO CH.sub.2 OEt Ms Q9Et H MeO CH.sub.2 OPr-i Ms HEt H MeO CH.sub.2 OPr-i Cl HEt H MeO CH.sub.2 OPr-i MeS HEt H MeO CH.sub.2 OPr-i MeSO HEt H MeO CH.sub.2 OPr-i Ms Q1Et H MeO CH.sub.2 OPr-i Ms Q2Et H MeO CH.sub.2 OPr-i Ms Q3Et H MeO CH.sub.2 OPr-n Ms HEt H MeO CH.sub.2 OPr-n Cl HEt H MeO CH.sub.2 OPr-n MeS HEt H MeO CH.sub.2 OPr-n MeSO HEt H MeO CH.sub.2 OCHCH.sub.2 Ms HEt H MeO CH.sub.2 OCHCH.sub.2 Cl HEt H MeO CH.sub.2 OCHCH.sub.2 MeS HEt H MeO CH.sub.2 OCHCH.sub.2 MeSO HEt H MeO CH.sub. 2 OCH.sub.2 CHCH.sub.2 Ms 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COCH.sub.3 CHMeOMe Ms HPr-i H COCH.sub.3 CH.sub.2 OMe Ms HPr-i H COCH.sub.3 CH.sub.2 OEt Ms HMe Me COCH.sub.3 CH.sub.2 OMe Ms HEt Me COCH.sub.3 CH.sub.2 OMe Ms HEt Me COCH.sub.3 CH.sub.2 OEt Ms HPr-i Me COCH.sub.3 CH.sub.2 OMe Ms HMe H SCH.sub.3 CH.sub.2 OMe Ms HMe H SCH.sub.3 CH.sub.2 OEt Ms HEt H SCH.sub.3 CH.sub.2 OMe Ms HEt H SCH.sub.3 CH.sub.2 OEt Ms HEt H SCH.sub.3 CHMeOEt Ms HPr-i H SCH.sub.3 CH.sub.2 OMe Ms HMe Me SCH.sub.3 CH.sub.2 OMe Ms HEt Me SCH.sub.3 CH.sub.2 OMe Ms HEt Me SCH.sub.3 CH.sub.2 OEt Ms HPr-i Me SCH.sub.3 CH.sub.2 OMe Ms HMe H OCHF.sub.2 CH.sub.2 OMe Ms HMe H OCHF.sub.2 CH.sub.2 OEt Ms HEt H OCHF.sub.2 CH.sub.2 OMe Ms HEt H OCHF.sub.2 CH.sub.2 OEt Ms HEt H OCHF.sub.2 CHMeOEt Ms HPr-i H OCHF.sub.2 CH.sub.2 OMe Ms HPr-i H OCHF.sub.2 CH.sub.2 OEt Ms HMe Me OCHF.sub.2 CH.sub.2 OMe Ms HMe Me OCHF.sub.2 CH.sub.2 OEt Ms HEt Me OCHF.sub.2 CH.sub.2 OMe Ms HEt Me OCHF.sub.2 CH.sub.2 OEt Ms HPr-i Me OCHF.sub.2 CH.sub.2 OMe Ms HPr-i Me OCHF.sub.2 CH.sub.2 OEt Ms HMe H OCF.sub.3 CH.sub.2 OMe Ms HMe H OCF.sub.3 CH.sub.2 OEt Ms HEt H OCF.sub.3 CH.sub.2 OMe Ms HEt H OCF.sub.3 CH.sub.2 OEt Ms HEt H OCF.sub.3 CHMeOEt Ms HPr-i H OCF.sub.3 CH.sub.2 OMe Ms HPr-i H OCF.sub.3 CH.sub.2 OEt Ms HMe Me OCF.sub.3 CH.sub.2 OMe Ms HEt Me OCF.sub.3 CH.sub.2 OMe Ms HEt Me OCF.sub.3 CH.sub.2 OEt Ms HPr-i Me OCF.sub.3 CH.sub.2 OMe Ms HMe H CH.sub.2 SMe CH.sub.2 OMe Ms HEt H CH.sub.2 SMe CH.sub.2 OMe Ms HEt H CH.sub.2 SMe CH.sub.2 OEt Ms HEt H CH.sub.2 SMe CHMeOEt Ms HPr-i H CH.sub.2 SMe CH.sub.2 OMe Ms HPr-i H CH.sub.2 SMe CHMeOMe Ms HMe Me CH.sub.2 SMe CH.sub.2 OMe Ms HEt Me CH.sub.2 SMe CH.sub.2 OMe Ms HEt Me CH.sub.2 SMe CH.sub.2 OEt Ms HPr-i Me CH.sub.2 SMe CH.sub.2 OMe Ms HMe H CN CH.sub.2 OMe Ms HEt H CN CH.sub.2 OMe Ms HEt H CN CH.sub.2 OEt Ms HPr-i H CN CH.sub.2 OMe Ms HMe Me CN CH.sub.2 OMe Ms HEt Me CN CH.sub.2 OMe Ms HPr-i Me CN CH.sub.2 OMe Ms HMe H CO.sub.2 Me CH.sub.2 OMe Ms HEt H CO.sub.2 Me CH.sub.2 OMe Ms HEt H CO.sub.2 Me CH.sub.2 OEt Ms HPr-i H CO.sub.2 Me CH.sub.2 OMe Ms HMe Me CO.sub.2 Me CH.sub.2 OMe Ms HEt Me CO.sub.2 Me CH.sub.2 OMe Ms HPr-i Me CO.sub.2 Me CH.sub.2 OMe Ms HMe H CONMe.sub.2 CH.sub.2 OMe Ms HEt H CONMe.sub.2 CH.sub.2 OMe Ms HPr-i H CONMe.sub.2 CH.sub.2 OMe Ms HMe H Me CH.sub.2 OMe NO.sub.2 HMe H Me CH.sub.2 OEt NO.sub.2 HEt H Me CH.sub.2 OMe NO.sub.2 HEt H Me CH.sub.2 OEt NO.sub.2 HEt H Me CHMeOMe NO.sub.2 HPr-i H Me CH.sub.2 OMe NO.sub.2 HPr-i H Me CH.sub.2 OEt NO.sub.2 HMe H Cl CH.sub.2 OMe NO.sub.2 HMe H Cl CH.sub.2 OEt NO.sub.2 HEt H Cl CH.sub.2 OMe NO.sub.2 HEt H Cl CH.sub.2 OEt NO.sub.2 HEt H Cl CHMeOMe NO.sub.2 HPr-i H Cl CH.sub.2 OMe NO.sub.2 HPr-i H Cl CH.sub.2 OEt NO.sub.2 HMe Me Me CH.sub.2 OMe NO.sub.2 HEt Me Me CH.sub.2 OMe NO.sub.2 HEt Me Me CH.sub.2 OEt NO.sub.2 HPr-i Me Me CH.sub.2 OMe NO.sub.2 HMe Me Cl CH.sub.2 OMe NO.sub.2 HEt Me Cl CH.sub.2 OMe NO.sub.2 HEt Me Cl CH.sub.2 OEt NO.sub. 2 HEt Me Cl CHMeOMe NO.sub.2 HPr-i Me Cl CH.sub.2 OMe NO.sub.2 HMe H Me CH.sub.2 OMe CF.sub.3 HMe H Me CH.sub.2 OEt CF.sub.3 HEt H Me CH.sub.2 OMe CF.sub.3 HEt H Me CH.sub.2 OEt CF.sub.3 HEt H Me CHMeOMe CF.sub.3 HPr-i H Me CH.sub.2 OMe CF.sub.3 HPr-i H Me CH.sub.2 OEt CF.sub.3 HMe H Cl CH.sub.2 OMe CF.sub.3 HMe H Cl CH.sub.2 OEt CF.sub.3 HEt H Cl CH.sub.2 OMe CF.sub.3 HEt H Cl CH.sub.2 OEt CF.sub.3 HEt H Cl CHMeOMe CF.sub.3 HPr-i H Cl CH.sub.2 OMe CF.sub.3 HPr-i H Cl CH.sub.2 OEt CF.sub.3 HMe Me Me CH.sub.2 OMe CF.sub.3 HEt Me Me CH.sub.2 OMe CF.sub.3 HEt Me Me CH.sub.2 OEt CF.sub.3 HPr-i Me Me CH.sub.2 OMe CF.sub.3 HMe Me Cl CH.sub.2 OMe CF.sub.3 HEt Me Cl CH.sub.2 OMe CF.sub.3 HEt Me Cl CH.sub.2 OEt CF.sub.3 HEt Me Cl CHMeOMe CF.sub.3 HPr-i Me Cl CH.sub.2 OMe CF.sub.3 HMe H Me CH.sub.2 OMe CN HMe H Me CH.sub.2 OEt CN HEt H Me CH.sub.2 OMe CN HEt H Me CH.sub.2 OEt CN HEt H Me CHMeOMe CN HPr-i H Me CH.sub.2 OMe CN HPr-i H Me CH.sub.2 OEt CN HMe H Cl CH.sub.2 OMe CN HMe H Cl CH.sub.2 OEt CN HEt H Cl CH.sub.2 OMe CN HEt H Cl CH.sub.2 OEt CN HEt H Cl CHMeOMe CN HPr-i H Cl CH.sub.2 OMe CN HPr-i H Cl CH.sub.2 OEt CN HMe Me Me CH.sub.2 OMe CN HEt Me Me CH.sub.2 OMe CN HEt Me Me CH.sub.2 OEt CN HPr-i Me Me CH.sub.2 OMe CN HMe Me Cl CH.sub.2 OMe CN HEt Me Cl CH.sub.2 OMe CN HEt Me Cl CH.sub.2 OEt CN HEt Me Cl CHMeOMe CN HPr-i Me Cl CH.sub.2 OMe CN HMe H Me CH.sub.2 OMe OMe HMe H Me CH.sub.2 OEt OMe HEt H Me CH.sub.2 OMe OMe HEt H Me CH.sub.2 OEt OMe HEt H Me CHMeOMe OMe HPr-i H Me CH.sub.2 OMe OMe HPr-i H Me CH.sub.2 OEt OMe HMe H Cl CH.sub.2 OMe OMe HMe H Cl CH.sub.2 OEt OMe HEt H Cl CH.sub.2 OMe OMe HEt H Cl CH.sub.2 OEt OMe HEt H Cl CHMeOMe OMe HPr-i H Cl CH.sub.2 OMe OMe HPr-i H Cl CH.sub.2 OEt OMe HMe Me Me CH.sub.2 OMe OMe HEt Me Me CH.sub.2 OMe OMe HEt Me Me CH.sub.2 OEt OMe HPr-i Me Me CH.sub.2 OMe OMe HMe Me Cl CH.sub.2 OMe OMe HEt Me Cl CH.sub.2 OMe OMe HEt Me Cl CH.sub.2 OEt OMe HEt Me Cl CHMeOMe OMe HPr-i Me Cl CH.sub.2 OMe OMe HMe H Me CH.sub.2 OMe Br HMe H Me CH.sub.2 OEt Br HEt H Me CH.sub.2 OMe Br HEt H Me CH.sub.2 OEt Br HEt H Me CHMeOMe Br HPr-i H Me CH.sub.2 OMe Br HPr-i H Me CH.sub.2 OEt Br HMe H Cl CH.sub.2 OMe Br HMe H Cl CH.sub.2 OEt Br HEt H Cl CH.sub.2 OMe Br HEt H Cl CH.sub.2 OEt Br HEt H Cl CHMeOMe Br HPr-i H Cl CH.sub.2 OMe Br HPr-i H Cl CH.sub.2 OEt Br HMe Me Me CH.sub.2 OMe Br HEt Me Me CH.sub.2 OMe Br HEt Me Me CH.sub.2 OEt Br HPr-i Me Me CH.sub.2 OMe Br HMe Me Cl CH.sub.2 OMe Br HEt Me Cl CH.sub.2 OMe Br HEt Me Cl CH.sub.2 OEt Br HEt Me Cl CHMeOMe Br HPr-i Me Cl CH.sub.2 OMe Br HMe H Me CH.sub.2 OMe I HMe H Me CH.sub.2 OEt I HEt H Me CH.sub.2 OMe I HEt H Me CH.sub.2 OEt I HEt H Me CHMeOMe I HPr-i H Me CH.sub.2 OMe I HPr-i H Me CH.sub.2 OEt I HMe H Cl CH.sub.2 OMe I HMe H Cl CH.sub.2 OEt I HEt H Cl CH.sub.2 OMe I HEt H Cl CH.sub.2 OEt I HEt H Cl CHMeOMe I HPr-i H Cl CH.sub.2 OMe I HPr-i H Cl CH.sub.2 OEt I HMe Me Me CH.sub.2 OMe I HEt Me Me CH.sub.2 OMe I HEt Me Me CH.sub.2 OEt I HPr-i Me Me CH.sub.2 OMe I HMe Me Cl CH.sub.2 OMe I HEt Me Cl CH.sub.2 OMe I HEt Me Cl CH.sub.2 OEt I HEt Me Cl CHMeOMe I HPr-i Me Cl CH.sub.2 OMe I HMe H Me CH.sub.2 OMe SCF.sub.3 HMe H Me CH.sub.2 OEt SCF.sub.3 HEt H Me CH.sub.2 OMe SCF.sub.3 HEt H Me CH.sub.2 OEt SCF.sub.3 HEt H Me CHMeOMe SCF.sub.3 HPr-i H Me CH.sub.2 OMe SCF.sub.3 HPr-i H Me CH.sub.2 OEt SCF.sub.3 HMe H Cl CH.sub.2 OMe SCF.sub.3 HMe H Cl CH.sub.2 OEt SCF.sub.3 HEt H Cl CH.sub.2 OMe SCF.sub.3 HEt H Cl CH.sub.2 OEt SCF.sub.3 HEt H Cl CHMeOMe SCF.sub.3 HPr-i H Cl CH.sub.2 OMe SCF.sub.3 HPr-i H Cl CH.sub.2 OEt SCF.sub.3 HMe Me Me CH.sub.2 OMe SCF.sub.3 HEt Me Me CH.sub.2 OMe SCF.sub.3 HEt Me Me CH.sub.2 OEt SCF.sub.3 HPr-i Me Me CH.sub.2 OMe SCF.sub.3 HMe Me Cl CH.sub.2 OMe SCF.sub.3 HEt Me Cl CH.sub.2 OMe SCF.sub.3 HEt Me Cl CH.sub.2 OEt SCF.sub.3 HEt Me Cl CHMeOMe SCF.sub.3 HPr-i Me Cl CH.sub.2 OMe SCF.sub.3 HMe H Me CH.sub.2 OMe SO.sub.2 CF.sub.3 HMe H Me CH.sub.2 OEt SO.sub.2 CF.sub.3 HEt H Me CH.sub.2 OMe SO.sub.2 CF.sub.3 HEt H Me CH.sub.2 OEt SO.sub.2 CF.sub.3 HEt H Me CHMeOMe SO.sub.2 CF.sub.3 HPr-i H Me CH.sub.2 OMe SO.sub.2 CF.sub.3 HPr-i H Me CH.sub. 2 OEt SO.sub.2 CF.sub.3 HMe H Cl CH.sub.2 OMe SO.sub.2 CF.sub.3 HMe H Cl CH.sub.2 OEt SO.sub.2 CF.sub.3 HEt H Cl CH.sub.2 OMe SO.sub.2 CF.sub.3 HEt H Cl CH.sub.2 OEt SO.sub.2 CF.sub.3 HEt H Cl CHMeOMe SO.sub.2 CF.sub.3 HPr-i H Cl CH.sub.2 OMe SO.sub.2 CF.sub.3 HPr-i H Cl CH.sub.2 OEt SO.sub.2 CF.sub.3 HMe Me Me CH.sub.2 OMe SO.sub.2 CF.sub.3 HEt Me Me CH.sub.2 OMe SO.sub.2 CF.sub.3 HEt Me Me CH.sub.2 OEt SO.sub.2 CF.sub.3 HPr-i Me Me CH.sub.2 OMe SO.sub.2 CF.sub.3 HMe Me Cl CH.sub.2 OMe SO.sub.2 CF.sub.3 HEt Me Cl CH.sub.2 OMe SO.sub.2 CF.sub.3 HEt Me Cl CH.sub.2 OEt SO.sub.2 CF.sub.3 HEt Me Cl CHMeOMe SO.sub.2 CF.sub.3 HPr-i Me Cl CH.sub.2 OMe SO.sub.2 CF.sub.3 HMe H Me COOMe Ms NaMe H Me COOMe Ms KMe H Me COOMe Ms Ca.sub.1/2Me H Me COOMe Ms Mg.sub.1/2Me H Me COOMe Ms EtN.sup.+ H.sub.3Me H Me COOMe Ms i-PrN.sup.+ H.sub.3Me H Me COOMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Me COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me COOMe Ms NaEt H Me COOMe Ms KEt H Me COOMe Ms Ca.sub.1/2Et H Me COOMe Ms Mg.sub.1/2Et H Me COOMe Ms EtN.sup.+ H.sub.3Et H Me COOMe Ms i-PrN.sup.+ H.sub.3Et H Me COOMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Me COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me COOMe Ms Nai-Pr H Me COOMe Ms Ki-Pr H Me COOMe Ms Ca.sub.1/2i-Pr H Me COOMe Ms Mg.sub.1/2i-Pr H Me COOMe Ms EtN.sup.+ H.sub.3i-Pr H Me COOMe Ms i-PrN.sup.+ H.sub.3i-Pr H Me COOMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Me COOMe Ms i-PrN.sup.+ H.sub.3Et Me Me COOMe Ms NaEt Me Me COOMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Me COOMe Ms i-PrN.sup.+ H.sub.3Me H Cl COOMe Ms NaMe H Cl COOMe Ms KMe H Cl COOMe Ms Ca.sub.1/2Me H Cl COOMe Ms Mg.sub.1/2Me H Cl COOMe Ms EtN.sup.+ H.sub.3Me H Cl COOMe Ms i-PrN.sup.+ H.sub.3Me H Cl COOMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl COOMe Ms NaEt H Cl COOMe Ms KEt H Cl COOMe Ms Ca.sub.1/2Et H Cl COOMe Ms Mg.sub.1/2Et H Cl COOMe Ms EtN.sup.+ H.sub.3Et H Cl COOMe Ms i-PrN.sup.+ H.sub.3Et H Cl COOMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Cl COOMe Ms Nai-Pr H Cl COOMe Ms Ki-Pr H Cl COOMe Ms Ca.sub.1/2i-Pr H Cl COOMe Ms Mg.sub.1/2i-Pr H Cl COOMe Ms EtN.sup.+ H.sub.3i-Pr H Cl COOMe Ms i-PrN.sup.+ H.sub.3i-Pr H Cl COOMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl COOMe Ms i-PrN.sup.+ H.sub.3Et Me Cl COOMe Ms NaEt Me Cl COOMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl COOMe Ms i-PrN.sup.+ H.sub.3Me H OMe COOMe Ms NaMe H OMe COOMe Ms KMe H OMe COOMe Ms Ca.sub.1/2Me H OMe COOMe Ms Mg.sub.1/2Me H OMe COOMe Ms EtN.sup.+ H.sub.3Me H OMe COOMe Ms i-PrN.sup.+ H.sub.3Me H OMe COOMe Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe COOMe Ms NaEt H OMe COOMe Ms KEt H OMe COOMe Ms Ca.sub.1/2Et H OMe COOMe Ms Mg.sub.1/2Et H OMe COOMe Ms EtN.sup.+ H.sub.3Et H OMe COOMe Ms i-PrN.sup.+ H.sub.3Et H OMe COOMe Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe COOMe Ms Nai-Pr H OMe COOMe Ms Ki-Pr H OMe COOMe Ms Ca.sub.1/2i-Pr H OMe COOMe Ms Mg.sub.1/2i-Pr H OMe COOMe Ms EtN.sup.+ H.sub.3i-Pr H OMe COOMe Ms i-PrN.sup.+ H.sub.3i-Pr H OMe COOMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe COOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt Me OMe COOMe Ms i-PrN.sup.+ H.sub.3Me H Me COOEt Ms NaMe H Me COOEt Ms KMe H Me COOEt Ms Ca.sub.1/2Me H Me COOEt Ms Mg.sub.1/2Me H Me COOEt Ms EtN.sup.+ H.sub.3Me H Me COOEt Ms i-PrN.sup.+ H.sub.3Me H Me COOEt Ms Et.sub.2 N.sup.+ H.sub.2Me H Me COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me COOEt Ms NaEt H Me COOEt Ms KEt H Me COOEt Ms Ca.sub.1/2Et H Me COOEt Ms Mg.sub.1/2Et H Me COOEt Ms EtN.sup.+ H.sub.3Et H Me COOEt Ms i-PrN.sup.+ H.sub.3Et H Me COOEt Ms Et.sub.2 N.sup.+ H.sub.2Et H Me COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me COOEt Ms Nai-Pr H Me COOEt Ms Ki-Pr H Me COOEt Ms Ca.sub.1/2i-Pr H Me COOEt Ms Mg.sub.1/2i-Pr H Me COOEt Ms EtN.sup.+ H.sub.3i-Pr H Me COOEt Ms i-PrN.sup.+ H.sub.3i-Pr H Me COOEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me COOEt Ms Me.sub.3 N.sup.+ CH.sub. 2 CH.sub.2 OHMe Me Me COOEt Ms i-PrN.sup.+ H.sub.3Et Me Me COOEt Ms NaEt Me Me COOEt Ms i-PrN.sup.+ H.sub.3i-Pr Me Me COOEt Ms i-PrN.sup.+ H.sub.3Me H Cl COOEt Ms NaMe H Cl COOEt Ms KMe H Cl COOEt Ms Ca.sub.1/2Me H Cl COOEt Ms Mg.sub.1/2Me H Cl COOEt Ms EtN.sup.+ H.sub.3Me H Cl COOEt Ms i-PrN.sup.+ H.sub.3Me H Cl COOEt Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl COOEt Ms NaEt H Cl COOEt Ms KEt H Cl COOEt Ms Ca.sub.1/2Et H Cl COOEt Ms Mg.sub.1/2Et H Cl COOEt Ms EtN.sup.+ H.sub.3Et H Cl COOEt Ms i-PrN.sup.+ H.sub.3Et H Cl COOEt Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Cl COOEt Ms Nai-Pr H Cl COOEt Ms Ki-Pr H Cl COOEt Ms Ca.sub.1/2i-Pr H Cl COOEt Ms Mg.sub.1/2i-Pr H Cl COOEt Ms EtN.sup.+ H.sub.3i-Pr H Cl COOEt Ms i-PrN.sup.+ H.sub.3i-Pr H Cl COOEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl COOEt Ms i-PrN.sup.+ H.sub.3Et Me Cl COOEt Ms NaEt Me Cl COOEt Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl COOEt Ms i-PrN.sup.+ H.sub.3Me H OMe COOEt Ms NaMe H OMe COOEt Ms KMe H OMe COOEt Ms Ca.sub.1/2Me H OMe COOEt Ms Mg.sub.1/2Me H OMe COOEt Ms EtN.sup.+ H.sub.3Me H OMe COOEt Ms i-PrN.sup.+ H.sub.3Me H OMe COOEt Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe COOEt Ms NaEt H OMe COOEt Ms KEt H OMe COOEt Ms Ca.sub.1/2Et H OMe COOEt Ms Mg.sub.1/2Et H OMe COOEt Ms EtN.sup.+ H.sub.3Et H OMe COOEt Ms i-PrN.sup.+ H.sub.3Et H OMe COOEt Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe COOEt Ms Nai-Pr H OMe COOEt Ms Ki-Pr H OMe COOEt Ms Ca.sub.1/2i-Pr H OMe COOEt Ms Mg.sub.1/2i-Pr H OMe COOEt Ms EtN.sup.+ H.sub.3i-Pr H OMe COOEt Ms i-PrN.sup.+ H.sub.3i-Pr H OMe COOEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe COOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt Me OMe COOEt Ms i-PrN.sup.+ H.sub.3Me H Me COOPr-i Ms NaMe H Me COOPr-i Ms KMe H Me COOPr-i Ms Ca.sub.1/2Me H Me COOPr-i Ms Mg.sub.1/2Me H Me COOPr-i Ms EtN.sup.+ H.sub.3Me H Me COOPr-i Ms i-PrN.sup.+ H.sub.3Me H Me COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2Me H Me COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me COOPr-i Ms NaEt H Me COOPr-i Ms KEt H Me COOPr-i Ms Ca.sub.1/2Et H Me COOPr-i Ms Mg.sub.1/2Et H Me COOPr-i Ms EtN.sup.+ H.sub.3Et H Me COOPr-i Ms i-PrN.sup.+ H.sub.3Et H Me COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2Et H Me COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me COOPr-i Ms Nai-Pr H Me COOPr-i Ms Ki-Pr H Me COOPr-i Ms Ca.sub.1/2i-Pr H Me COOPr-i Ms Mg.sub.1/2i-Pr H Me COOPr-i Ms EtN.sup.+ H.sub.3i-Pr H Me COOPr-i Ms i-PrN.sup.+ H.sub.3i-Pr H Me COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Me COOPr-i Ms i-PrN.sup.+ H.sub.3Et Me Me COOPr-i Ms NaEt Me Me COOPr-i Ms i-PrN.sup.+ H.sub.3i-Pr Me Me COOPr-i Ms i-PrN.sup.+ H.sub.3Me H Cl COOPr-i Ms NaMe H Cl COOPr-i Ms KMe H Cl COOPr-i Ms Ca.sub.1/2Me H Cl COOPr-i Ms Mg.sub.1/2Me H Cl COOPr-i Ms EtN.sup.+ H.sub.3Me H Cl COOPr-i Ms i-PrN.sup.+ H.sub.3Me H Cl COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl COOPr-i Ms NaEt H Cl COOPr-i Ms KEt H Cl COOPr-i Ms Ca.sub.1/2Et H Cl COOPr-i Ms Mg.sub.1/2Et H Cl COOPr-i Ms EtN.sup.+ H.sub.3Et H Cl COOPr-i Ms i-PrN.sup.+ H.sub.3Et H Cl COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Cl COOPr-i Ms Nai-Pr H Cl COOPr-i Ms Ki-Pr H Cl COOPr-i Ms Ca.sub.1/2i-Pr H Cl COOPr-i Ms Mg.sub.1/2i-Pr H Cl COOPr-i Ms EtN.sup.+ H.sub.3i-Pr H Cl COOPr-i Ms i-PrN.sup.+ H.sub.3i-Pr H Cl COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl COOPr-i Ms i-PrN.sup.+ H.sub.3Et Me Cl COOPr-i Ms NaEt Me Cl COOPr-i Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl COOPr-i Ms i-PrN.sup.+ H.sub.3Me H OMe COOPr-i Ms NaMe H OMe COOPr-i Ms KMe H OMe COOPr-i Ms Ca.sub.1/2Me H OMe COOPr-i Ms Mg.sub.1/2Me H OMe COOPr-i Ms EtN.sup.+ H.sub.3Me H OMe COOPr-i Ms i-PrN.sup.+ H.sub.3Me H OMe COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe COOPr-i Ms NaEt H OMe COOPr-i Ms KEt H OMe COOPr-i Ms Ca.sub.1/2Et H OMe COOPr-i Ms Mg.sub.1/2Et H OMe COOPr-i Ms EtN.sup.+ H.sub.3Et H OMe COOPr-i Ms i-PrN.sup.+ H.sub.3Et H OMe COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe COOPr-i Ms Nai-Pr H OMe COOPr-i Ms Ki-Pr H OMe COOPr-i Ms Ca.sub.1/2i-Pr H OMe COOPr-i Ms Mg.sub.1/2i-Pr H OMe COOPr-i Ms EtN.sup.+ H.sub.3i-Pr H OMe COOPr-i Ms i-PrN.sup.+ H.sub.3i-Pr H OMe COOPr-i Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe COOPr-i Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt Me OMe COOPr-i Ms i-PrN.sup.+ H.sub.3Me H Me COOCH.sub.2 CH.sub.2 OMe Ms NaMe H Me COOCH.sub.2 CH.sub.2 OMe Ms KMe H Me COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2Me H Me COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2Me H Me COOCH.sub. 2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Me H Me COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Me COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Me COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me COOCH.sub.2 CH.sub.2 OMe Ms NaEt H Me COOCH.sub.2 CH.sub.2 OMe Ms KEt H Me COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2Et H Me COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2Et H Me COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Et H Me COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et H Me COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Me COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms Nai-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms Ki-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2i-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2i-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3i-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Me COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et Me Me COOCH.sub.2 CH.sub.2 OMe Ms NaEt Me Me COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Me COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Cl COOCH.sub.2 CH.sub.2 OMe Ms NaMe H Cl COOCH.sub.2 CH.sub.2 OMe Ms KMe H Cl COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2Me H Cl COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2Me H Cl COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Me H Cl COOCH.sub. 2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Cl COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl COOCH.sub.2 CH.sub.2 OMe Ms NaEt H Cl COOCH.sub.2 CH.sub.2 OMe Ms KEt H Cl COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2Et H Cl COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2Et H Cl COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Et H Cl COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et H Cl COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms Nai-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms Ki-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2i-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2i-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3i-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et Me Cl COOCH.sub.2 CH.sub.2 OMe Ms NaEt Me Cl COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H OMe COOCH.sub.2 CH.sub.2 OMe Ms NaMe H OMe COOCH.sub.2 CH.sub.2 OMe Ms KMe H OMe COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2Me H OMe COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2Me H OMe COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Me H OMe COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H OMe COOCH.sub. 2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe COOCH.sub.2 CH.sub.2 OMe Ms NaEt H OMe COOCH.sub.2 CH.sub.2 OMe Ms KEt H OMe COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2Et H OMe COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2Et H OMe COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Et H OMe COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et H OMe COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms Nai-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms Ki-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms Ca.sub.1/2i-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms Mg.sub.1/2i-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms EtN.sup.+ H.sub. 3i-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe COOCH.sub.2 CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt Me OMe COOCH.sub.2 CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Me CH.sub.2 OMe Ms NaMe H Me CH.sub.2 OMe Ms KMe H Me CH.sub.2 OMe Ms Ca.sub.1/2Me H Me CH.sub.2 OMe Ms Mg.sub.1/2Me H Me CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Me H Me CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Me CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Me CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me CH.sub.2 OMe Ms NaEt H Me CH.sub.2 OMe Ms KEt H Me CH.sub.2 OMe Ms Ca.sub.1/2Et H Me CH.sub.2 OMe Ms Mg.sub.1/2Et H Me CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Et H Me CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et H Me CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Me CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me CH.sub.2 OMe Ms Nai-Pr H Me CH.sub.2 OMe Ms Ki-Pr H Me CH.sub.2 OMe Ms Ca.sub.1/2i-Pr H Me CH.sub.2 OMe Ms Mg.sub.1/2i-Pr H Me CH.sub.2 OMe Ms EtN.sup.+ H.sub.3i-Pr H Me CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr H Me CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Me CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et Me Me CH.sub.2 OMe Ms NaEt Me Me CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Me CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Cl CH.sub. 2 OMe Ms NaMe H Cl CH.sub.2 OMe Ms KMe H Cl CH.sub.2 OMe Ms Ca.sub.1/2Me H Cl CH.sub.2 OMe Ms Mg.sub.1/2Me H Cl CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Me H Cl CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Cl CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl CH.sub.2 OMe Ms NaEt H Cl CH.sub.2 OMe Ms KEt H Cl CH.sub.2 OMe Ms Ca.sub.1/2Et H Cl CH.sub.2 OMe Ms Mg.sub.1/2Et H Cl CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Et H Cl CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et H Cl CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Cl CH.sub.2 OMe Ms Nai-Pr H Cl CH.sub.2 OMe Ms Ki-Pr H Cl CH.sub.2 OMe Ms Ca.sub.1/2i-Pr H Cl CH.sub.2 OMe Ms Mg.sub.1/2i-Pr H Cl CH.sub.2 OMe Ms EtN.sup.+ H.sub.3i-Pr H Cl CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr H Cl CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et Me Cl CH.sub.2 OMe Ms NaEt Me Cl CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H OMe CH.sub.2 OMe Ms NaMe H OMe CH.sub.2 OMe Ms KMe H OMe CH.sub.2 OMe Ms Ca.sub.1/2Me H OMe CH.sub.2 OMe Ms Mg.sub.1/2Me H OMe CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Me H OMe CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H OMe CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe CH.sub.2 OMe Ms NaEt H OMe CH.sub.2 OMe Ms KEt H OMe CH.sub.2 OMe Ms Ca.sub.1/2Et H OMe CH.sub.2 OMe Ms Mg.sub.1/2Et H OMe CH.sub.2 OMe Ms EtN.sup.+ H.sub.3Et H OMe CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Et H OMe CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe CH.sub.2 OMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe CH.sub.2 OMe Ms Nai-Pr H OMe CH.sub.2 OMe Ms Ki-Pr H OMe CH.sub.2 OMe Ms Ca.sub.1/2i-Pr H OMe CH.sub.2 OMe Ms Mg.sub.1/2i-Pr H OMe CH.sub.2 OMe Ms EtN.sup.+ H.sub.3i-Pr H OMe CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3i-Pr H OMe CH.sub.2 OMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe CH.sub.2 OMe Ms Me.sub.3 N.sup. + CH.sub.2 CH.sub.2 OHEt Me OMe CH.sub.2 OMe Ms i-PrN.sup.+ H.sub.3Me H Me CH.sub.2 OEt Ms NaMe H Me CH.sub.2 OEt Ms KMe H Me CH.sub.2 OEt Ms Ca.sub.1/2Me H Me CH.sub.2 OEt Ms Mg.sub.1/2Me H Me CH.sub.2 OEt Ms EtN.sup.+ H.sub.3Me H Me CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Me H Me CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2Me H Me CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me CH.sub.2 OEt Ms NaEt H Me CH.sub.2 OEt Ms KEt H Me CH.sub.2 OEt Ms Ca.sub.1/2Et H Me CH.sub.2 OEt Ms Mg.sub.1/2Et H Me CH.sub.2 OEt Ms EtN.sup.+ H.sub.3Et H Me CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Et H Me CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2Et H Me CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me CH.sub.2 OEt Ms Nai-Pr H Me CH.sub.2 OEt Ms Ki-Pr H Me CH.sub.2 OEt Ms Ca.sub.1/2i-Pr H Me CH.sub.2 OEt Ms Mg.sub.1/2i-Pr H Me CH.sub.2 OEt Ms EtN.sup.+ H.sub.3i-Pr H Me CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3i-Pr H Me CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Me CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Et Me Me CH.sub.2 OEt Ms NaEt Me Me CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3i-Pr Me Me CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Me H Cl CH.sub.2 OEt Ms NaMe H Cl CH.sub.2 OEt Ms KMe H Cl CH.sub.2 OEt Ms Ca.sub.1/2Me H Cl CH.sub.2 OEt Ms Mg.sub.1/2Me H Cl CH.sub.2 OEt Ms EtN.sup.+ H.sub.3Me H Cl CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Me H Cl CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl CH.sub.2 OEt Ms NaEt H Cl CH.sub.2 OEt Ms KEt H Cl CH.sub.2 OEt Ms Ca.sub.1/2Et H Cl CH.sub.2 OEt Ms Mg.sub.1/2Et H Cl CH.sub.2 OEt Ms EtN.sup.+ H.sub.3Et H Cl CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Et H Cl CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Cl CH.sub.2 OEt Ms Nai-Pr H Cl CH.sub.2 OEt Ms Ki-Pr H Cl CH.sub.2 OEt Ms Ca.sub.1/2i-Pr H Cl CH.sub.2 OEt Ms Mg.sub.1/2i-Pr H Cl CH.sub.2 OEt Ms EtN.sup.+ H.sub.3i-Pr H Cl CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3i-Pr H Cl CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Et Me Cl CH.sub.2 OEt Ms NaEt Me Cl CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Me H OMe CH.sub.2 OEt Ms NaMe H OMe CH.sub.2 OEt Ms KMe H OMe CH.sub.2 OEt Ms Ca.sub.1/2Me H OMe CH.sub.2 OEt Ms Mg.sub.1/2Me H OMe CH.sub.2 OEt Ms EtN.sup.+ H.sub.3Me H OMe CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Me H OMe CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe CH.sub.2 OEt Ms NaEt H OMe CH.sub.2 OEt Ms KEt H OMe CH.sub.2 OEt Ms Ca.sub.1/2Et H OMe CH.sub.2 OEt Ms Mg.sub.1/2Et H OMe CH.sub.2 OEt Ms EtN.sup.+ H.sub.3Et H OMe CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Et H OMe CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe CH.sub.2 OEt Ms Nai-Pr H OMe CH.sub.2 OEt Ms Ki-Pr H OMe CH.sub.2 OEt Ms Ca.sub.1/2i-Pr H OMe CH.sub.2 OEt Ms Mg.sub.1/2i-Pr H OMe CH.sub.2 OEt Ms EtN.sup.+ H.sub.3i-Pr H OMe CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3i-Pr H OMe CH.sub.2 OEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe CH.sub.2 OEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt Me OMe CH.sub.2 OEt Ms i-PrN.sup.+ H.sub.3Me H Me CHMeOMe Ms NaMe H Me CHMeOMe Ms KMe H Me CHMeOMe Ms Ca.sub.1/2Me H Me CHMeOMe Ms Mg.sub.1/2Me H Me CHMeOMe Ms EtN.sup.+ H.sub.3Me H Me CHMeOMe Ms i-PrN.sup.+ H.sub.3Me H Me CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Me CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me CHMeOMe Ms NaEt H Me CHMeOMe Ms KEt H Me CHMeOMe Ms Ca.sub.1/2Et H Me CHMeOMe Ms Mg.sub.1/2Et H Me CHMeOMe Ms EtN.sup.+ H.sub.3Et H Me CHMeOMe Ms i-PrN.sup.+ H.sub.3Et H Me CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Me CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me CHMeOMe Ms Nai-Pr H Me CHMeOMe Ms Ki-Pr H Me CHMeOMe Ms Ca.sub.1/2i-Pr H Me CHMeOMe Ms Mg.sub.1/2i-Pr H Me CHMeOMe Ms EtN.sup.+ H.sub.3i-Pr H Me CHMeOMe Ms i-PrN.sup.+ H.sub.3i-Pr H Me CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me CHMeOMe Ms Me.sub.3 N.sup. + CH.sub.2 CH.sub.2 OHMe Me Me CHMeOMe Ms i-PrN.sup.+ H.sub.3Et Me Me CHMeOMe Ms NaEt Me Me CHMeOMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Me CHMeOMe Ms i-PrN.sup.+ H.sub.3Me H Cl CHMeOMe Ms NaMe H Cl CHMeOMe Ms KMe H Cl CHMeOMe Ms Ca.sub.1/2Me H Cl CHMeOMe Ms Mg.sub.1/2Me H Cl CHMeOMe Ms EtN.sup.+ H.sub.3Me H Cl CHMeOMe Ms i-PrN.sup.+ H.sub.3Me H Cl CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl CHMeOMe Ms NaEt H Cl CHMeOMe Ms KEt H Cl CHMeOMe Ms Ca.sub.1/2Et H Cl CHMeOMe Ms Mg.sub.1/2Et H Cl CHMeOMe Ms EtN.sup.+ H.sub.3Et H Cl CHMeOMe Ms i-PrN.sup.+ H.sub.3Et H Cl CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub. 2 OHi-Pr H Cl CHMeOMe Ms Nai-Pr H Cl CHMeOMe Ms Ki-Pr H Cl CHMeOMe Ms Ca.sub.1/2i-Pr H Cl CHMeOMe Ms Mg.sub.1/2i-Pr H Cl CHMeOMe Ms EtN.sup.+ H.sub.3i-Pr H Cl CHMeOMe Ms i-PrN.sup.+ H.sub.3i-Pr H Cl CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl CHMeOMe Ms i-PrN.sup.+ H.sub.3Et Me Cl CHMeOMe Ms NaEt Me Cl CHMeOMe Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl CHMeOMe Ms i-PrN.sup.+ H.sub.3Me H OMe CHMeOMe Ms NaMe H OMe CHMeOMe Ms KMe H OMe CHMeOMe Ms Ca.sub.1/2Me H OMe CHMeOMe Ms Mg.sub.1/2Me H OMe CHMeOMe Ms EtN.sup.+ H.sub.3Me H OMe CHMeOMe Ms i-PrN.sup.+ H.sub.3Me H OMe CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe CHMeOMe Ms NaEt H OMe CHMeOMe Ms KEt H OMe CHMeOMe Ms Ca.sub.1/2Et H OMe CHMeOMe Ms Mg.sub.1/2Et H OMe CHMeOMe Ms EtN.sup.+ H.sub.3Et H OMe CHMeOMe Ms i-PrN.sup.+ H.sub.3Et H OMe CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe CHMeOMe Ms Nai-Pr H OMe CHMeOMe Ms Ki-Pr H OMe CHMeOMe Ms Ca.sub.1/2i-Pr H OMe CHMeOMe Ms Mg.sub.1/2i-Pr H OMe CHMeOMe Ms EtN.sup.+ H.sub.3i-Pr H OMe CHMeOMe Ms i-PrN.sup.+ H.sub.3i-Pr H OMe CHMeOMe Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe CHMeOMe Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt Me OMe CHMeOMe Ms i-PrN.sup.+ H.sub.3Me H Me CHMeOEt Ms NaMe H Me CHMeOEt Ms KMe H Me CHMeOEt Ms Ca.sub.1/2Me H Me CHMeOEt Ms Mg.sub.1/2Me H Me CHMeOEt Ms EtN.sup.+ H.sub.3Me H Me CHMeOEt Ms i-PrN.sup.+ H.sub.3Me H Me CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2Me H Me CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Me CHMeOEt Ms NaEt H Me CHMeOEt Ms KEt H Me CHMeOEt Ms Ca.sub.1/2Et H Me CHMeOEt Ms Mg.sub.1/2Et H Me CHMeOEt Ms EtN.sup.+ H.sub.3Et H Me CHMeOEt Ms i-PrN.sup.+ H.sub.3Et H Me CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2Et H Me CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Me CHMeOEt Ms Nai-Pr H Me CHMeOEt Ms Ki-Pr H Me CHMeOEt Ms Ca.sub.1/2i-Pr H Me CHMeOEt Ms Mg.sub.1/2i-Pr H Me CHMeOEt Ms EtN.sup.+ H.sub.3i-Pr H Me CHMeOEt Ms i-PrN.sup.+ H.sub.3i-Pr H Me CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Me CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Me CHMeOEt Ms i-PrN.sup.+ H.sub.3Et Me Me CHMeOEt Ms NaEt Me Me CHMeOEt Ms i-PrN.sup.+ H.sub.3i-Pr Me Me CHMeOEt Ms i-PrN.sup.+ H.sub.3Me H Cl CHMeOEt Ms NaMe H Cl CHMeOEt Ms KMe H Cl CHMeOEt Ms Ca.sub.1/2Me H Cl CHMeOEt Ms Mg.sub.1/2Me H Cl CHMeOEt Ms EtN.sup.+ H.sub.3Me H Cl CHMeOEt Ms i-PrN.sup.+ H.sub.3Me H Cl CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2Me H Cl CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H Cl CHMeOEt Ms NaEt H Cl CHMeOEt Ms KEt H Cl CHMeOEt Ms Ca.sub.1/2Et H Cl CHMeOEt Ms Mg.sub.1/2Et H Cl CHMeOEt Ms EtN.sup.+ H.sub.3Et H Cl CHMeOEt Ms i-PrN.sup.+ H.sub.3Et H Cl CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2Et H Cl CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H Cl CHMeOEt Ms Nai-Pr H Cl CHMeOEt Ms Ki-Pr H Cl CHMeOEt Ms Ca.sub.1/2i-Pr H Cl CHMeOEt Ms Mg.sub.1/2i-Pr H Cl CHMeOEt Ms EtN.sup.+ H.sub.3i-Pr H Cl CHMeOEt Ms i-PrN.sup.+ H.sub.3i-Pr H Cl CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H Cl CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHMe Me Cl CHMeOEt Ms i-PrN.sup.+ H.sub.3Et Me Cl CHMeOEt Ms NaEt Me Cl CHMeOEt Ms i-PrN.sup.+ H.sub.3i-Pr Me Cl CHMeOEt Ms i-PrN.sup.+ H.sub.3Me H OMe CHMeOEt Ms NaMe H OMe CHMeOEt Ms KMe H OMe CHMeOEt Ms Ca.sub.1/2Me H OMe CHMeOEt Ms Mg.sub.1/2Me H OMe CHMeOEt Ms EtN.sup.+ H.sub.3Me H OMe CHMeOEt Ms i-PrN.sup.+ H.sub.3Me H OMe CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2Me H OMe CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt H OMe CHMeOEt Ms NaEt H OMe CHMeOEt Ms KEt H OMe CHMeOEt Ms Ca.sub.1/2Et H OMe CHMeOEt Ms Mg.sub.1/2Et H OMe CHMeOEt Ms EtN.sup.+ H.sub.3Et H OMe CHMeOEt Ms i-PrN.sup.+ H.sub.3Et H OMe CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2Et H OMe CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHi-Pr H OMe CHMeOEt Ms Nai-Pr H OMe CHMeOEt Ms Ki-Pr H OMe CHMeOEt Ms Ca.sub.1/2i-Pr H OMe CHMeOEt Ms Mg.sub.1/2i-Pr H OMe CHMeOEt Ms EtN.sup.+ H.sub.3i-Pr H OMe CHMeOEt Ms i-PrN.sup.+ H.sub.3i-Pr H OMe CHMeOEt Ms Et.sub.2 N.sup.+ H.sub.2i-Pr H OMe CHMeOEt Ms Me.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHEt Me OMe CHMeOEt Ms i-PrN.sup.+ H.sub.3Me H Me CH.sub.2 CO.sub.2 Me Ms HEt H Me CH.sub.2 CO.sub.2 Me Ms Hi-Pr H Me CH.sub.2 CO.sub.2 Me Ms HMe H Me CH.sub.2 CO.sub.2 Et Ms HEt H Me CH.sub.2 CO.sub.2 Et Ms Hi-Pr H Me CH.sub.2 CO.sub.2 Et Ms HMe H Me CH.sub.2 CO.sub. Pr-i Ms HEt H Me CH.sub.2 CO.sub. Pr-i Ms Hi-Pr H Me CH.sub.2 CO.sub. Pr-i Ms HMe H Me CHMeCO.sub.2 Me Ms HEt H Me CHMeCO.sub.2 Me Ms Hi-Pr H Me CHMeCO.sub.2 Me Ms HMe H Me CHMeCO.sub.2 Et Ms HEt H Me CHMeCO.sub.2 Et Ms Hi-Pr H Me CHMeCO.sub.2 Et Ms HMe H Me CHMeCO.sub.2 Pr-i Ms HEt H Me CHMeCO.sub.2 Pr-i Ms Hi-Pr H Me CHMeCO.sub.2 Pr-i Ms HMe H Me CH.sub.2 CH.sub.2 CO.sub.2 Me Ms HEt H Me CH.sub.2 CH.sub.2 CO.sub.2 Me Ms Hi-Pr H Me CH.sub.2 CH.sub.2 CO.sub.2 Me Ms HMe H Me CH.sub.2 CH.sub.2 CO.sub.2 Et Ms HEt H Me CH.sub.2 CH.sub.2 CO.sub.2 Et Ms Hi-Pr H Me CH.sub.2 CH.sub.2 CO.sub.2 Et Ms HMe H Me CH.sub.2 CH.sub.2 CO.sub.2 Pr-i Ms HEt H Me CH.sub.2 CH.sub.2 CO.sub.2 Pr-i Ms Hi-Pr H Me CH.sub.2 CH.sub.2 CO.sub.2 Pr-i Ms HMe H Me CHCHOMe Ms HEt H Me CHCHOMe Ms Hi-Pr H Me CHCHOMe Ms HMe H Me CHCHOEt Ms HEt H Me CHCHOEt Ms Hi-Pr H Me CHCHOEt Ms HMe H Me CHCHOPr-i Ms HEt H Me CHCHOPr-i Ms Hi-Pr H Me CHCHOPr-i Ms HMe H Cl CH.sub.2 CO.sub.2 Me Ms HEt H Cl CH.sub.2 CO.sub.2 Me Ms Hi-Pr H Cl CH.sub.2 CO.sub.2 Me Ms HMe H Cl CH.sub.2 CO.sub.2 Et Ms HEt H Cl CH.sub.2 CO.sub.2 Et Ms Hi-Pr H Cl CH.sub.2 CO.sub.2 Et Ms HMe H Cl CH.sub.2 CO.sub. Pr-i Ms HEt H Cl CH.sub.2 CO.sub. Pr-i Ms Hi-Pr H Cl CH.sub.2 CO.sub. Pr-i Ms HMe H Cl CHMeCO.sub.2 Me Ms HEt H Cl CHMeCO.sub.2 Me Ms Hi-Pr H Cl CHMeCO.sub.2 Me Ms HMe H Cl CHMeCO.sub.2 Et Ms HEt H Cl CHMeCO.sub.2 Et Ms Hi-Pr H Cl CHMeCO.sub.2 Et Ms HMe H Cl CHMeCO.sub.2 Pr-i Ms HEt H Cl CHMeCO.sub.2 Pr-i Ms Hi-Pr H Cl CHMeCO.sub.2 Pr-i Ms HMe H Cl CH.sub.2 CH.sub.2 CO.sub.2 Me Ms HEt H Cl CH.sub.2 CH.sub.2 CO.sub.2 Me Ms Hi-Pr H Cl CH.sub.2 CH.sub.2 CO.sub.2 Me Ms HMe H Cl CH.sub.2 CH.sub.2 CO.sub.2 Et Ms HEt H Cl CH.sub.2 CH.sub.2 CO.sub.2 Et Ms Hi-Pr H Cl CH.sub.2 CH.sub.2 CO.sub.2 Et Ms HMe H Cl CH.sub.2 CH.sub.2 CO.sub.2 Pr-i Ms HEt H Cl CH.sub.2 CH.sub.2 CO.sub.2 Pr-i Ms Hi-Pr H Cl CH.sub.2 CH.sub.2 CO.sub.2 Pr-i Ms HMe H Cl CHCHOMe Ms HEt H Cl CHCHOMe Ms Hi-Pr H Cl CHCHOMe Ms HMe H Cl CHCHOEt Ms HEt H Cl CHCHOEt Ms Hi-Pr H Cl CHCHOEt Ms HMe H Cl CHCHOPr-i Ms HEt H Cl CHCHOPr-i Ms Hi-Pr H Cl CHCHOPr-i Ms H__________________________________________________________________________When the compound of the present invention is to be used as anagricultural or horticultural herbicide, it is usually mixed with asuitable carrier, for instance, a solid carrier such as clay, talc,bentonite or diatomaceous earth, or a liquid carrier such as water, analcohol (such as methanol or ethanol), an aromatic hydrocarbon (such asbenzene, toluene or xylene), a chlorinated hydrocarbon, an ether, aketone, an ester (such as ethyl acetate) or an acid amide (such asdimethylformamide). If desired, an emulsifier, a dispersing agent, asuspending agent, a penetrating agent, a spreader or a stabilizer may beadded to prepare an optional formulation such as a liquid formulation, anemulsifiable concentrate, a wettable powder, a dust, a granule or a
Further, if desired, other herbicides, various insecticides, bacteriocides, plant regulating agents or synergism agents may be combined at the time of the preparation of the formulations or at a time of the application of the herbicides.
As other herbicides to be combined with the herbicide of the present invention, there may be mentioned, for instance, compounds disclosed in Farm Chemicals Handbook, the 73rd Edition (1987). Among them, there may be mentioned, for example, atrazine, cyanazine, alachlor, metolachlor, EPTC, 2,4-D, butylate, dicamba, bromoxynil and tridiphane. Further, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-chloro-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide or N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-bromo-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide as disclosed in U.S. Pat. No. 4,668,277 may also be combined with the herbicide of the present invention.
The dose varies depending upon the application site, the season for application, the method for application, the type of the crop plant, etc. In general, however, the dose is usually within a range of from 0.001 to 10 kg per hectare as the amount of the active ingredient.
Now, Formulation Examples of the herbicides containing the compounds of the present invention as active ingredients, will be given. However, it should be understood that the present invention is by no means restricted to such specific Examples. In the following Formulation Examples, "parts" means "parts by weight".
______________________________________FORMULATION EXAMPLE 1: Wettable powder______________________________________Compound No. 3 of the present invention 60 partsZeeklite PFP (tradename for a kaolin-type 33 partsclay, manufactured by Zeeklite Industries,Co., Ltd.)Sorpol 5039 (tradename for a mixture of a 5 partsnonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)Carplex (tradename for a coagulation- 2 partspreventing agent composed of a mixture ofa surfactant and fine silica powder,manufactured by Shionogi PharmaceuticalCo., Ltd.)______________________________________
The above ingredients are homogeneously pulverized and mixed to form a wettable powder.
______________________________________FORMULATION EXAMPLE 2: Wettable powderCompound No. 7 of the present invention 60 partsZeeklite PFP (tradename for a kaolin-type 33 partsclay, manufactured by Zeeklite Industries,Co., Ltd.)Sorpol 5039 (tradename for a mixture of a 5 partsnonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)Carplex (tradename for a coagulation- 2 partspreventing agent composed of a mixture ofa surfactant and fine silica powder,manufactured by Shionogi PharmaceuticalCo., Ltd.)FORMULATION EXAMPLE 3: Wettable powderCompound No. 15 of the present invention 60 partsZeeklite PFP (tradename for a kaolin-type 33 partsclay, manufactured by Zeeklite Industries,Co., Ltd.)Sorpol 5039 (tradename for a mixture of a 5 partsnonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)Carplex (tradename for a coagulation- 2 partspreventing agent composed of a mixture ofa surfactant and fine silica powder,manufactured by Shionogi PharmaceuticalCo., Ltd.)FORMULATION EXAMPLE 4: Wettable powderCompound No. 21 of the present invention 60 partsZeeklite PFP (tradename for a kaolin-type 33 partsclay, manufactured by Zeeklite Industries,Co., Ltd.)Sorpol 5039 (tradename for a mixture of a 5 partsnonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)Carplex (tradename for a coagulation- 2 partspreventing agent composed of a mixture ofa surfactant and fine silica powder,manufactured by Shionogi PharmaceuticalCo., Ltd.)FORMULATION EXAMPLE 5: Wettable powderCompound No. 25 of the present invention 60 partsZeeklite PFP (tradename for a kaolin-type 33 partsclay, manufactured by Zeeklite Industries,Co., Ltd.)Sorpol 5039 (tradename for a mixture of a 5 partsnonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)Carplex (tradename for a coagulation- 2 partspreventing agent composed of a mixture ofa surfactant and fine silica powder,manufactured by Shionogi PharmaceuticalCo., Ltd.)FORMULATION EXAMPLE 6: Wettable powderCompound No. 35 of the present invention 60 partsZeeklite PFP (tradename for a kaolin-type 33 partsclay, manufactured by Zeeklite Industries,Co., Ltd.)Sorpol 5039 (tradename for a mixture of a 5 partsnonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)Carplex (tradename for a coagulation- 2 partspreventing agent composed of a mixture ofa surfactant and fine silica powder,manufactured by Shionogi PharmaceuticalCo., Ltd.)FORMULATION EXAMPLE 7: Emulsifiable concentrateCompound No. 3 of the present invention 1.5 partsXylene 78.5 partsN,N-dimethylformamide 15 partsSorpol 2680 (tradename for a mixture of 5 partsa nonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)______________________________________
The above ingredients are homogeneously mixed to obtain an emulsifiable concentrate.
______________________________________FORMULATION EXAMPLE 8: Emulsifiable concentrateCompound No. 11 of the present invention 1.5 partsXylene 78.5 partsN,N-dimethylformamide 15 partsSorpol 2680 (tradename for a mixture of 5 partsa nonionic surfactant and an anionicsurfactant, manufactured by Toho ChemicalCo., Ltd.)FORMULATION EXAMPLE 9: FlowableCompound No. 3 of the present invention 40 partsAgrizole B-710 (tradename for a nonionic 10 partssurfactant, manufactured by Kao Corporation)Runox 1000C (tradename for an anionic 0.5 partsurfactant, manufactured by Toho ChemicalCo., Ltd.)1% Rodopol water (tradename for a 20 partsthickener, manufactured by Rhone-Poulenc)Water 29.5 parts______________________________________
The above ingredients are homogeneously mixed to form a flowable.
______________________________________FORMULATION EXAMPLE 10: FlowableCompound No. 10 of the present invention 40 partsAgrizole B-710 (tradename for a nonionic 10 partssurfactant, manufactured by Kao Corporation)Runox 1000C (tradename for an anionic 0.5 partsurfactant, manufactured by Toho ChemicalCo., Ltd.)1% Rodopol water (tradename for a 20 partsthickener, manufactured by Rhone-Poulenc)Water 29.5 partsFORMULATION EXAMPLE 11: Liquid formulationCompound No. 39 of the present invention 30 partsNippol (tradename for a nonionic surfactant, 10 partsmanufactured by Nissan Chemical Industries,Ltd.)Water 60 parts______________________________________
The above ingredients are homogeneously mixed to obtain a liquid formulation.
______________________________________FORMULATION EXAMPLE 12: Liquid formulationCompound No. 40 of the present invention 30 partsNippol (tradename for a nonionic surfactant, 10 partsmanufactured by Nissan Chemical Industries,Ltd.)Water 60 partsFORMULATION EXAMPLE 13: Liquid formulationCompound No. 46 of the present invention 30 partsNippol (tradename for a nonionic surfactant, 10 partsmanufactured by Nissan Chemical Industries,Ltd.)Water 60 partsFORMULATION EXAMPLE 14: Liquid formulationCompound No. 41 of the present invention 10 partsSorpol W-150 (tradename for a nonionic 10 partssurfactant, manufactured by TohoChemical Co., Ltd.)Water 80 parts______________________________________
The above ingredients are homogeneously mixed to form a liquid formulation.
In their use, the above wettable powders, emulsifiable concentrates, flowables or liquid formulations are diluted with water from 50 to 1,000 times and applied so that the respective active ingredients will be from 0.001 to 5 kg per hectare.
The compounds of the present invention are applicable not only to agricultural and horticultural fields such as upland fields, paddy fields and orchards, but to non-agricultural fields such as athletic fields, vacant fields and railway sides for the control of various weeds. The dose in their application varies depending upon the application site, the season for application, the type of crop plants, etc. However, it is usually within a range of from 0.001 to 5 kg per hectare.
Now, the herbicidal activities of the compounds of the present invention will be described with respect to specific Test Examples.
TEST EXAMPLE
Test on the herbicidal effects in soil treatment
A plastic box having a length of 15 cm, a width of 22 cm and a depth of 6 cm was filled with a sterilized diluvium soil, and seeds Echinochloa crus-galli, Setaria viridis, Eleusine indica, Digitaria adscendens, Panicum dichotomiflorum, Abutilon theophrasti, Amaranthus lividus, Polygonum longisetum and Zea mays were sown, and tubers of Cyperus esculentus were further planted. The soil was covered thereon in the thickness of about 1.5 cm, and then a herbicide solution was applied onto the surface of the soil uniformly so that the active ingredient is distributed at a predetermined concentration. The herbicide solution was prepared by diluting a wettable powder, an emulsifiable concentrate, a liquid formulation or a flowable with water and applied onto the entire soil surface by means of a small spray. Three weeks after the application of the herbicidal solution, the herbicidal effects against each weed were determined on the basis of the following standard ratings. The results thereby obtained are shown in Table 6. The Compound Nos. correspond to the Compound Nos. in Table 3.
Standard ratings:
5 Growth control rate of more than 90% (almost completely withered)
4 Growth control rate of from 70 to 90%
3: Growth control rate of from 40 to 70%
2: Growth control rate of from 20 to 40%
1: Growth control rate of from 5 to 20%
0: Growth control rate of less than 5% (almost non-effective)
The above growth control rates were calculated by the following equation: ##EQU1## where T: Weight of the weed growth above the soil surface of the treated area
N: Weight of the weed grown above the soil surface of the non-treated area
TEST EXAMPLE 2
Test on the herbicidal effects in foliage treatment
A plastic box having a length of 15 cm, a width of 22 cm and a depth of 6 cm was filled with a sterilized diluvium soil, and seeds of Echinochloa crus-galli, Setaria viridis, Eleusine indica, Digitaria adscendens, panicum dichotomiflorum, Xanthium strumarium, Abutilon theophrasti, Amaranthus lividus, Polygonum longisetum and Zea mays were spot-wisely sown, and tubers of Cyperus esculentus were further planted. Then, the soil was covered thereon in a thickness of about 1.5 cm. When the various weeds and crops grew to the 2 or 3 leaf stage, a herbicidal solution was uniformly sprayed on the foliages so that the active ingredient is applied in a predetermined concentration.
The herbicidal solution was prepared by diluting the wettable powder, the emulsifiable concentrate, the liquid formulation or the flowable as described in the above Formulation Examples with water and applied onto the entire surface of the foliages of the weeds and the crop plants by a small spray. Two weeks after the application of the herbicide solution, the herbicidal effects against each weed were determined on the basis of the standard ratings described in Test Example 1, and the phytotoxicity against each crop plant was determined on the basis of the standard ratings in Test Example 1. The results are shown in Table 7. The Compound Nos. in Table 7 correspond to the Compound Nos. in Table 3.
In Tables 6 and 7, the following abbreviations are used:
Dose: Dose of active ingredient (g/are)
EC: Echinochloa crus-galli (barnyardgrass)
SE: Setaria viridis (green foxtail)
EL: Eleusine indica (goosegrass)
DI: Digitaria adscendens (large crabgrass)
PA: Panicum dichotomiflorum (fall panicum)
AB: Abutilon theophrasti (velvet leaf)
AM: Amaranthus lividus (livid amaranth)
PO: Polygonum longisetum (persicaria blumei gross)
XA: Xanthium strumarium (cocklebur)
CY: Cyperus esculentus (yellow nutsedge)
ZE: Zea mays (corn)
TABLE 6__________________________________________________________________________CompoundNo. Dose EC SE EL DI PA AB AM PO CY ZE__________________________________________________________________________ 1 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0 2 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0 3 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0 4 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0 6 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0 7 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0 8 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0 9 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 010 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 011 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 012 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 013 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 014 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 015 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 016 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 017 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 018 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 019 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 020 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 021 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 022 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 023 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 024 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 025 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 026 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 027 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 028 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 029 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 030 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 034 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 035 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 036 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 037 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 039 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 040 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 041 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 042 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 043 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 044 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 045 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 046 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 047 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 048 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 049 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 050 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 056 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 058 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 061 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 063 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 064 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 065 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 066 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 067 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 068 0.5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 0Reference 4 3 1 3 3 1 4 5 5 0 0Example 8 4 2 4 4 2 5 5 5 0 0A 16 5 3 5 5 3 5 5 5 1 1Reference 4 5 5 5 5 5 1 1 1 2 0Example 8 5 5 5 5 5 2 2 2 3 0B 16 5 5 5 5 5 3 3 3 4 1__________________________________________________________________________
TABLE 7__________________________________________________________________________CompoundNo. Dose EC SE EL DI PA AB AM PO XA CY ZE__________________________________________________________________________ 1 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0 2 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0 3 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0 4 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0 6 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0 7 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0 8 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0 9 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 010 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 011 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 012 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 013 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 014 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 015 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 016 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 017 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 018 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 019 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 020 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 021 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 022 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 023 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 024 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 025 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 026 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 027 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 028 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 029 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 030 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 034 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 035 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 036 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 037 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 039 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 040 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 041 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 042 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 043 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 044 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 045 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 046 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 047 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 048 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 049 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 050 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 056 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 058 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 061 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 063 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 064 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 065 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 066 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 067 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 068 0.5 5 5 5 5 5 5 5 5 5 5 0 1 5 5 5 5 5 5 5 5 5 5 0 2 5 5 5 5 5 5 5 5 5 5 0Reference 4 3 1 2 3 0 3 5 5 4 0 0Example 8 4 2 3 4 1 5 5 5 5 0 1A 16 5 3 4 5 2 5 5 5 5 1 2Reference 4 4 3 3 4 3 0 2 2 0 1 0Example 8 4 4 4 4 4 1 3 3 1 2 1B 16 5 5 5 5 5 2 4 4 2 3 2__________________________________________________________________________
In Tables 6 and 7, the Comparative Compounds are as follows:
Comparative Compound A: Atrazine ##STR38##
Comparative Compound B: Alachlor ##STR39##
Claims
  • 1. A pyrazole derivative having the formula:
  • wherein A is an alkyl group having from 1 to 3 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms or an alkynyl group having from 2 to 4 carbon atoms; B is a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, a halogen atom, a haloalkyl group having from 1 to 3 carbon atoms, an alkoxy group having from 1 to 3 carbon atoms, an alkylthio group having from 1 to 3 carbon atoms, an alkoxyalkyl group having from 2 to 4 carbon atoms, an alkylthioalkyl group having from 2 to 4 carbon atoms or an alkoxycarbonyl group having from 2 to 4 carbon atoms; X is an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, a haloalkyl group having from 1 to 6 carbon atoms, an alkoxyalkyl group having from 2 to 6 carbon atoms, an alkylcarbonyl group having from 2 to 6 carbon atoms, an alkoxycarbonyl group having from 2 to 6 carbon atoms, an aminocarbonyl group substituted independently by hydrogen or alkyl having from 1 to 6 carbon atoms, a haloalkoxy group having from 1 to 6 carbon atoms, an alkylthio group having from 1 to 6 carbon atoms or an alkylthioalkyl group having from 2 to 6 carbon atoms; Y is a --COOR1 group (wherein R1 is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, a cycloaklyl group having from 3 to 8 carbon atoms, a cycloalkylalkyl group having from 4 to 8 carbon atoms, an alkynyl group having from 3 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, a halocycloalkyl group having from 3 to 8 carbon atoms, a haloalkynyl group having from 3 to 6 carbon atoms, a haloalkenyl group having from 2 to 6 carbon atoms or a phenyl group which may be substituted by alkyl having from 1 to 3 carbon atoms, halogen, nitro or alkoxy having from 1 to 3 carbon atoms), a --COO--L--OR1 group (wherein L is an alkylene group having from 1 to 6 carbon atoms which may be substituted by alkyl having from 1 to 3 carbon atoms, and R1 is as defined above), a --COO--L--R2 group (wherein L is as defined above, and R2 is aphenyl group which may be substituted by alkyl having from 1 to 3 carbon atoms, halogen, nitro or alkoxy having from 1 to 3 carbon atoms), a --COO--M group (wherein M is a 3 to 6-membered alicyclic residue containing not more than a total of 2 sulfur or oxygen atoms and formed by a linkage of from 1 to 4 carbon atoms), a --COO--L--M group (wherein L and M are as defined above), a --COO--L--O--L--R2 group (wherein L and R2 are as defined above), a --COO--L--S(O).sub.n --R1 group (wherein L and R1 are as defined above, and n is an integer of from 0 to 2), a --CON(R3) (R4) group (wherein each of R3 and R4 is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms, a cycloalkylalkyl group having from 4 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an alkynyl group having from 2 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, a halocycloalky group having from 3 to 8 carbon atoms, a haloalkynyl group having from 2 to 6 carbon atoms, a haloalkynyl group having from 2 to 6 carbon atoms, or a phenyl group which may be substituted by alkyl having from 1 to 3 carbon atoms, halogen, nitro or alkoxy having from 1 to 3 carbon atoms,), a --CON--(CH.sub.2).sub.[n] group (wherein [n] s is an integer of from 4 to 6), a ##STR40## group (wherein R5 is an alkyl group having from 1 to 3 carbon atoms),a ##STR41## group, a --CONHSO.sub.2 CH.sub.3 group, a --CONHSO.sub.2 CF.sub.3 group, a --COO--L--N(R.sub.3) (R.sub.4) group (wherein L, R.sub.3 and R.sub.4 are as defined above), a --COO--L--CO--R1 group (wherein L and R1 are as defined above), a --COO--L--CO--O--R1 group (wherein L and R1 are as defined above), a --COO--L--CN group (wherein L is as defined above, a --COO--L--NO2 group (wherein L is as defined above), a --COOSi(R5)3 group (wherein R5 is as defined above), a --COO--N.dbd.C(R6) (R7) group (wherein each of R6 and R7 which may be the same or different is an alkyl group having from 1 to 3 carbon atoms), a --COO--N=C--(CH.sub.2).sub.[n] group (wherein [n] m is an integer of from 4 to 6), a --COO--L--O--SO.sub.2 --R1 group (wherein L and R1 are as defined above), a --COO--L--O--CO--R1 group (wherein L and R1 are as defined above), a --COO--L--O--L--O--R1 group (wherein L and R1 are as defined above), a --COO--L--Si(R5).sub.3 group (wherein L and R5 are as defined above), a --C(O)S--R1 group (wherein R1 is as defined above), a --C(S)O--R1 group (wherein R1 is as defined above), a --C(S)S--R1 group (wherein R1 is as defined above), a --L--O--R1 group (wherein L and R1 are as defined above), a --L--0--L--O--R8 group (wherein L is as defined above, and R8 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms), a --L--O--M group (wherein L and M are as defined above), a --L--O--L--M group (wherein L and M are as defined above), a --L--NR8R9 group (wherein R8 is as defined above, and R9 is an alkyl group having from 1 to 6 carbon atoms), a --L--O--CH2Ph group (wherein L is as defined above and Ph is phenyl), a --L--O--L--COOR9 group (wherein L and R9 are defined above), a --L--CN group (wherein L is as defined above), a --L--S(O).sub.[n]p --R1 group (wherein L and R1 is as defined above), and [n] is an integer of from 0 to 2), a --L--S--L--O--R9 group (wherein L and R9 are as ,o defined above), a --L--O--COR9 group (wherein L and R9 are as defined above), a --L--O--S02R9 group (wherein L and--R9 are as defined above), a --L--COOR8 group (wherein L and R8 are as defined above), a --CH.dbd.CHOR8 group (wherein R8is as defined above) or a --L--0--L--CN group (wherein L is as defined above); Z is a halogen atom, a nitro group, an alkoxy group having from 1 to 3 carbon atoms, a trifluoromethyl group, a cyano group or a --S(O).sub.[n]q R10 group (wherein R10 is an alkyl group having from 1 to 3 carbon atoms or a haloalkyl group having from 1 to 3 carbon atoms, and [n] q is an integer of from 0 to 2); V is a hydrogen atom, a halogen atom, an alkyl group having from 1 to 4 carbon atoms or an alkoxy group having from 1 to 4 carbon atoms; W is a hydrogen atom, a halogen atom, an alkyl group having from 1 to 4 carbon atoms, a haloalkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, an alkoxyalkyl group having from 2 to 6 carbon atoms, an alkoxycarbonyl group having from 2 to 5 carbon atoms, a haloalkoxy group having from 1 to 3 carbon atoms, a nitro group, a cyano group or a --S(O).sub.[n]r --R group (wherein [n] r is [as defined above]an integer of 0 to 2 and R is an alkyl group having from 1 to 4 carbon atoms); Q is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms which may be substituted by halogen, an alkenyl group having from 1 to 6 carbon atoms which may be substituted by halogen, an alkynyl group having from 1 to 6 carbon atoms which may be substituted by halogen, a cyanomethyl group, a --C(O)--R11 group (wherein R11 is a phenyl group which may be substituted by the same or different substituents selected from the group consisting of alkyl having from 1 to 6 carbon atoms, alkenyl having from 1 to 6 carbon atoms, alkynyl having from 1 to 6 carbon atoms, haloalkyl having from 1 to 6 carbon atoms, haloalkenyl having from 1 to 6 carbon atoms, haloalkynyl having from 1 to 6 carbon atoms, halogen, nitro and trifluoromethyl, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms or a hydroxyl group), a --S(O)2R11 group (wherein R11 is as defined above), a --P(O)(OR11 ).sub.2 group (wherein R11 is as defined above), a --L--C(O)--R11 group (wherein L and R11 are as defined above), a --L--C(O)--N(R12)(R13) (wherein L is as defined above, each of R12 and R13 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms), a --L--R14 group (wherein L is as defined above, R14 is a phenyl group which may be substituted by the same or different substituents selected from the group consisting of halogen, nitro and trifluoromethyl, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms or a hydroxy group), a --L--N(R12) (R13) group (wherein L, R12 and R13 are as defined above), a --L--OR15 group (wherein R15 is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms or an alkenyl group having from 1 to 6 carbon atoms), a --L--OC(O)R16 group (wherein R16 is an alkyl group having from 1 to 6 carbon atoms or an alkoxy group having from 1 to 6 carbon atoms), a --L--S(O).sub.[n] t R15 group (wherein R15 is as defined above, and [n] t is an integer of 0 or 2), a --L--SC(O)R12 group (wherein R12 is as defined above), ##STR42## (wherein each of L1 and L2 is a methylene group, an oxygen atom or a sulfur atom, R16 is a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, and [n] u is an integer of 2 or 3), and a salt thereof
  • 2. The pyrazole derivative according to claim 1, wherein A, B, X, Y, Z and Q in the formula I are respectively selected from the following substituents:
  • A: Me, Et, n-Pr, i-Pr, CH.sub.2 CH.dbd.CH.sub.2, CH2C.tbd.CH
  • B: H, Me, Et, n-Pr, i-Pr, Cl, Br, CH.sub.2 Cl, CF.sub.2, OMe, OEt, OPr-i, SMe, CH.sub.2 OMe, CH.sub.2 SMe, CO.sub.2 Me, CO.sub.2 Et
  • X: Me, Et, N-Pr, i-Pr, N-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, OPr-n, OPr-i, OBu-n OBu-i, OBu-s, OBu-t, F, Cl, Br, I, NO.sub.2, CN, CH.sub.2 F, CHF.sub.2, CF.sub.3, CF.sub.2, CH.sub.2 CF.sub.3, CH.sub.2 Cl, CCl.sub.3, CHClMe, CH.sub.2 CH.sub.2 Cl, CHClCH.sub.2 Cl, CH.sub.2 Cl Br, CHBrMe, CH.sub.2 CH.sub.2 Br, CH.sub.2 OMe, CH.sub.2 OEt, CH.sub.2 OPr-n, CH.sub.2 OPr-i, CH.sub.2 OBu-n, CH.sub.2 OBu-i, CH.sub.2 OBu-s, CH.sub.2 OBu-t, CHMeOMe, CHMeOEt, CHMeOPr-n, CHMeOPr-i, CHMeOBu-n, CHMeOBu-i, CHMeOBu-s, CHMeOBu-t, CH.sub.2 CH.sub.2 OMe, CH.sub.2 CH.sub.2 OEt, CH.sub.2 CH.sub.20 Pr-i, Ac, COEt, COPr-n, COPr-i, COOMe, COOEt, COOPr-i, CONHMe, CONHEt, CONMe.sub.2, CONEt.sub.2, CONEtMe, OCHF.sub.2, OCF.sub.3, OCH.sub.2 CF.sub.3, SMe, SEt, CH.sub.2 SMe, CH.sub.2 SEt, CHMeSMe, CHMeSEt
  • Y: CH.sub.2 OH, CH.sub.2 OMt, CH.sub.2 OEt, CH.sub.2 OPr-n, CH.sub.2 OPr-i, CH.sub.2 OBu-n, CH.sub.2 OBu-i, CH.sub.2 OBu-s, CH.sub.2 OBu-t, CH.sub.2 OAm-n, CH.sub.2 OAm-i, CH.sub.2 OAm-t, CH.sub.2 OC.sub.6 H.sub.13 --n, ##STR43## CH.sub.2 OCH.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 CMe.dbd.CH.sub.2, CH.sub.2 OCHMeCH.dbd.H.sub.2, CH.sub.2 OCH.sub.2 C.tbd.CH, CH.sub.2 OCH.sub.2 CH.sub.2 F, CH.sub.2 OCH.sub.2 CF.sub.3, CH.sub.2 OCH.sub.2 CH.sub.2 Cl, CH.sub.2 OCH.sub.2 Cl.sub.3, CH.sub.2 OCH.sub.2 CH.sub.2 Br, ##STR44## CH.sub.2 OCH.sub.2 CCl.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 CC.dbd.CHCl, CH.sub.2 OCH.sub.2 CH.sub.2 OMe, CH.sub.2 OCH.sub.2 CH.sub.2 OEt, CH.sub.2 OCH.sub.2 CH.sub.2 OPr-i, ##STR45## ##STR46## CH.sub.2 OPh, CH.sub.2 OPh-Cl-4, CH.sub.2 OPh-NO.sub.2 -4, CH.sub.2 NHMe, CH.sub.2 NHEt, CH.sub.2 NMe.sub.2, CH.sub.2 Net.sub.2, CH.sub.2 NEtMe, CH.sub.2 OCH.sub.2 Ph, CH.sub.2 OCH.sub.2 COOMe, CH.sub.2 CH.sub.2 COOEt, CH.sub.2 OCHMeCOOMe, CH.sub.2 OCH.sub.2 COOBu-t, CH.sub.2 OCHMeCOOEt, CH.sub.2 CN, CH.sub.2 SMe, CH.sub.2 SEt, CH.sub.2 SPr-n, CH.sub.2 SPr-i, CH.sub.2 SBu-t, CH.sub.2 SCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 SCH.sub.2 C.sub.57 CH, ##STR47## CH.sub.2 SCH.sub.2 CH.sub.2 C, CH.sub.2 SOMe, CH.sub.2 SOEt, CH.sub.2 SO.sub.2 Me, CH.sub.2 SO.sub.2 Et, CH.sub.2 SO.sub.2 Pr-n, CH.sub.2 SO.sub.2 Pr-i, CH.sub.2 SCH.sub.2 CH.sub.2 OMe, CH.sub.2 SCH.sub.2 CH.sub.2 OEt, CH.sub.2 SPh, CH.sub.2 OAc, CH.sub.2 OCOEt, CH.sub.2 OCOPr-i, CH.sub.2 OSO.sub.2 Me, CH.sub.2 OSO.sub.2 Et, CH.sub.2 OCH.sub.2 CH.sub.2 CN, CHMeOH, CHMeOMe, CHMeOEt, CHMeOPr-n, CHMeOPr-i, CHMeOBu-n, CHMeOBu-i, CHMeOBu-s, CHMeOBu-t ##STR48## CHMeOCH.dbd.CH.sub.2, CHMeOCH.sub.2 CH.dbd.CH.sub.2, CHMeOCH.sub.2 C.tbd.CH, CHMeOCH.sub.2 CF.sub.2, CHMeOCH.sub.2 CH.sub.2 Cl, CHMeOCH.sub.2 CCl.sub.2, CHMeOCH.sub.2 CH.sub.2 Br, ##STR49## CHMeOCH.sub.2 CH.sub.2 OMe, CHMeOCH.sub.2 CH.sub.2 Et, ##STR50## CHMeOPh, CHMeNHMe, CHMeOCH.sub.2 COOMe, CHMeNMe.sub.2, CHMeNEt.sub.2, CHMeOCH.sub.2 COOEt, CHMeOCHM eCOOMe, CHMeCN, CHMeSMe, CHMeSEt, CHMeSPr-n, CHMeSPr-i, CHMeSCH.sub.2 CH.dbd.CH.sub.2, CHMeSCH.sub.2 C.tbd.CH, ##STR51## CHMeSCH.sub.2 CH.sub.2 Cl, CHMeSOMe, CHMeSOEt, CHMeSO.sub.2 Me, CHMeSO.sub.2 Et, CHMeSO.sub.2 Pr-i, CHMeSCH.sub.2 CH.sub.2 OMe, CHMeSPH, CHMeOAc, CHMeOCOEt, CHMeOSO.sub.2 Me, CHMeOSO.sub.2 Et, CHMeOCH.sub.2 CH.sub.2 CN, CMe.sub.2 OH, CMe.sub.2 OMe, CMe.sub.2 OE, CMe.sub.2 OPr-n, CMe.sub.2 OPr-i CMe.sub.2 OCH.dbd.CH.sub.2, CMe.sub.2 OCH.sub.2 CH.dbd.CH.sub.2, CMe.sub.2 OCH.sub.2 C.tbd.CH, CMe.sub.2 OCH.sub.2 CH.sub.2 Cl, CMeOCH.sub.2 CH.sub.2 OMe, ##STR52## CMe.sub.2 NHMe, CMe.sub.2 NMe.sub.2 CMe.sub.2 OCH.sub.2 COOMe, CMe.sub.2 CN, CMe.sub.2 SMe, CMe.sub.2 SEt CMe.sub.2 OCH.sub.2 COOMe, CMe.sub.2 CN, CMe.sub.2 SMe, CMe.sub.2 SEt, CMe.sub.2 SO.sub.2 Me, CMe.sub.2 SO.sub.2 Et, CMe.sub.2 OAc, CMe.sub.2 OSO.sub.2 Me, CH.sub.2 COOMe, CH.sub.2 COOEt, CH.sub.2 COOPr-i, CHMeCOOMe, CHMeCOOEt, CHMeCOOPr-i, CH.sub.2 CH.sub.2 COOMe, CH.sub.2 CH.sub.2 COOEt, CH.sub.2 CH.sub.2 COOPr-i, CH.dbd.CHOMe, CH.dbd.CHOEt, CH.dbd.CHOPr-i, COOH, COOMe, COOEt, COOPr-n, COOPr-i, COOBu-n, COOBu-s, COOBu-i, COOBu-t, COOAm-i, ##STR53## COOCH.sub.2 CH.dbd.CH.sub.2, COOCH.sub.2 C.tbd.CH, COOCH.sub.2 CMe.dbd.CH.sub.2, COOCH.sub.2 Br, COOCH.sub.2 CH.sub.2 Cl COOCH.sub.2 CH.sub.2 F, COOCH.sub.2 CCl.sub.3, COOCH.sub.2 CHF.sub.2, COOCH.sub.2 CF.sub.3, ##STR54## COOCH.sub.2 CCl.dbd.CH.sub.2, COOCH.sub.2 CCl.dbd.CHCl, COOCH.sub.2 OMe, COOCH.sub.2 CH.sub.2 OMe, COOCH.sub.2 OEt, COOCH.sub.2 OEt, COOCH.sub.2 SMe, COOCH.sub.2 CH.sub.2 SMe, COOCH.sub.2 CH.sub.2 SEt, COOCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 Cl, COOCH.sub.2 SOMe, COOCH.sub.2 CH.sub.2 SOMe, COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl, COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Br, COOCH.sub.2 CH.sub.2 OSO.sub.2 Me, COOCH.sub.2 CH.sub.2 OSO.sub.2 Ph-Me-4, COOCH.sub.2 OCH.sub.2 CH.sub.2 OMe, COOCH.sub.2 CH.sub.2 SO.sub.2 Me, COOCH.sub.2 CH.sub.2 SO.sub.2 Et, COOCH.sub.2 SO.sub.2 Me, COOCH.sub.2 CN, COOCH.sub.2 CH.sub.2 CN, COOCH.sub.2 CH.sub.2 CH.sub.2 CN, COOCH.sub.2 CH.sub.2 NHMe, COOCH.sub.2 CH.sub.2 NMe.sub.2, COOCH.sub.2 NMe.sub.2, COOCH.sub.2 CH.sub.2 NO.sub.2, COOCH.sub.2 CH.sub.2 CH.sub.2 NO.sub.2, COOCH.sub.2 OH, ##STR55## COOCH.sub.2 COMe, COOCH.sub.2 COBu-t, COOCH.sub.2 COPr-i, COOCH.sub.2 COPh, COOCH.sub.2 COOMe, COOCH.sub.2 COOEt, COOCHMeCOOMe, COOCMe.sub.2 OOMe, COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2, COOCH.sub.2 CH.sub.2 OCH.sub.2 C.tbd.CH, COOCH.sub.2 CH.sub.2 OPh, COOCH.sub.2 OPh, COOCH.sub.2 CH.sub.2 OCH.sub.2 Ph, COOCH.sub.2 SiMe.sub.3, COOSiMe.sub.2, COOSiEt.sub.3, COOPh, COOPh-Cl-4, COOPh-Me-4, COOPh-OMe-4, COOPh NO.sub.2 -4, COOCH.sub.2 Ph, COOCH.sub.2 Ph-Cl-2, COOCH.sub.2 Ph-Cl-4, COOCHMePh, COOCH.sub.2 CH.sub.2 Ph, ##STR56## C(O)SMe, C(O)SEt, C(O)SPr-i, C(O)SPr-n, C(O)SBu-n, C(O)SBu-t, C(O)SBu-s, C(O)SBu-i, C(S)OMe, C(S)OEt, Cl(S)OPr-i, C(S)OPr-n, C(S)OBu-n, C(S)OBu-t, C(S)OBu-s, C(S)OBu-i, CSSMe, CSSEt, CSSPr-n, CSSPr-i, CONMe.sub.2, CONHMe, CONEt.sub.2, CONHEt, CONHPr-n, CONHPr-i, CONHBu t, CONHBu-s, CONHBu-i, CONHBu-n, CONHAm t, CONHPr.sub.2 -i, CONPr.sub.2 -n, CONHPh, CONHPh-Me-4, CONHPh-NO.sub.2 -4, ##STR57## CONMeOMe, CONHCH.sub.2 CH.dbd.CH.sub.2, CON(CH.sub.2 CH.dbd.CH.sub.2).sub.2, CONHCH.sub.2 C.tbd.CH, CON(CH.sub.2 C.tbd.CH).sub.2, CONMePh, CONMePh, CONEtPh, CON(Me)Ph-Me-4, CONHSO.sub.2 Me, CONHSO.sub.2 CF.sub.2, COON=CMe.sub.2, ##STR58## COOCH.sub.2 OCOMe, COOCH.sub.2 OCOBu-t, Z : F, Cl, Br, I, NO.sub.2, OMe, OEt, OPr-n, OPr-i, CF.sub.3, CN, SMe, SOMe, So.sub.2 Me, SCF.sub.2, SOCF.sub.3, SO.sub.2 CF.sub.3
  • Q: H, Me, Et, n-Pr, i-Pr, N-Bu, i-Bu, s-Bu, t-Bu, CH.sub.2 CH.sub.2 Cl, CH.sub.2 CF.sub.2, CHClMe, CH.sub.2 CH.sub.2 Br, CHClCH.sub.2 Cl, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 CMe.dbd.CH.sub.2, CH.sub.2 CH.dbd.CHMe, CH.sub.2 C.tbd.CH, CH.sub.2 CCl.dbd.CH.sub.2, CH.sub.2 CN, CH.sub.2 Ph, CH.sub.2 Ph Cl-2 , CH.sub.2 Ph-Cl-3, CH.sub.2 Ph-Me-.sub.2, ##STR59## CH.sub.2 Ph-Me.sub.2 -2,4, CH.sub.2 Ph-Me-4, CHMePh, CHEtPh, CH.sub.2 Ph NO.sub.2 -2, CH.sub.2 Ph-CF.sub.3 -3, CH.sub.2 OMe, CH.sub.2 OEt, CH.sub.2 OH, CHMeOH, CH.sub.2 NHMe, CH.sub.2 NMe.sub.2, CHMeNMe.sub.2, CH.sub.2 COPh, CH.sub.2 COPh-NO.sub.2 -4, CH.sub.2 COPh-Me-4, CH.sub.2 COPh-Cl-4, CH.sub.2 COPh-Me-.sub.2 2,4, CH.sub.2 COPh-CF.sub.3 -4, CH.sub.2 Ac, CH.sub.2 COEt, CHMeAc, CH.sub.2 CO.sub.2 Me, CH.sub.2 CO.sub.2 Et, CH.sub.2 CO.sub.2 Pr-n, CH.sub.2 CO.sub.2 Pr-i, CH.sub.2 CO.sub.2 Bu-t, CH.sub.2 Co.sub.2 H, CHMeCO.sub.2 H, CH.sub.2 CONHMe, CH.sub.2 CONHMe.sub.2, CH.sub.2 CONHEt, CH.sub.2 CONEt.sub.2, CH.sub.2 CONPr-n.sub.2, CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 OAc, CH.sub.2 COEt, CH.sub.2 COPr-i, CH.sub.2 COBu-t, CH.sub.2 OCO.sub.2 Me, CH.sub.2 OCO.sub.2 Et, CH.sub.2 OCO.sub.2 Pr-i, CH.sub.2 OCO.sub.2 Bu-t, CH.sub.2 SMe, CH.sub.2 SEt, CH.sub.2 SCH.sub.2 CH.dbd.CH.sub.2 , CH.sub.2 SAc, CH.sub.2 SCOBu-t, CH.sub.2 SO.sub.2 Me, CH.sub.2 SO.sub.2 Et, CH.sub.2 SO.sub.2 CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 NHCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 NMeCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 NHAc, CH.sub.2 NHCOEt, CH.sub.2 NHCO.sub.2 Me, CH.sub.2 NHCO.sub.2 Et, CH.sub.2 NMeCO.sub.2 Me, COPh, COPh-Me-4, COPh-NO.sub.2 -.sub.2, COPh-Cl.sub.2 -2,4, Ac, COEt, COPr-n, COPr-i, COBu-n, COBu-t, COCH.sub.2 Cl, COCHCl.sub.2, COCCl.sub.2, COCF.sub.2, COCH.sub.2 OMe, COCH.sub.2 OPh, COCH.sub.2 CH.dbd.CHCH.sub.2, CO.sub.2 Me, CO.sub.2 Et, CO.sub.2 Bu-t, CO.sub.2 Pr-i, CONHMe, CONMe.sub.2, CONHEt, CONEt.sub.2, CONPr-n.sub.2, CON(CH.sub.2 CH.dbd.CH.sub.2).sub.2, CONMePh, ##STR60## CO.sub.2 CH.sub.2 Ph, CO.sub.2 Ph, SO.sub.2 Me, SO.sub.2 Et, SO.sub.2 CH.sub.2 CH.dbd.CH.sub.2, SO.sub.2 Ph, SO.sub.2 Ph-Me-4, SO.sub.2 Ph-Cl-4, SO.sub.2 Ph-(NO.sub.2).sub.2 -2, 4, SO.sub.2 CF.sub.3, P(.dbd.0)(OMe).sub.2, F(.dbd.0)(OEt).sub.2, P(.dbd.0)(OlPr-n).sub.2, P(.dbd.0)(OPr i).sub.2, P(.dbd.S)(OMe).sub.2, P(.dbd.S)(OEt).sub.2, P(.dbd.0)OMeOPh, P(.dbd.0)(OCH.sub.2 CH.dbd.CH.sub.2).sub.2, P(.dbd.0)OPhOCH.sub.2 CH.dbd.CH.sub.2
  • 3. The pyrazole derivative according to claim 1, wherein v and w are hydrogen atoms, and A, B, X, Y, Z and Q in the formula I are respectively selected from the following substituents:
  • A: Me, Et, n Pr, i-Pr, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 C.tbd.CH
  • B: H, Me,
  • X: Me Et, i-Pr, OMe, OEt, OPr-i, F, Cl, Br, I, NO.sub.2, CN, OBU-t, CF.sub.3, CH.sub.2 OMe, Ac, COOMe, COOEt, COOPr-i, OCHF.sub.2, OCF.sub.3, OCH.sub.2 CF.sub.3, SMe, CH.sub.2 SMe,
  • Y: CH.sub.2 OMe, CH.sub.2 OEt, CH.sub.2 OPr-n, CH.sub.2 OPr-i, CH.sub.2 OBu-t, CH.sub.2 OAm-n, CH.sub.2 OCH.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 OCH.sub.2 C.tbd.CH, CH.sub.2 OCH.sub.2 CF.sub.3, CH.sub.2 OCH.sub.2 CH.sub.2 Cl, CH.sub.2 OCH.sub.2 CH.sub.2 OMe, Ch.sub.2 NMe.sub.2, CH.sub.2 SMe, CH.sub.2 SEt, CH.sub.2 SOMe, CH.sub.2 SOEt, CH.sub.2 SO.sub.2 Me, CH.sub.2 SO.sub.2 Et, CH.sub.2 OAc, CH.sub.2 OSO.sub.2 Me, CH.sub.2 OCH.sub.2 CH.sub.2 CN, CH.sub.2 OCH.sub.2 COOBu-t, CHMeOMe, CHMeOEt, CHMeOAc, CHMeOSO.sub.2 Me CMe.sub.2 OMe, CMe.sub.2 OEt, CH.sub.2 CO.sub.2 Me, CH.sub.2 CO.sub.2 Et, CH.dbd.CHOMe, CH.dbd.CHOEt, CH.sub.2 CH.sub.2 COOMe, CH.sub.2 CH.sub.2 COOEt,
  • Z: F, Cl, Br, I, NO.sub.2, OMe, CF.sub.3, CN, SMe, SOMe, SO.sub.2 Me, SCF.sub.3, SOCF.sub.3, SO.sub.2 CF.sub.3
  • Q: H, --CH.sub.2 Ph, CH.sub.2 COPh, SO.sub.2 (4-Me-phenyl) CH.sub.2 OC(O)Bu-t, CH.sub.2 COMe, CH.sub.2 OMe, CH.sub.2 CO(4-Me-phenyl), CH.sub.2 COOH
  • 4. The pyrazole derivative according to claim 1, wherein v and W are hydrogen atoms, and A, B, X, Y, Z and Q in the formula I are respectively selected from the following substituents:
  • A: Me, Et, n-Pr, i-Pr, CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 CH
  • B: H, Me,
  • X: Me, Et, i-Pr, OMe, OEt, OPr-i, F, Cl, Br, I, NO.sub.2, CN, OBu-t, ClF.sub.3, CH.sub.2 OMe, Ac, COOMe, COOEt, COOPr-i, OCHF.sub.2, OCF.sub.3, OCH.sub.2 CF.sub.3, SMe, CH.sub.2 SMe,
  • Y: COOMe, COOEt, COOPr-n, COOPr-i, COOBu-t, COOAm-i, COOCH.sub.2 CH.dbd.CH.sub.2, COOCH.sub.2 C.tbd.CH, COOCH.sub.2 CH.sub.2 Cl, COOCH.sub.2 CF.sub.3, COOCH.sub.2 CH.sub.2 OMe, COOCH.sub.2 CH.sub.2 CN COOCH.sub.2 COOMe, COOCH.sub.2 COOEt, COOCH.sub.2 COOPr-i, COOCH.sub.2 COOBu-t, CONMe.sub.2, COON.dbd.CMe.sub.2, CH.sub.2 COOMe, CH.sub.2 COOEt, CH.sub.2 CH.sub.2 COOMe, CH.sub.2 CH.sub.2 COOEt, CH.dbd.CHOMe, CH.dbd.CHOEt
  • Z: F, Cl, Br, I, NO.sub.2, OMe, CF.sub.3, CN, SMe, SOMe, SO.sub.2 Me, SCF.sub.3, SOCF.sub.3, SO.sub.2 CF.sub.3
  • Q:H, --CU.sub.2 Ph, CU.sub.2 COPh, SO.sub.2 (4-Me-Phenyl) CH.sub.2 OC(O)Bu-t, CH.sub.2 COMe, CH.sub.2 OMe, CH.sub.2 CO(4-Me-Phenyl), CH.sub.2 COOH
  • 5. The pyrazole derivative according to claim 1, which has the formula: ##STR61## wherein A is an alkyl group having from 1 to 3 carbon atoms; B is a hydrogen atom or a methyl group; X is an alkyl group having from 1 to 3 carbon atoms, an alkoxy group having from 1 to 3 carbon atoms or a halogen atom; Y is an alkoxycarbonyl group having from 1 to 3 carbon atoms, a --CH.sub.2 --O--R group (wherein R is an alkyl group having from 1 to 3 carbon atoms) or a --CH(CH.sub.3)--O--R group (wherein R is as defined above); Z is a --S(O).sub.n CH.sub.3 group (wherein n is an integer of from 0 to 2); V and W are hydrogen atoms; and Q is a hydrogen atom, a benzyl group, a phenacyl group or a tosyl group, and a salt thereof.
  • 6. The pyrazole derivative according to claim 1, which is
  • 5-hydroxy-4-(4-methanesulfonyl-3-methoxymethyl-methylbenzoyl)-1-methylpyrazole,
  • 1-ethyl-5-hydroxy-4-(4-methanesulfonyl-3-methoxymethyl-2-methylbenzoyl)pyrazole,
  • 5-hydroxy-1-isopropyl-4-(4-methanesulfonyl-3l-methoxymethyl-2-methylbenzoyl)pyrazole,
  • 5-hydroxy-4-(4-methanesulfonyl-3-methoxycarbonyl-methylbenzoyl)-1-methylpyrazole,
  • 1-ethyl-5-hydroxy-4-(4-methanesulfonyl-3-methoxycarbony-2-methylbenzoyl)pyrazole, 4-(3-ethoxycarbonyl-4-methanesulfonyl-2-methylbenzoyl)-5-hydroxy-1-methylpyrazole,
  • 4-(3-ethoxycarbonyl-4-methanesulfonyl-2-methylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 5-hydroxy-4-(3-isopropoxycarbonyl-4-methanesulfonyl-2-methylbenzoyl)-1-methylpyrazole,
  • 1-ethyl-5-hydroxy-4-(3-isopropoxycarbonyl-4-methanesulfonyl-2-methylbenzoyl)pyrazole,
  • 4-(2,4-dichloro-3-methoxycarbonylbenzoyl)-5-hydroxy-1-methylpyrazole,
  • 4-(3-ethoxymethyl-4-methanesulfonyl-2-methylbenzoyl)-5-hydroxy-1-methylpyrazole,
  • 3-ethoxymethyl-4-methanesulfonyl-2-methylbenzoyl)-1-ethyl-5-hydroxypyrazole
  • 4-(3-ethoxymethyl-4-methanesulfonyl-2-methylbenzoyl)-5-hydroxy-1-isopropylpyrazole,
  • 1,3-dimethyl-4-(3-ethoxymethyl-4-methanesulfonyl-2-methylbenzoyl)-5-hydroxypyrazole,
  • 5-hydroxy-4-[4-methanesulfonyl-3-(1-methoxyethyl)-2-methylbenzoyl]-1-methylpyrazole,
  • 1-ethyl-5-hydroxy-4-[4-methanesulfonyl-3-(1-methoxyethyl)-2-methylbenzoyl pyrazole,
  • 4-(2-chloro-4-methanesulfonyl-3- methoxymethylbenzoly-5-hydroxy-1-methylpyrazole,
  • 4-(2-chloro-4-methanesulfonyl-1-methoxymethylbenzoyll)-1-ethyl-5-hydroxypyrazole,
  • 4-(2-chloro-4-methanesulfonyl-1-methoxymethylbenzoyl)-5-hydroxy-1-isopropylpyrazole,
  • 1-ethyl-5-hydroxy-4-(3-isopropoxymethyl-4-methanesulfonyl-2-methylbenzoyl)pyrazole,
  • 5-hydroxy-4-[4-methanesulfonyl-3-(2-methoxyethyl)oxycarbonyl-2-methylbenzoyl]-1-methylpyrazole,
  • 1-ethyl-5-hydroxy-4-[4-methanesulfonyl-3-(2-methoxyethyl)oxycarbonyl-2-methylbenzoyl]pyrazole,
  • 4-[2-chloro-4-methanesulfonyl-3-(2-methoxyethyl)oxymethylbenzoyl)-5-hydroxy-1-methylpyrazole,
  • 4-(2-chloro-3-ethylthiomethyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(2-chloro-3-ethanesulfinyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(2-chloro-3-ethanesulfonyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 1-ethyl-5-hydroxy-4-(3-n-propoxycarbonyl-4-methanesulfonyl-2-methylbenzoyl)pyrazole,
  • 4-(2-chloro-4-methanesulfonyl-3-methoxycarbonylbenzoyl)-5-hydroxy-1-methylpyrazole,
  • 4-(2-chloro-4-methanesulfonyl-3-methoxycarbonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(2-chloro-4-methanesulfonyl-3-methoxycarbonylbenzoyl)-5-hydroxy-1-isopropylpyrazole,
  • 4-[2-chloro-4-methanesulfonyl-3-(3-propargyl)oxymethylbenzoyl]-1-ethyl-5-hydroxypyrazole,
  • 5-hydroxy-4-(4-methanesulfonyl-2-methoxy-3-methoxycarbonylbenzoyl)-1-methylpyrazole,
  • 4-(2-chloro-4-methanesulfonyl-3-isopropoxycarbonylbenzoyl)-5-hydroxy-1-methylpyrazole,
  • 4-(2-chloro-4-methanesulfonyl-3-isopropoxycarbonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-[2-chloro-4-methanesulfonyl-3-(2,2,2-trifluoroethyl)oxymethylbenzoyl]-5-hydroxy-1-methylpyrazole,
  • 5-hydroxy-1-isopropyl-4-(4-methanesulfonyl-3-methoxycarbonyl-2-methylbenzoyl)pyrazole,
  • 5-hydroxy-4-(4-methanesulfonyl-2-methoxy-3methoxymethylbenzoyl)-1-methylpyrazole,
  • 4-[3-(2-chloroethyl)oxycarbonyl-4-methanesulfonyl-2-methylbenzoyl]-1-ethyl-5-hydroxypyrazole,
  • 1-ethyl-5-hydroxy-4-(4-methanesulfonyl-2-methoxy-3-methoxycarbonylbenzoyl)pyrazole,
  • 4(2,4-dichloro-3-methoxycarbonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(2,4-dichloro-3-methoxycarbonylbenzoyl)-5-hydroxy-1-isopropylpyrazole,
  • 4-(2-chloro-3-cyanomethyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(2-chloro-3-hydroxymethyl-4-methansulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(2,4-dichloro-3-methoxymethylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(.sub.2, 4-dichloro-3-methoxymethylbenzoyl)-5-hydroxy-1-methylpyrazole,
  • 4-[2-chloro-4-methanesulfonyl-3-(2-methoxyvinyl)benzoyl]-ethyl-5-hydroxypyrazole,
  • 5-benzyloxy-4-(.sub.2, 4-dichloro-3-methoxycarbonylbenzoyl)-1-ethylpyrazole,
  • 5-benzyloxy-4-(2, 4-dichloro-3-methoxycarbonylbenzoyl)-1-isopropylpyrazole,
  • 4-(2-chloro-3-ethoxycarbonyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole,
  • 4-(2-chloro-3-ethoxycarbonyl-4-methanesulfonylbenzoyl)5-hydroxy-1-isopropylpyrazole or
  • 4-(2-chloro-3-ethoxycarbonyl-4-methanesulfonylbenzoyl)-5-hydroxy-1-methylpyrazole.
  • 7. A selective herbicidal composition comprising a herbicidally effective amount of a pyrazole derivative of the formula I as defined in claim 1 or its salt and an agricultural carrier or diluent.
  • 8. A method for controlling weeds, which comprises applying a herbicidally effective amount of a pyrazole derivative of the formula I as defined in claim 1 or its salt to a locus to be protected.
Priority Claims (4)
Number Date Country Kind
62-61937 Mar 1987 JPX
62-179797 Jul 1987 JPX
62-247601 Sep 1987 JPX
63-5449 Jan 1988 JPX
Parent Case Info

This is a continuation-in-part of application Ser. No. 07/122,366, filed Nov. 18, 1987.

US Referenced Citations (6)
Number Name Date Kind
4146726 Konotsune et al. Mar 1979
4230481 Nishiyama et al. Oct 1980
4301293 Konotsune et al. Nov 1981
4406688 Konno et al. Sep 1983
4460597 Yanai et al. Jul 1984
4557753 Tanaka et al. Dec 1985
Continuation in Parts (1)
Number Date Country
Parent 122366 Nov 1987