Substituted phthalides and heterocyclic phthalides

The present invention concerns substituted phthalides and heterocyclic phthalides and derivatives thereof, processes for their production, compositions containing them and their use in agriculture.
More particularly, the invention concerns compounds of formula I ##STR1## wherein ring system A is selected from c) pyrazinyl-N-oxide
d) pyrimidinyl
e) pyrazinyl
f) 3- or 4- cinnolynyl or 2-quinoxalinyl, and
g) a five membered heteroaromatic ring comprising oxygen, sulphur or nitrogen as heteroatom(s) which ring may be fused to a benzene ring or may comprise nitrogen as an additional heteroatom.
R is cyano, formyl, CX.sub.1 X.sub.2 X.sub.3, a ketone forming group, a carboxyl group which may be in the form of the free acid or in ester or salt form, a thio-carboxyl group which may be in the form of the free acid or in ester form, a carbamoyl group or a mono- or di-substituted carbamoyl group, hydroxyalkyl, hydroxybenzyl, --CH.dbd.NOH, --CH.dbd.NO-lower alkyl, the group --CH.sub.2 --O--C(O)-- which bridges adjacent carbon atoms in ring A, or a ring C ##STR2## Y.sub.1, Y.sub.2 and Y.sub.3 are attached to carbon atoms and are independently hydrogen, halogen, hydroxy, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylsulfonyloxy, dialkylsulfamoyloxy, alkylsulfonyl, alkylsulfinyl, dialkylcarbamoyloxy, alkylthio, alkenylthio or alkynylthio each of which may in turn be substituted by 1 to 6 halogen atoms; dialkoxymethyl, conjugated alkoxy, hydroxyalkyl, carboxyl, acyl, acylalkyl, acyloxy, acyloxyalkyl, trialkylsilyloxy, trialkylsilyl, cyano, nitro, amino or substituted amino, aminosulfonyl; cycloalkyl, aryl, aralkyl, aralkenyl, aralkynyl, aryloxy, aralkoxy, arylsulfonyl, arylsulfinyl, arylthio or aralkylthio, each of which may be substituted by one to three substituents selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio, acyl, amino or substituted amino; a group ##STR3## wherein R' is hydrogen, lower alkyl, or lower alkoxy; or Y.sub.1 and R taken together on adjacent carbon atoms form a bridge having the formula ##STR4## wherein E is a direct bond or a 1 to 3 membered linking group with elements selected from methylene, substituted methylene, ##STR5## and oxygen, or Y.sub.1 and Y.sub.2 taken together on adjacent carbon atoms form a 3- to 5-membered bridge comprised of elements selected from methylene, substituted methylene, ##STR6## oxygen, and ##STR7## each of W.sub.1, W.sub.2, W.sub.3, W.sub.4 and W.sub.5 is independently CH, CR.sub.3 or nitrogen; W.sub.6 is NH, oxygen, sulfur, ##STR8## Z is a 2- or 3-membered bridge comprised of elements selected from methylene, substituted methylene, ##STR9## --N.dbd., oxygen and ##STR10## R.sub.1 and R.sub.3 each is independently hydrogen; halogen; alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio, each of which may in turn be substituted by 1 to 6 halogen atoms; cycloalkyl, heterocycloalkoxy, aryloxy, aralkoxy or aralkylthio each of which may be substituted by 1 to 3 substituents selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio, acyl, amino or substituted amino; aminoxy; substituted aminoxy; iminoxy; substituted iminoxy; amino; substituted amino; amido; substituted amido; alkylsulfonylmethyl; cyano; nitro; or ##STR11##
wherein Y.sub.4 is hydrogen, lower alkyl, lower alkoxy, hydroxy or unsubstituted or substituted phenyl.
R.sub.4 is as defined for Y.sub.1 except for hydrogen.
X and Y each is independently hydrogen, hydroxy, halogen, cyano, nitro, alkyl, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, hydroxyalkyl, haloalkyl, acyl, acyloxy, carbamoyl, carbamoyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylsulfonyloxy; aryl, aryloxy, arylS(O)p, aralkyl, aralkoxy, aralkS(O).sub.p, arylsulphonyloxy, each of which may in turn be substituted by 1 to 3 substituents selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio, acyl; amino, substituted amino or together represent .dbd.O, .dbd.S , .dbd.NH, .dbd.NOR.sub.12 or .dbd.CR.sub.13 R.sub.14 ; or
X and R together may form a bridge having the formula --O--E--, ##STR12## wherein the carbonyl is attached to A, E is defined above and R.sub.2 represents hydrogen, hydroxy, alkyl, haloalkyl, alkoxyalkyl, alkoxy, aralkoxy, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl or is as otherwise defined for R.sub.7 hereinafter.
P is 0, 1 or 2.
X.sub.1, X.sub.2 and X.sub.3 are independently hydrogen, hydroxy, alkoxy, alkylthio, hydroxyalkyl or hydroxybenzyl whereby at least one of X.sub.1, X.sub.2 and X.sub.3 is other than hydrogen; or X.sub.3 represents hydrogen and X.sub.1 and X.sub.2 together form a four or five membered bridge comprising elements selected from --O(CH.sub.2).sub.n,O--, ##STR13## and --S(CH.sub.2).sub.n,S--. R.sub.12 is hydrogen or alkyl,
R.sub.13 and R.sub.14 are independently hydrogen, alkyl or halogen,
m is one or two,
n' is two or three
with the proviso that when R is carboxyl in free ester or salt form and X and Y together are .dbd.O one of rings A and B contains a hetero atom.
When R is a ketone forming group this is preferably ##STR14## where R" is alkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl.
When R is a carboxyl or thio-carboxyl group in ester form it is preferably of formula --COOR.sub.5 or --COSR.sub.5 wherein R.sub.5 is alkyl, haloalkyl, alkoxyalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl, hydroxyalkyl, cycloalkyl, cyanoalkyl, aralkoxyalkyl; a group --N.dbd.C(R.sub.15)(R.sub.16); a group --(CH.sub.2).sub.n, CH(R.sub.17)(R.sub.18); a group ##STR15## R.sub.15 and R.sub.16 are independently hydrogen or alkyl, R.sub.17 and R.sub.18 are independently S(O).sub.n alkyl, COOR.sub.9, alkoxy, amino, substituted amino, benzyloxy, trimethylsilyl, cyano, --C(R.sub.19)SR.sub.20 or additionally one thereof may be hydrogen.
R.sub.19 is hydrogen or alkyl,
R.sub.20 is alkyl or aryl,
R.sub.9, R.sub.10 and R.sub.11 are independently hydrogen, alkyl, haloalkyl, alkoxyalkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl,
n and n" are independently zero, one or two, and
X.sub.4 is oxygen or sulfur.
When R is a carbamoyl group or a mono- or di-substituted carbamoyl group it is preferably of formula CONR.sub.7 R.sub.8 wherein R.sub.7 and R.sub.8 are independently hydrogen or an aliphatic or a saturated or unsaturated cyclic or heterocyclic group each of which may be unsubstituted or substituted.
R.sub.7 and R.sub.8 are preferably each independently a) hydrogen; halogen; b) alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkoxy, alkenyloxy, alkynyloxy, alkylS(O).sub.p, alkenylS(O).sub.p or alkynylS(O).sub.p, alkylS(O).sub.p alkyl, alkenylS(O).sub.p alkyl, alkylnylS(O).sub.p alkyl, each of which may in turn be substituted by 1 to 6 halogen atoms or hydroxy and each of which may be attached to the adjacent nitrogen atom via alkyl; c) acyl, acylalkyl, acyloxy or acyloxyalkyl; d) cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocycloalkyl, heterocycloalkoxy, aryl, aralkyl, aryloxy, aralkoxy, arylS(O).sub.p, aralkylS(O).sub.p or arylS(O).sub.p alkyl, each of which is unsubstituted or may be substituted by 1 to 3 substituents selected from (i) halogen; (ii) alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkoxy, alkenyloxy, alkynyloxy, alkylS(O).sub.p, alkenylS(O).sub.p or alkynylS(O).sub.p, alkylS(O).sub.p alkyl, alkenylS(O).sub.p alkyl, alkynylS(O).sub.p alkyl, each of which may in turn be substituted by 1 to 6 halogen atoms; and (iii) nitro, cyano, acyl, amino or substituted amino, aminosulfonyl; aminoalkyl or substituted aminoalkyl; e) amino, substituted amino, amido, substituted amido; aminosulfonyl, cyano, nitro; or ##STR16## wherein Y.sub.4 ' is hydrogen, lower alkyl, lower alkoxy or hydroxy and n'" is 0, 1, 2 or 3, and
p is 0, 1 or 2.
R.sub.4 ' is as defined for Y.sub.1.
X or Y as carbamoyl is also preferably of formula CONR.sub.7 R.sub.8 as defined above.
When R is carboxyl in salt form the salt is preferably formed with an alkali metal, alkali earth metal, optionally substituted ammonium cation, a trialkyl sulfonium cation, a trialkylsulfoxonium cation or a phosphonium cation, especially the cation of an alkali metal (e.g. the Li or Na cation) or of an earth alkali metal (e.g. the Ca or Mg cation); the ammonium cation; a substituted ammonium cation [such as a C.sub.1-5 alkylammonium cation, a di-C.sub.1-5 alkylammonium cation, a tri-C.sub.1-5 alkylammonium cation, a tetra-C.sub.1-5 ammonium cation, a (C.sub.1-5 alkoxy-alkyl)ammonium cation, a (hydroxy-C.sub.1-5 alkyl)ammonium cation]; a phosphonium cation; a tri(C.sub.1-8 alkyl)sulfonium cation; or a tri(C.sub.1-8 alkyl)sulfoxonium cation.
When Y.sub.1, Y.sub.2 and/or Y.sub.3 is a carboxyl group this may be in ester or salt form or in amide form (i.e. a carbamoyl) and as such is as described above for R in these forms. Where A has meaning g) it contains one to three heteroatoms and signifies for example thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl or thiadiazolyl.
Where A has one of the above defined heteroaromatic significances, b) through g), the substituted hetero ring is particularly selected from pyridyl, quinolyl, pyridyl-N-oxide, pyrimidinyl, pyrazinyl, thienyl or furyl, more particularly from pyridyl or thienyl.
Alkyl moieties unless otherwise specified contain 1 to 8 carbon atoms, preferably 1 to 5, especially 1 to 4, e.g. 1 or 2 carbon atoms. Lower alkyl moieties contain 1 to 4, e.g. 1 or 2 carbon atoms. Alkyl moieties as are present in R.sub.5, R.sub.7 or R.sub.8 contain 1 to 24 preferably 1 to 12, especially 1 to 6 carbon atoms whereby one of R.sub.7 and R.sub.8 is preferably hydrogen when the other is alkyl.
Alkyl moieties as bridging groups may be straight chain or branched and preferably contain 1 to 4, e.g. 1 or 2 carbon atoms. They may be optionally substituted by aryl or substituted aryl and may optionally be interrupted by or attached via an oxygen or sulfur atom.
"Conjugated alkoxy" stands for an alkoxy group interrupted in its alkyl moiety by one or more oxygen atoms eg alkoxyalkoxy, alkoxyalkoxyalkoxy, etc.
Alkenyl and alkynyl moieties contain 2 to 8, preferably 2 to 4, especially 2 or 3 carbon atoms.
Halogen is preferably F, Cl or Br, especially Cl
Aryl moieties are preferably as defined for meanings a) to g) of ring system A or as ring B and preferred meanings of each, especially phenyl. Such aryl moieties may be unsubstituted or substituted and in the latter case carry 1 to 3 substituents as defined for Y.sub.1 unless otherwise specified. Substituted amino, -amido, -aminoxy, -aminoalkyl, -iminoxy, -carbamoyl (other than as R) is preferably substituted by one or two substituents selected from alkylalkoxy, haloalkl, acyl, alkoxyalkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl.
Substituted methylene is preferably substituted by one or two groups as defined for Y.sub.1.
Acyl as or as part of a substituent is conveniently ##STR17## wherein R'" is as defined for Y.sub.1 [for example alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, unsubstituted or substituted aryl (especially phenyl)]. Examples of acyl include acetyl, propionyl, butyryl, unsubstituted or substituted benzoyl, pivaloyl or chloracetyl, especially acetyl or unsubstituted or substituted benzoyl.
Cycloalkyl is preferably of 3 to 6 carbon atoms especially cyclopropyl, cyclopentyl or cyclohexyl, heterocyclo is preferably 5 or 6 membered and as defined for A definitions b) to g) and preferences or saturated and containing O, S or N as heteroatom, eg tetrahydrofuryl, piperidinyl, morpholinyl.
For convenience bridging members such as ##STR18## are so written but are to be understood as embracing ##STR19##
Carbamoyl or substituted carbamoyl moieties are attached to the molecule which they substitute via their carbonyl. Amido or substituted amido moieties are attached to the molecule which they substitute via their nitrogen atom.
A particular group of compounds of formula I (compounds Ia) comprises those wherein ring system A is selected from phenyl, pyridyl or pyridyl-N-oxide.
R is a carboxyl group which may be in the form of the free acid or in ester or salt form, a thiocarboxyl group which may be in the form of the free acid or in ester form, a carbamoyl group or a mono- or di-substituted carbamoyl group.
Y.sub.1, Y.sub.2 and Y.sub.3 are attached to carbon atoms and are independently hydrogen, halogen, alkyl, alkoxy;
each of W.sub.1, W.sub.2, W.sub.3, W.sub.4 and W.sub.5 is independently CH, CR.sub.3 or nitrogen;
W.sub.6 is NH or oxygen;
Z is a 2- or 3-membered bridge comprised of elements selected from methylene, substituted methylene or ##STR20## R.sub.1 and R.sub.3 each is independently hydrogen, halogen, alkyl, alkoxy, aryloxy or aralkoxy.
X and Y each is independently hydrogen, hydroxy, cyano, alkoxy, acyloxy or together represent .dbd.O; or
X and R together form a bridge having the formula ##STR21## wherein the carbonyl is attached to A.
When R is carboxyl or thio-carboxyl in ester form it is preferably of formula --COOR.sub.5 or COSR.sub.5 ;
wherein each R.sub.5 is independently alkyl, alkoxyalkyl, alkenyl, alkynyl, substituted aryl or unsubstituted or substituted aralkyl.
When R is carboxy or thiocarboxyl in salt form the salt is preferably formed with an alkali metal, alkali earth metal, optionally substituted ammonium cation especially the cation of an alkali metal (e.g. the Li or Na cation) or of an earth alkali metal (e.g. the Ca or Mg cation); the ammonium cation; a substituted ammonium cation [such as a C.sub.1-5 alkylammonium cation, a di-C.sub.1-5 alkylammonium cation, a tri-C.sub.1-5 alkylammonium cation, a tetra-C.sub.1-5 ammonium cation.
When R is carbamoyl or mono- or di-substituted carbamoyl it is preferably of formula CONR.sub.7 R.sub.8 wherein R.sub.7 is hydrogen, alkyl, haloalkyl, alkoxyalkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl and R.sub.8 is hydrogen, alkyl, NH.sub.2, NHR.sub.6 or OR.sub.6 wherein R.sub.6 is as defined for R.sub.7.
A particular compound group (compounds Ib) comprises those compounds of formula I wherein ring system A represents phenyl, pyridyl or thienyl; B represents pyrimidinyl or triazinyl; R represents a ring C especially oxazole, oxazolone, oxazolidine or oxazolidinone; carboxyl in the form of the free acid or in ester or salt form; substituted carbamoyl, cyano or together with X represent ##STR22## Y.sub.1, Y.sub.2 and Y.sub.3 each represent independently hydrogen, halogen, alkyl, alkoxy, alkylthio or arylthio.
X, Y each represent independently hydrogen, hydroxy, alkoxy, acyloxy, a ring B, halogen, alkylthio or arylthio or together .dbd.O or .dbd.NH
and R.sub.1 and R.sub.3 each represent independently halogen, alkoxy, alkyl, haloalkoxy, optionally substituted aryloxy, aralkoxy, alkylnyloxy, alkenyloxy.
A further compound group comprises compounds Ib wherein Y.sub.1, Y.sub.2 and Y.sub.3 additionally may each represent independently aralkoxy, alkenyloxy or alkynyloxy.
B is especially pyrimidinyl, particularly 4,6-dimethoxy-2-pyrimidinyl.
A is especially phenyl or pyridyl substituted as defined above.
X and Y are preferably hydrogen, halogen, cyano, hydroxy, alkoxy or together .dbd.O, especially hydrogen, hydroxy or together .dbd.O.
A further group of compounds according to the invention (Compounds Ic) comprises those of formula I wherein ring system A is pyridyl,
R is CONR.sub.7 'R.sub.8 '
wherein R.sub.7 ' and R.sub.8 ' represent independently hydrogen, alkoxy, alkyl; or aryl or aralkyl each of which may be unsubstituted or substituted,
X is hydrogen,
Y is OR.sub.3 ', SR.sub.3 ' or OCOR.sub.3 '
wherein R.sub.3 ' is alkyl; or aryl; or aralkyl each of which may be unsubstituted or substituted,
or X and Y together represent .dbd.O or .dbd.S and ring system B is m-CF.sub.3 phenyl.
Within the group Ib, compounds are preferred wherein X is OH and Y is H or X and Y together represent .dbd.O, A is 2- or 3-pyridyl, R.sub.7 is hydrogen or alkyl especially methyl, R.sub.8 is phenyl or benzoyl which may be unsubstituted or substituted eg 1-3 times by halogen, alkyl and/or alkoxy.
The following meanings are preferred independently for each substituent.
A
a) meanings a) and b)
b) phenyl
c) pyridyl
R
a) carboxyl in the form of the free acid or in salt or ester form or carbamoyl or mono- or di-substituted carbamoyl
b) COOR.sub.5 wherein R.sub.5 is hydrogen, alkyl, COO.sup.+ Ma.sup.- wherein Ma is an alkali metal or ammonium cation or CONR.sub.7 R.sub.8 wherein R.sub.7 is hydrogen or alkyl and R.sub.8 is alkyl, aryl or substituted aryl
c) COO.sup.- Na.sup.+, COOCH.sub.3, CONHC.sub.6 H.sub.13, CONH(CH.sub.3)phenyl, COO.sup.- H.sub.3 N.sup.+ iC.sub.3 H.sub.7, CON(CH.sub.3).sub.2, CONHCH.sub.3
Y.sub.1
a) hydrogen, halogen, alkyl or alkoxy
b) halogen, especially fluorine or chlorine
Y.sub.2, Y.sub.3
a) hydrogen or halogen, alkyl or alkoxy
b) hydrogen or halogen
c) chlorine
W.sub.1 N
W.sub.2
a) CH or N
b) CH
W.sub.3 CR.sub.3
W.sub.4 N
W.sub.5
a) CH or N
b) N
W.sub.6
a) O
b) NH
Z
a) elements selected from methylene, substituted methylene, ##STR23## b) ##STR24## X.sub.1, X.sub.2 a) alkoxy, especially methoxy
b) hydroxy
X.sub.3
a) hydrogen
b) alkoxy especially methoxy
R.sub.1, R.sub.3
a) alkoxy, especially methoxy
R.sub.4
a) halogen, especially chlorine
b) alkyl, especially methyl
R.sub.2
a) alkyl, especially methyl
b) hydrogen
R.sub.5
a) alkyl, alkenyl or alkynyl
b) C.sub.1-4 alkyl, especially methyl or ethyl
c) C.sub.2-4 alkenyl
d) C.sub.2-4 alkynyl, especially propargyl
R.sub.6, R.sub.7
a) alkyl
b) methyl, ethyl
R.sub.8
a) hydrogen
b) alkyl, especially methyl or ethyl
c) an aryl, especially a phenyl
R.sub.9, R.sub.10,
a) hydrogen or alkyl
R.sub.12, R.sub.15, R.sub.19
b) hydrogen or methyl
R.sub.11
a) alkyl
b) propyl (n-- or iso--)
Y.sub.4
a) alkyl or alkoxy
b) CH.sub.3 or CH.sub.3 O
R.sub.13, R.sub.14
a) hydrogen or halogen
b) hydrogen or fluorine
R.sub.16
a) alkyl
b) C.sub.1-4 alkyl, especially methyl or ethyl
R.sub.17
a) S(O).sub.n alkyl or COOR.sub.9
b) SO.sub.2 CH.sub.3 or COOCH.sub.3
R.sub.18
a) hydrogen
R.sub.20
a) alkyl or phenyl
b) methyl or phenyl
n
a) 2 b) 0
n'
a) 2 b) 3
n"
a) 1 b) 0
m
a) 1 b) 2
X
a) hydroxy
b) hydrogen
c) taken with Y, .dbd.O
d) acyloxy
e) alkoxycarbonyloxy
f) carbamoyloxy
g) sulphonyloxy
Y
a) taken with X, .dbd.O
b) hydrogen ##STR25## X+R R'
a) alkyl b) alkoxy
R"
a) alkyl
b ) methyl
R'"
a) alkyl
b) aryl, especially phenyl
Ring A, Ring B
a) at least one contains a heteroatom
b) ring A=a phenyl or a pyridine
ring B=a pyrimidine especially 3,5 dimethoxy pyrimidine
Combinations Of the above listed preferred meanings are especially preferred. One such combination comprises compounds of formula (I) in which
A is phenyl or pyridyl;
R is a carboxyl group in the form of a free acid, ester or salt; carbamoyl: especially COOR.sub.5 " wherein R.sub.5 " is C.sub.1-5 alkyl or C.sub.2-5 alkenyl or CONR.sub.7 "R.sub.8 " wherein
R.sub.7 " is C.sub.1-12 alkyl, amino, C.sub.1-4 alkylamino, anilino, haloanilino, benzyl, halobenzyl, C.sub.1-4 alkylbenzyl, C.sub.1-4 alkoxybenzyl, phenyl, halophenyl, C.sub.1-4 alkylphenyl or C.sub.1-4 alkoxyphenyl;
R.sub.8 " is hydrogen or C.sub.1-4 alkyl;
Y.sub.1, Y.sub.2 and Y.sub.3 are independently hydrogen or halogen;
W.sub.1 and W.sub.4 are N;
W.sub.2 is CH;
W.sub.3 is CR.sub.3 wherein R.sub.3 is C.sub.1-5 alkoxy;
R.sub.1 is C.sub.1-5 alkoxy;
X is hydroxyl or C.sub.1-4 alkoxycarbonyloxy or taken with Y is .dbd.O;
Y is hydrogen or taken with X is .dbd.O; or
X and R together form a bridge having the formula --C(O)O-- wherein the carbonyl is attached to A, and Y is hydrogen or C.sub.2-8 acyloxy.
A further group of compounds includes those of formula I wherein X may additionally represent COOR.sub.5 as defined above; and/or R.sub.15 and R.sub.16 may additionally independently represent halogen, alkylthio, alkoxycarbonyl or optionally substituted carbamoyl; and/or R.sub.18 may additionally represent optionally substituted aryl.
Further preferred substituent meanings include compounds according to claim 1 wherein A is other than phenyl, naphthyl, pyridyl which may be fused on its (b) or (c) side to benzene, or pyridyl-N-oxide.
Compounds according to claim 1 wherein R is other than formyl, a carboxyl group which may be in the form of the free acid or in ester or salt form, a thiocarboxyl group which may be in the form the free acid or in ester form or the group CX.sub.1 X.sub.2 X.sub.3.
Compounds according to claim 1 wherein R is other than formyl, dimethoxymethyl, COOR.sub.30 or COSR.sub.31 wherein R.sub.30 represents hydrogen, an alkali metal cation, an alkaline earth metal cation, an ammonium cation, an alkylammonium cation, C.sub.1-3 alkyl, C.sub.2-3 haloalkyl, allyl, propargyl, benzyl optionally substituted by halogen, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl or nitro, C.sub.2-4 alkoxyalkyl, N.dbd.CR.sub.32 R.sub.33, CH.sub.2 S(O).sub.t R.sub.34 or CH(CH.sub.3)S(O).sub.t R.sub.34 wherein R.sub.32 is chlorine, methyl, ethyl or methylthio, R.sub.33 is methyl, ethyl, COOCH.sub.3, COOC.sub.2 H.sub.5 or C(O)N(CH.sub.3).sub.2, R.sub.34 is methyl, ethyl, propyl, isopropyl or phenyl optionally substituted by halogen, methyl, methoxy or nitro and t is 0, 1 or 2; and R.sub.31 represents methyl, ethyl or benzyl.
Compounds of formula I wherein A is pyridyl or pyridyl-N-oxide and at least two of Y.sub.1, Y.sub.2 and Y.sub.3 are other than hydrogen.
Compounds of formula I wherein one of Y.sub.1, Y.sub.2 and Y.sub.3 is other than hydrogen, fluorine, chlorine, methyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl.
Compounds of formula I wherein A is phenyl and one of Y.sub.1, Y.sub.2 and Y.sub.3 is other than hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, C.sub.2-3 alkenyl, C.sub.2-3 alkynyl, SO.sub.(t) CH.sub.3, SO.sub.(t) C.sub.2 H.sub.5, nitro, phenoxy, C.sub.1-4 alkylcarbonyl, C(OCH.sub.3).sub.2 CH.sub.3 or C(SCH.sub.3).sub.2 CH.sub.3 and t is 0, 1 or 2.
Compounds of formula I wherein each of Y.sub.1, Y.sub.2 and Y.sub.3 is other than hydrogen.
Compounds of formula I wherein one of W.sub.1 and W.sub.4 is other than nitrogen.
Compounds of formula I wherein W.sub.2 is other than nitrogen or CH.
Compound of formula I wherein R.sub.1 is other than methoxy or ethoxy.
Compound of formula I wherein W.sub.3 is other than CR.sub.3 wherein R.sub.3 is methyl, ethyl, methoxy, ethoxy, difluormethoxy, or chlorine.
Compounds of formula I wherein both of X and Y are other than hydrogen.
Compounds of formula I wherein one of X and Y is other than hydrogen, fluorine, chlorine, methyl, hydroxy, cyano, carbamoyl, methylcarbamoyl, dimethylcarbamoyl or COOR.sub.35, wherein R.sub.35 is C.sub.1-3 alkyl, C.sub.2-5 haloalkyl, C.sub.3-5 alkenyl, C.sub.3-5 alkynyl, C.sub.2-5 alkoxyalkyl, or benzyl optionally substituted by methyl, methoxy, methylthio, trifluoromethyl, halogen or nitro.
Combinations of these further preferred meanings with each other and with those set out above also deserve mention.
Examples of preferred compounds according to the invention are compound nos. 13, 40, 53, 55, 58, 64, 77, 78, 82, 91, 103, 108, 110, 111, 124, 125, 130, 143, 149, 163, 170, 175, 183, 199, 204, 205, 211, 219, 220, 224, 228, 247, 249, 258, 262, 263, 265, 266, 267, 272, 273, 277, 286, 294, 302, 310, 385, 403, 413, 452, 454, 455, 456, 457, 464, 473, 477, 479, 480, 481, 483, 487, 489, 504, 510, 522, 528, 531, 532, 539, 545, 547, 571, 576, 584, 590, 591, 593, 594, 595, 599, 605, 606, 607, 608, 612 and 622.
Compounds having the formula ##STR26## especially those wherein X is CN and at least one of W.sub.1 and W.sub.4 is nitrogen may exist in the alternate tautomeric form ##STR27##
The compounds of formula I according to the invention may be prepared as follows.
a) when X and R combine to form a bridging group as defined above and Y is hydrogen, cyano, arylthio, arylsulfinyl or arylsulfonyl, reacting a compound of formula II ##STR28## wherein A is as defined above, Y' represents hydrogen, cyano, arylthio, arylsulfinyl or arylfulfonyl and Z.sub.1 represents oxygen, sulfur or NR.sub.2 wherein R.sub.2 is as defined above except for hydrogen, with a compound of formula III ##STR29## wherein W.sub.1, W.sub.2, W.sub.3, W.sub.4 are as defined above except that at least one of W.sub.1 and W.sub.4 is nitrogen and R.sub.21 represents methylsulfonyl, or halogen to obtain the corresponding compound of formula Ip ##STR30## b) treating a compound of formula Ip wherein Y' represents cyano or arylsulfonyl and Z' represents oxygen and the other symbols are as defined above.
(i) by hydrolysis to give a corresponding compound of formula I wherein R and X form a bridge and Y is hydroxy or a compound of formula I wherein X and Y together form .dbd.O
(ii) with an amine to give a corresponding compound of formula I wherein R is an optionally substituted carbamoyl group and X and Y together form .dbd.O
(iii) with a group
MOR.sub.22
wherein M is an alkali metal and R.sub.22 is alkyl, to give a corresponding compound wherein R and X form a bridge and Y is alkoxy
c) hydrolyzing a compound of formula Ip wherein Y' represents hydrogen and Z.sub.1 represents oxygen to give a compound of formula I wherein R is a carboxyl group optionally in salt form, X is hydrogen and Y is hydroxy
d) ring opening a compound of formula Ip wherein Y' represents hydroxy and Z.sub.1 represents oxygen to give a compound of formula I wherein R is a carboxyl group optionally in salt form and X and Y together are .dbd.O
e) esterifying a compound of formula I wherein R is a carboxyl group optionally in salt form and X and Y are .dbd.O to give the corresponding compound wherein R is a carboxyl group in ester form
f) halogenating a compound of formula Ip wherein Y' represents hydroxy to give a compound of formula I wherein X and R together form a bridging group and Y' is halogen
g) reacting a compound of formula Ip wherein Z.sub.1 is oxygen and Y' is halogen with a group R.sub.2 NH.sub.2 and a group HOR.sub.23 wherein R.sub.23 represents alkyl, acyl or aryl and R.sub.2 is as defined above to give the corresponding compound wherein Z.sub.1 is NR.sub.2 and Y' is alkoxy, aryloxy or acyloxy
h) oxidizing a compound of formula Ip wherein Y' represents hydrogen to give the corresponding compound wherein Y' represents hydroxy
i) reacting a compound of formula IV ##STR31## with a compound of formula V ##STR32## to produce a compound of formula Iq ##STR33## wherein A, R, R.sub.1, W.sub.1, W.sub.2, W.sub.3, W.sub.4, Y.sub.1, Y.sub.2 and Y.sub.3 are as defined above and X" and Y" are hydrogen and R.sub.24 is alkyl, especially methyl, cyanomethyl, alkoxycarbonylmethyl, carbamoylmethyl,
j) mono-or di-halogenating a compound of formula Iq wherein X" and Y" are hydrogen to produce the corresponding compound of formula Iq wherein one or both of X" and Y" are halogen
k) oxidizing a compound of formula Iq wherein X" and Y" are both hydrogen or X" is halogen and Y" is hydrogen to produce the corresponding compound wherein X" and Y" together represent .dbd.O or one represents hydrogen and the other represents hydroxy
l) alkylating a compound of formula Iq wherein X" represents hydrogen and Y" represents hydrogen to produce the corresponding compound wherein X" represents alkyl and Y" represents hydrogen
m) introducing an alkoxy or alkylthio group into a compound of formula Iq wherein X" represents halogen and Y" represents hydrogen to produce the corresponding compound wherein X" represents alkoxy or alkylthio and Y" represents hydrogen
n) acylating a compound of formula Iq wherein X" represents hydroxy and Y represents hydrogen to produce the corresponding compound wherein X" represents acyloxy and Y" represents hydrogen
o) reacting a compound of formula Ip wherein Z.sub.1 is oxygen and Y' is hydrogen with a group R.sub.7 NH2 wherein R.sub.7 is as defined above to give a compound of formula I wherein R is monosubstituted carbamoyl, X is hydrogen and Y is hydroxy
p) sulfonylating, carbamoylating, acylating or carbalkoxylating a compound of formula Ip wherein Z.sub.1 is oxygen and Y' is hydroxy to produce the corresponding compound of formula Ip wherein Y' represents sulfonyloxy, carbamoyloxy, acyloxy or alkoxycarbonyloxy
q) reacting a compound of formula Ip wherein Z.sub.1 is oxygen and Y' is halogen with a group R.sub.7 R.sub.8 NH wherein R.sub.7 and R.sub.8 are as defined above (R.sub.7 and R.sub.8 .noteq.H) to give a compound of formula I wherein R is disubstituted carbamoyl, and X and Y together represent .dbd.O.
r) oxidizing a compound of formula ##STR34## to give a corresponding compound of formula I wherein X and Y together represent .dbd.O.
s) reacting a compound of formula III with a compound of formula IV each as defined above to produce a compound of formula Iq wherein X" and Y" are hydrogen.
t) oxidizing a compound of formula I wherein X.dbd.Y.dbd.H to give a compound Ip wherein Z.sub.1 is oxygen and Y' is hydroxy.
u) reacting a compound of formula V ##STR35## with a compound of formula IV wherein R is cyano and R.sub.24 is halogen and oxidizing the product to give a compound of formula I where R is cyano and X and Y together represent .dbd.O or of formula Ip wherein Z.sub.1 represents .dbd.O and y.sup.1 is cyano.
and in each case recovering any compound wherein R is a carboxyl or thiocarboxyl group in free form or in ester form and any compound wherein R is carboxyl in free form or in salt form.
The following table is illustrative of suitable reaction conditions.
__________________________________________________________________________REACTION CONDITIONSReaction Reagents Solvents Temperature Others__________________________________________________________________________a) 1) a) base eg LDA 1) and 2) inert eg DMF, a) reduced eg -70.degree. or b) base eg NaH ether, cyclic ether eg THF b) R.T. 2) III .thrfore.b) i)1) base eg NaOH inert eg ether, R.T. cyclic ether eg THF or 2) acidity alcohol eg methanolb) ii) 1) amine inert eg ether, cyclic ether eg THFb) iii) MOR.sub.21 alcohol eg methanol, cyclic ether eg THFc) base eg LiOH water optionally with an alcohol or cyclic ether eg THF R.T.d) base eg NaOH as c) R.T.e) halide eg IR.sub.5 inert eg DMF, elevated eg base eg K.sub.2 CO.sub.3, NaH 2-butanone (MEK) 50-80.degree.f) halogenating inert eg chlorinated elevated eg agent eg SOCl.sub.2, DMF hydrocarbon eg CCl.sub.4 CH.sub.2 Cl.sub.2 40-80.degree.g) 1) R.sub.7 NH.sub.22 ; R.sub.23 OH as f) elevated eg 50-80.degree.h) 1) oxidizing agent 1), 2) and 3) inert eg elevated eg 50.degree. eg NaOCl H.sub.2 O optionally with alcoholo 2) base eg NaOH eg methanol R.T. 3) acid eg HCl cyclic ether eg THF R.T.i) 1) base eg LDA 1) anhydr. inert eg ether such reduced eg -30.degree. as cyclic ether eg THF 2) AcOH 2), 3) and 4) ether, H.sub.2 O R.T. 3) DDQ reduced eg 0.degree. 4) aq NaOH elevated eh 75.degree.j) NBS, benzoylperoxide inert eh halogenated elevated eg 75.degree. hydrocarbon such as CCl.sub.4k) A. when X" = halogen and Y" = H to give X + Y are = O DMSO, Na.sub.2 CO.sub.3 DMSO elevated eg 50-60.degree. B. when X- and Y" = H to give X" + Y" are = O a) SeO.sub.2 AcOH 110.degree., 1 hr; or b) t-butylhydro- CH.sub.3 CN 85.degree.; or peroxide Co.sub.2 (CO).sub.8 c) 1) Mn(OAc).sub.3 AcOH 25 .fwdarw. 100.degree. 2) H.sub.2 O C. when X" and Y" = H to give X" = OH, Y" = H i) nBuLi THF -78.degree. ii) t-butyl peroxy- THF -78.degree. .fwdarw. 20.degree. benzoate iii) BF.sub.3.MeOH toluene 40.degree. .fwdarw. 100.degree.l) base eg NaH, alkyl inert eg ether, THF 0.degree. .fwdarw. R.T. halidem) MOR.sub.22, MSR.sub.22 inert eg DMF, alcohol R.T. .fwdarw. 50.degree. eg NaOCH.sub.3 On) acyl chloride eg CH.sub.3 CCl inert eg ether, THF R.T. .fwdarw. 30.degree. or anhydride eg Ac.sub.2 O; pyridine amine eg triethylamineo) amine, eg .alpha.-methyl alcohol eg methanol R.T. .fwdarw. 80.degree. benzylamine or amine, eg aniline, inert eg toluene R.T. CH.sub.3 SO.sub.2 NH.sub.2 ; Me.sub.3 Al (catalyst) CH.sub.2 Cl.sub.2p) acylchloride eg acetyl- inert eg ether R.T. chloride, ethylchloro- THF, puridine formate or anhyydride; amine eg DMAP, triethylamine or isocyanate eg methylisocyanate; .thrfore. .thrfore. amine eg triethylamine or sulfonyl chloride eg methyl .thrfore. .thrfore. sulfonyl chloride; amine eg triethylamineq) R.sub.7 R.sub.8 NH, triethylamine, inert eg CH.sub.2 Cl.sub.2 .thrfore. DMAPr) i) m-chlorobenzoic acid inert eg CH.sub.2 Cl.sub.2 20.degree., 30 min ii) base eg NaOH inert eh cyclic ether 20.degree., 30 mins) 1) LDA THF -78.degree. 2) III THF -78.degree. .fwdarw. 20.degree.t) KMnO.sub.4 H.sub.2 O 100.degree. C.u) i) base eg K.sub.2 CO.sub.3, KOBu.sup.t, inert eg DMF, THF RT .fwdarw. 100.degree. C. NaH ii) oxidizing agent eh NaOCl water optionally with inert RT or H.sub.2 O.sub.2 /AcOH eg cyclic ether or CH.sub.3 CM__________________________________________________________________________
Processes a) through u) also form part of the invention.
The starting materials of formula II or III are either known or may be prepared analogously to known methods.
The compounds of formula I have herbicidal activity as observed after their pre-emergent or post-emergent application to weeds or a weed locus.
The term "herbicide" (or "herbicidal") refers to an active ingredient (or an effect) which modifies the growth of plants because of plant growth regulating or phytotoxic properties so as to retard the growth of the plant or damage the plant sufficiently to kill it.
Application of a compound of formula I is made according to conventional procedure to the weeds or their locus using a herbicidally effective amount of the compound, usually from 10 g to 10 kg/ha.
Compounds according to the invention may be used in the control of both broad-leaf and grassy weeds on both pre- and post-emergent application. Compounds may also exhibit selectivity in various crops and are thus suited for use in weed control in crops such as corn, cotton, wheat, soybean and rice.
The optimum usage of a compound of formula I is readily determined by one of ordinary skill in the art using routine testing such as greenhouse testing and small plot testing. It will depend on the compound employed, the desired effect (a phytotoxic effect requiring a higher rate than a plant growth regulating effect), the conditions of treatment and the like. In general satisfactory phytotoxic effects are obtained when the compound of formula I is applied at a rate in the range of from 0.01 to 5.0 kg, more preferably of from 0.05 to 2.5 kg per hectare, eg 0.05 to 5.0 kg per hectare, especially 0.1 to 2.5 kg per hectare.
The compounds of formula I may be advantageously combined with other herbicides for broadspectrum weed control. Examples of herbicides which can be combined with a compound of the present invention include those selected from the carbamates, thiocarbamates, chloroacetamides, dinitroanilines, benzoic acids, glycerol ethers, pyridazinones, semicarbazones, uracils and ureas for controlling a broad spectrum of weeds.
The compounds of formula I are conveniently employed as herbicidal compositions in association with agriculturally acceptable diluents. Such compositions also form part of the present invention. They may contain, aside from a compound of formula I as active agent, other active agents, such as herbicides or compounds having antidotal, fungicidal, insecticidal or insect attractant activity. They may be employed in either solid or liquid forms eg in the form of a wettable powder or an emulsifiable concentrate incorporating conventional diluents. Such compositions may be produced in conventional manner, eg by mixing the active ingredient with a diluent and optionally other formulating ingredients such as surfactants.
Agriculturally acceptable additives may be employed in herbicidal compositions to improve the performance of the active ingredient and to reduce foaming, caking and corrosion, for example.
The term "diluent" as used herein means any liquid or solid agriculturally acceptable material which may be added to the active constituent to bring it in an easier or improved applicable form, respectively, to a usable or desirable strength of activity. It can for example be talc, kaolin, diatomaceous earth, xylene or water.
"Surfactant" as used herein means an agriculturally acceptable material which imparts emulsifiability, spreading, wetting, dispersibility or other surface-modifying properties. Examples of surfactants are sodium lignin sulfonate and lauryl sulfate.
Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, for example the condensation product of formaldehyde with naphthylene sulphonate, an ethoxylated alkylphenol and an ethoxylated fatty alcohol.
In general, the formulations include from 0.01 to 90% by weight of active agent and from 0 to 20% by weight of agriculturally acceptable surfactant, the active agent consisting either of at least one compound of formula I or mixtures thereof with other active agents. Concentrate forms of compositions generally contain between about 2 and 90%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight of active agent.

Typical herbicidal compositions, according to this invention, are illustrated by the following Examples A, B and C in which the quantities are in parts by weight.
EXAMPLE A
Preparation of a Dust
10 Parts of a compound according to this invention and 90 parts of powdered talc are mixed in a mechanical grinder-blender and are ground until a homogeneous, free-flowing dust of the desired particle size is obtained. This dust is suitable for direct application to the site of the weed infestation.
EXAMPLE B
Preparation of a Wettable Powder
25 Parts of a compound according to this invention are mixed and milled with 25 parts of synthetic fine silica, 2 parts of sodium lauryl sulphate, 3 parts of sodium ligninsulphonate and 45 parts of finely divided kaolin until the mean particle size is about 5 micron. The resulting wettable powder is diluted with water before use to a spray liquor with the desired concentration.
EXAMPLE C
Preparation of Emulsifiable Concentrate (EC)
13.37 Parts of a compound according to this invention are mixed in a beaker with 1.43 parts of Toximul 360A (a mixture of anionic and non-ionic surfactants containing largely anionic surfactants), 5.61 parts of Toximul 360A (a mixture of anionic and non-ionic surfactants containing largely non-ionic surfactants), 23.79 parts of dimethylformamide and 55.8 parts of Tenneco 500-100 (predominantly a mixture of alkylated aromatics such as xylene and ethylbenzene) until solution is effected. The resulting EC is diluted with water for use.
The following examples are provided to illustrate the practice of the present invention. Temperature is given in degrees Celsius. Abbreviations used in this specification.
THF=tetrahydrofuran
LDA=lithium diisopropylamide
RT=room temperature
DMF=dimethylformamide
DDQ=2,3-dichloro-5,6-dicyanobenzoquinone
NBS=N-bromosuccinimide
DMSO=Dimethylsulfoxide
MEK=Methylethylketone
DMAP=4-Dimethylaminopyridine
Individual alkyl substituents listed in the following tables from A to F are in the "n" isomeric form unless otherwise indicated.
EXAMPLE 1
7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 6)
1.68 g (0.01 mol) of 7-chlorophthalide is added to 100 ml of dry THF and the mixture cooled to -70.degree. C. 6.8 ml (0.01 mol) of 1.5M LDA is then added over 3 minutes and the reaction mixture stirred at -70.degree. C. for 15 minutes. 2.18 g (0.01 mol) of 2-methylsulfonyl-4,6-dimethoxypyrimidine in 50 ml of THF is then added and the mixture stirred for 4 hrs with temperature being maintained at -75.degree. to -70.degree. C. The reaction mixture is neutralized with 1.5 g of NH.sub.4 Cl in 5 ml of water, warmed and concentrated on a rotovaporator. The concentrate is partitioned between CH.sub.2 Cl.sub.2 /H.sub.2 O (50 ml each) and the aqueous phase separated and treated with further 30 ml of CH.sub.2 Cl.sub.2. The combined CH.sub.2 Cl.sub.2 phases are washed with 30 ml of water, separated and concentrated. The concentrate was flash chromatographed on silica gel using 80/20 hexane/ethyl acetate (500 ml), 50/50 hexane/ethyl acetate (500 ml) and 80/20 acetone/methanol (500 ml) (30 fractions.times.50 ml). The title compound (fractions 9-23) was obtained after recrystallization from hexane/CH.sub.2 Cl.sub.2 as a white solid, m.p. 148.degree.-149.degree. C.
EXAMPLE 2
5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4-b] pyridine-7(5H)-one (Table B, cpd. no. 40)
A solution of 1.3 g (0.0096 mols) of furo[3,4-b]pyridine-7(5H)-one in 50 ml of dry THF is cooled to -75.degree. C. and 8 ml (0.0192 mols) of 2.5M LDA added dropwise over 5 minutes. The mixture is allowed to react for 1 hr at -75.degree. C. and 2.1 g (0.0096 mol) of 2-methylsulfonyl-4,6-dimethoxypyrimidine in 30 ml of dry THF added dropwise over 10 minutes. The mixture is allowed to warm to RT, 1.6 ml of HCl added and the THF evaporated off. The residue is dissolved in 75 ml of CH.sub.2 Cl.sub.2, washed with water (2.times.50 ml) and the organic phase concentrated to give a yellowish white gummy solid. This is chromatographed on a silica gel column using 50/50 hexane/ethyl acetate (500 ml), ethyl acetate (500 ml) and 80/20 acetone/methanol (1000 ml) (30 fractions). The crystalline residue (fractions 18-21) of the title product has m.p. of 167-168.degree. C.
EXAMPLE 3
7-chloro-3-methoxy-3-(4,6-dimethoxy-2-pyrimidinyl)-2-methyl-isoindol-1(3H)-one (Table C, cpd. no. 54)
A mixture of 0.5 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 30 ml of CCl.sub.4, 2 ml of SOCl.sub.2 and 4 drops of DMF is heated at 65.degree. C. for 11/2 hrs, cooled and excess SOCl.sub.2 and CCl.sub.4 removed on a rotovaporator. The residue is diluted with 20 ml of CH.sub.2 Cl.sub.2 and added to a mixture of 5 ml of 40% aq methylamine and 10 ml of methanol with stirring over 1/2 hr. The mixture is placed on a rotovaporator and the residue partitioned between 50 ml each of CH.sub.2 Cl.sub.2 and water. The organic phase is concentrated and flash chromatographed on silica gel using 50/50 hexane/ethyl acetate (800 ml), ethyl acetate (500 ml) and 80/20 acetone/methanol (200 ml) (30 fractions .times.50 ml). The product (fractions 19-21) was obtained as a yellow gum.
EXAMPLE 4
7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 13)
A mixture of 1.8 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 50 ml of 1% NaOH and 50 ml of THF are stirred at room temperature for 3 hrs. The THF is removed by evaporation and the mixture is diluted with water and extracted twice with ethyl acetate. The aqueous solution is acidified with 2N--H.sub.2 SO.sub.4. The resulting acid solution is extracted with 3.times.100 ml ethyl acetate and the organic phases combined, dried over Na.sub.2 SO.sub.4 and concentrated to give a pale yellow solid. This residue is taken up in ethyl acetate and treated with activated charcoal until the yellow base line material is removed to give the title product as a white solid m.p. 188.degree.-190.degree. C.
EXAMPLE 5
7-chloro-3-methoxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 30)
1.0 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide is slurried in 20 ml of methanol and the solution cooled with ice and 0.6 ml of sodium methoxide added dropwise. After stirring for 10 min a further 1 ml of sodium methoxide is added and stirring continued for 10 min and the mixture is then quenched with 2N H.sub.2 SO.sub.4. Methanol is removed on a rotovaporator and the residue partitioned between water and ethyl acetate. The organic phase is dried over Na.sub.2 SO.sub.4 and concentrated. Flash chromatography of the residue over silica gel using 25% ethyl acetate/hexane yields a white solid m.p. 180.degree.14 183.degree. C.
EXAMPLE 6
a) Methyl 2-chloro-6-(4,6-dimethoxy-2-pyrimidinylcarbonyl)benzoate (Table C, cpd. no. 55), and
b) 7-chloro-3-chloro-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 21)
A mixture of 0.7 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 30 ml of CCl.sub.4, 2 ml of SOCl.sub.2 and 4 drops of DMF are refluxed at 60.degree. for 11/2 hrs. The mixture is then cooled, excess SOCl.sub.2 and CCl.sub.4 removed on a rotovaporator. The residue is diluted with 20 ml of CH.sub.2 Cl.sub.2 and added to a stirred mixture of 10 ml of methanol and 2 ml of diethylamine. After 21/2 hrs the mixture is stripped on a rotovaporator to remove excess CH.sub.2 Cl.sub.2 and methanol and the residue partitioned between CH.sub.2 Cl.sub.2 (50 ml) and water (50 ml). The organic phase is separated, concentrated and the gummy residue flash chromatographed over silica gel using 80/20 hexane/ethyl acetate (500 ml), 60/40 hexane/ethyl acetate (500 ml) (28 fractions.times.50 ml). Fractions 18 to 20 yielded title compound a) and fractions 11 to 16 the compound b).
EXAMPLE 7
7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 27)
600 mg of 7-chloro-3-cyanophthalide are added to an ice-cold suspension of hexane washed 60% NaH (160 mg) in DMF (20 ml). After 15 min, 710 mg of 2-methylsulfonyl-4,6-dimethoxypyrimidine are added. After stirring at RT for 11/2 hr the mixture is poured onto 200 ml of ice/water acidified with 2N H.sub.2 SO.sub.4 and stirred. The precipitate is filtered and dried in a vacuum oven to yield the title product, m.p. 159.degree.-161.degree. C.
EXAMPLE 8
7-chloro-3,3-bis(4,6-dimethoxy-1,3,5-triazin-2-yl)phthalide (Table A, cpd. no. 36)
1.48 g of 7-chlorophthalide are dissolved in 80 ml of THF. The solution is cooled to -70.degree. C. and 1.5M LDA in THF (6 ml) is syringed in at -70.degree. C. over 3 min. Stirring is continued for 15 min at -70.degree., 1.54 g of 2-chloro-4,6-dimethoxy-1,3,5-triazine in 50 ml of THF added dropwise and the mixture is then allowed to warm to -20.degree.. The mixture is again cooled to -70.degree. and 1 ml of conc. HCl in 10 ml of water is added. The mixture is stirred for 25 min and allowed to warm to RT and the THF is removed by evaporation. The residue is partitioned between CH.sub.2 Cl.sub.2 and water (50 ml each) and the aqueous phase extracted with an additional 30 ml of CH.sub.2 Cl.sub.2. The combined organic phases are washed with 30 ml of water and concentrated to give a yellow gum. This is flash chromatographed on silica gel using 60/40 hexane/ethyl acetate (1000 ml), ethyl acetate (400 ml), 80/20 acetone/methanol (500 ml) (30 fractions.times.50 ml, 1.times.200 ml). Fractions 21 and 22 yielded a yellow gum which upon recrystallization from hexane yielded title product m.p. 126.degree.-127.degree. as a yellow solid.
EXAMPLE 9
Lithium 2-chloro-6-(4,6-dimethoxy-.alpha.-hydroxy-2-pyrimidinylmethyl)benzoate (Table C, cpd. no. 53)
A mixture of 1.0 g of 7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 0.136 g of LiOH.H.sub.2 O, 2 ml of water and 10 ml of methanol is stirred overnight at RT. The mixture is evaporated to dryness on a rotovaporator. Further drying in a drying pistol yield the title compound as a white solid, m.p. 153.degree.-157.degree. C.
EXAMPLE 10
Lithium 3-[(4,6-dimethoxy-.alpha.-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxylate (Table E, cpd. no. 64)
A mixture of 0.490 g of 5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4,b]-pyridine7(5H)-one, 0.0768 gm of LiOH.H.sub.2 O, 10 ml of methanol and 2 ml of water is stirred for 24 hrs under nitrogen at RT and the solvent stripped off. The yellowish solid is dried for a further 2 hrs to yield the title product, m.p. >250.degree. C. (decomp.).
EXAMPLE 11
Sodium 2-chloro-6-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]benzoate (Table C, cpd. no. 58)
1.24 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 154 mg NaOH, 25 ml THF and 25 ml water are mixed until a yellow homogenous solution is achieved. The solvents are stripped on a rotovaporator and then on a Kugelrohr at 100.degree. C. to produce the title compound as a yellow solid, m.p. 276.degree.-278.degree. C.
EXAMPLE 12
3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-pyridine-2-carboxylic acid (Table E, cpd. no. 63)
490 mg of 5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4-b]pyridine-7(5H)-one is dissolved in 50 ml of methanol and the mixture heated with stirring at 50.degree. C. until a homogenous solution is formed (ca 1/2 hr). 2.6 g of NaOCl is added dropwise and the solution heated for a further 1/2 hr at 55.degree. C. 0.208 g of 50% NaOH is added at 55.degree. and the mixture heated for a further 1/2 hr at this temperature and then cooled in an ice-bath and acidified with 1 ml conc. HCl The solvent is evaporated and the residue partitioned between 50 ml of CH.sub.2 Cl.sub.2 and 50 ml of water. The organic phase is concentrated to give a white solid, m.p. 71.degree.-73.degree..
EXAMPLE 13
2-[(4,6-dimethoxy-2-pyrimidinyl)-.alpha.-iminomethyl]benzoic acid (Table C, cpd. no. 51)
2.67 g of isopropyl 2-bromobenzoate are dissolved in 100 ml of dry diethylether, the solution cooled to -100.degree. C. and 6.6 ml of 1.6M n-butyl-lithium solution added. Stirring is continued for 10 min and 12 g of 2-cyano-4,6-dimethoxypyrimidine in 60 ml of diethylether is added over 2 min at -100.degree. C. The mixture is stirred for 1/2 hr at -80.degree. and then allowed to warm to RT. 3 g of NH.sub.4 Cl in 30 ml of water is added to the reaction mixture, cooled in an ice-bath. The ether layer is separated off, washed with water (2.times.30 ml) and concentrated. The gummy residue is dissolved in 20 ml of 85/15 hexane/ethyl acetate, and CH.sub.2 Cl.sub.2, and flash chromatographed on silica gel using 800 ml 85/15 hexane/ethyl acetate, 500 ml 1% methanol in ethyl acetate, 500 ml 5% methanol in ethyl acetate and 500 ml of 80/20 acetone/methanol (40 fractions at 50 ml; 1 at 200 ml). Fractions 7 to 10 yielded title compound which on recrystallization from CH.sub.2 Cl.sub.2 melted at 225.degree.-235.degree. C.
EXAMPLE 14
5-Chloro-5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4-b]pyridine-7(5H)-one (Table B, cpd. no. 68)
A mixture of 490 mg of 5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4,b]-pyridine-7(5H)one and 50 ml of methanol is heated at 55.degree. for 1/2 hour or until a homogenous solution is formed. 2.6 g of NaOCl (common house bleach) is added dropwise. The mixture is taken up in dichloromethane an the organic phase separated and evaporated to dryness to yield the title compound, mp 146.degree.-148.degree. C.
EXAMPLE 15
3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-pyridine-2-carboxylic acid (Table E, cpd. no. 63)
0.208 g of 50% NaOH is added at 55.degree. to a solution of 0.551 g of 5-chloro-5-(4,6- dimethoxy-2-pyrimidinyl )-furo[3,4,b]pyridine (Table B, cpd. no. 68) in 50 ml methanol. The mixture stirred for a further 1/2 hr at 55.degree., cooled in an ice-bath, acidified with 1 ml of concentrated HCl and the solvent evaporated. The residue is partitioned between 50 ml of CH.sub.2 Cl.sub.2 and 50 ml H.sub.2 O and the CH.sub.2 Cl.sub.2 layer concentrated to give 0.39 g of the title product as a white solid, m.p. 71.degree.-73.degree. C.
EXAMPLE 16
2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dichloropyrimidine (Table C, cpd. no. 61)
To a mixture of 1.25 g of 2-o-tolyl-4,4-dimethyl-oxazoline in 20 ml of ether under N.sub.2 atmosphere at -30.degree. C. is added by syringe 4.2 ml of 1.6M n-butyllithium in hexane with stirring which is continued for 1 hr at -10.degree. C. 0.98 g of 4,6-dichloropyrimidine in 20 ml of ether are added slowly to the reaction mixture which is then stirred at -45.degree. to -30.degree. C. for 30 min and at 0.degree. C. for a further 30 min. The reaction mixture is quenched with acetic acid (0.4 ml) and water (0.1 ml) in THF (1.3 ml) and then treated with 1.5 g of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in 6 ml of THF. The temperature is brought to RT and the mixture stirred for 5 min after cooling to 0.degree. C. 7.6 ml of 1N NaOH (cooled) are added and the mixture stirred for 5 min. The organic phase is separated and dried over Na.sub.2 SO.sub.4 filtered and the solvent removed. Following chromatography (10/90 ether/hexane) the title product is obtained.
EXAMPLE 17
2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dimethoxypyrimidine (Table C, cpd. no. 48)
To a solution of 1.7 g of 2(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dichloropyrimidine in 100 ml of methanol are added 2.18 g of 25% methanolic NaOCH.sub.3 and the mixture heated for 10 hrs at 65.degree. C. with stirring. The temperature is lowered to 60.degree. and stirring continued overnight. The solvent is stripped and the residue taken up in 80 ml of toluene and 50 ml of water. The toluene layer was separated and washed with 50 ml of water, separated and concentrated to give the title compound as a yellow oil.
EXAMPLE 18
2-(2-(4,4-dimethyl-oxazolin-2-yl)-.alpha.-bromobenzyl)-4,6-dimethoxy pyrimidine (Table C, cpd. no. 62)
0.55 g of 2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dimethoxypyrimidine, 0.30 g of a N-bromosuccinimide, 0.03 g of benzoyl peroxide are dissolved in 60 ml of CCl.sub.4 and heated under reflux overnight at 75.degree. C. The reaction mixture is filtered and the filtrate washed with 5% NaHCO.sub.3 solution (50 ml), 50 ml of water and the organic phase separated and concentrated to give the title compound.
EXAMPLE 19
2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzoyl)4,6-dimethoxypyrimidine (Table C, cpd. no. 49)
A mixture of 1.2 g of 2-(2-(4,4-dimethyl-oxazolin-2-yl)-.alpha.-bromobenzyl)-4,6-dimethoxy-pyrimidine and 2 g of Na.sub.2 CO.sub.3 in 30 ml of DMSO is heated with stirring at 50.degree.-60.degree. C. for 3 hrs. The mixture is poured into 150 ml of water and extracted with toluene. The toluene extract is washed twice with water (2.times.50 ml) separated and concentrated. The thus obtained gum is chromatographed with 800 ml of 80/20 hexane/ethyl acetate, 500 ml 70/30 hexane/ethyl acetate, 60/40 ml hexane/ethyl acetate (50 ml fractions) fractions 29 to 34 yielded the title compound.
EXAMPLE 20
2-chloro-6-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-benzoic acid dimethylamide (Table C, cpd. no. 57)
1.0 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide is dissolved in 15 ml of THF. 0.7 ml of a 40% aqueous dimethylamine solution is then added via syringe whereupon the solution darkens. Stirring is continued at R.T. for 15 minutes and the mixture diluted with water and partitioned between ethyl acetate and water. The organic phase is separated, washed with 2N H.sub.2 SO.sub.4, then brine, dried and concentrated. The residue is purified on silica gel, eluant 200 ml of 50% ethyl acetate/hexane then 100% ethyl acetate. Fractions 12 to 15 yielded the title compound, m.p. 141.degree.-142.degree. C.
EXAMPLE 21
3-acetoxy-7-chloro-3-(4,6-dimethyloxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 125)
1.1 g of 7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxy-phthalide is dissolved in 20 ml of pyridine and 0.3 ml of acetic anhydride added with stirring. After stirring for 20 min the mixture is poured into 2N HCl and extracted with two portions of ethyl acetate. The combined ethyl acetate extracts are washed once with 2N HCl, once with H.sub.2 O and once with brine and dried over magnesium sulfate. Filtration and evaporation produced the title compound as a white solid, m.p. 213.degree.-215.degree..
EXAMPLE 22
3-[(4,6-dimethoxy-.alpha.-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxamide (Table E, cpd. no. 82)
To a solution of 0.9 g of ammonia, in 15 ml of methanol, is added 0.5 g of 3[(4,6-dimethoxy-2-pyrimidinyl)-7-azaphthalide. After stirring for 2 hrs at RT, the methanol is removed under reduced pressure and the concentrate recrystallized from toluene to give the title compound as a white solid, m.p. 135.degree.-137.degree. C.
EXAMPLE 23
3[(4,6-dimethoxy-2-hydroxy-2-pyrimidinyl)methyl]pyridine-2-[carboxy-(4-isopropyl)anilide] (Table E, cpd. no. 183)
To a solution of 3 ml of 4-isopropylaniline in 50 ml of toluene is syringed in 4 ml of 15.6% trimethylaluminum in hexane at RT. The mixture is stirred for 0.5 hr at RT and 0.5 g of 3-[(4,6-dimethoxy-2-pyrimidinyl)-7-azaphthalide is added. The mixture is stirred for 2 hrs at RT and acidified with 30 ml of 10% hydrochloric acid at 5.degree.-10.degree. C. The toluene solution is separated, washed with 20 ml of 10% hydrochloric acid, 20 ml of 5% sodium carbonate and 20 ml of water, dried and concentrated. The concentrate is recrystallized from hexane to yield the title compound as a white solid, m.p. 113.degree.-114.degree. C.
EXAMPLE 24
3-[(4,6-dimethoxy-.alpha.-(ethoxycarbonyloxy)-2-pyrimidinyl)methyl]-pyridine-2-carboxamide (Table E, cpd. no. 129)
To a solution of 0.5 g of 3-[(4,6-dimethoxy-.alpha.-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxamide, 0.05 g of 4-(dimethylamino)pyridine, and 1 ml of triethylamine, in 20 ml of toluene and 10 ml of dichloromethane is added 1 ml of ethyl chloroformate at RT. After stirring for 1 hr at ambient temperature, the mixture is washed with water (2.times.30 ml), dried and concentrated on a rotoevaporator. The concentrate is digested with 1/1 mixture of hexane-toluene, 10 ml, at 50.degree. C., cooled to RT and filtered to isolate 0.45 g of the title compound as a yellow solid, m.p. 112.degree.-114.degree. C.
EXAMPLE 25
3-[(4,6-dimethoxy-.alpha.-benzoyloxy-2-pyrimidinyl)methyl]pyridine-2-(N,N-dibenzoyl)carboxamide (Table E, cpd. no. 159)
To a solution of 0.05 g of 3-[(4,6-dimethoxy-.alpha.-hydroxy-2-pyrimidinyl)methyl]-2-carboxamide, 0.5 g, 4-(dimethylamino)pyridine and 4 ml of triethylamine in 30 ml of dichloromethane is added 1.4 g of benzoyl chloride at RT in two portions. The reaction mixture is stirred at RT for 17 hrs and washed with 30 ml of water, 30 ml of 5% hydrochloric acid and 30 ml of water. The dichloromethane solution is concentrated and the concentrate flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 L 70/30 hexane-ethyl acetic and 500 ml 50/50 hexane-ethyl acetate as eluting solvent mixtures. Fractions 18-21 gave after recrystallization from 70/30 hexane ethyl acetate the title compound as a white solid, m.p. 168.degree.-170.degree. C.
EXAMPLE 26
3-[(4,6-dimethoxy-.alpha.-(N-methylcarbamoyloxy)-2-pyrimidinyl)methyl]-2-pyridine carbox(N-allyl)amide (Table E, cpd. no. 133)
To a solution of 0.5 g of 3-[(4,6-dimethoxy-.alpha.-hydroxy-2-pyrimidinyl)methyl]-2-pyridine carbox(N-allyl)amide and 3 drops of triethylamine, in 20 ml of dichloromethane is added 3 ml of methyl isocyante, in three 1 ml portion/day while stirring at RT for 3 days. The reaction mixture is washed with water (2.times.50ml), dried and concentrated. The concentrate is flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 L 50/50 hexane-ethyl acetate, 500 ml ethyl acetate, 500 ml 80/20 ethyl acetate methanol taking 34 fractions (50 m/m). Fractions 21-25 give 0.4 g of the title product as a yellow gum.
EXAMPLE 27
Preparation of ethyl 2-bromo-4-[(4,6-dimethoxy-2-pyrimidinyl)methyl]nicotinate (Table D, cpd. no. 523)
7.32 g of ethyl 2-bromo-4-methyl nicotinate and 150 ml of THF are cooled in a dry ice/acetone bath under N.sub.2 atmosphere, 30 ml of LDA are added over 5 mins and the mixture stirred for 30 mins. 6.55 g of 2-methylsulphonyl-4,6-dimethoxypyrimidine are added as a solid, rinsing with 50 ml of THF, and the mixture stirred cold for 2 hrs and slowly allowed to warm. The THF is evaporated, ca 75 ml of water added and the mixture extracted three times with methylene dichloride. The combined extracts are evaporated and the residue taken up with 20 ml of 25% ethyl acetate/hexane and flash chromatographed using 2 l of 25% ethyl acetate/hexane in 50 ml fractions. Fractions 7 to 14 are combined, evaporated and placed in a Kugelrohr at ca 105.degree. for 2 hrs. The residue is taken up in 20 ml of 10% ethyl acetate/hexane and flash chromatographed with 2 l 10% ethyl acetate/hexane in 50 ml portions to yield title compound (NMR) in fractions 18 to 32.
EXAMPLE 28
Preparation of ethyl 2-bromo-4-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]nicotinate (Table D, cpd. no. 524)
3.28 g of ethyl 2-bromo-4-[(4,6-dimethoxy-2-pyrimidinyl)methyl]nicotinate, 3.61 g of SeO.sub.2 and 100 ml of glacial acetic acid are combined under nitrogen, heated to 110.degree. for 1.5 hrs and slowly cooled to RT still under nitrogen. The mixture is filtered, washed through with 10 ml of acetic acid and the filtrate evaporated to remove the acetic acid. 100 ml of methylene dichloride is added to the residue and the mixture washed twice with 100 ml of sat. aqueous NaHCO.sub.3. The CH.sub.2 Cl.sub.2 phase is filtered and evaporated and the residue digested with 25 ml of 25% ethyl acetate/hexane at 50.degree. for 15 mins. This solution is then poured onto a silica gel column and eluted with 3.times.125 ml of 25% ethyl acetate/hexane. Evaporation of combined fractions 1 and 2 yields the title product mp 98.degree.-99.degree..
EXAMPLE 29
Preparation of 1-(4,6-dimethoxy-2-pyrimidinyl)-1-hydroxy-4-methyl-furo[3,4-c]pyridine-3(1H)-one (Table B, cpd. no. 260)
0.37 g of ethyl 2-methyl-4-[4,6-dimethoxy-2-pyrimidinyl)methyl]nicotinate, 0.37 g of potassium permanganate and 100 ml of water are combined and heated at reflux for 45 mins. The mixture is cooled, a further 0.185 g of permanganate added and refluxing resumed for 45 mins. The mixture is cooled to RT, filtered through celite, and sodium sulfite added until the aqueous layer becomes colorless. The filtrate is once again filtered, washed with water and extracted with 4.times.75 ml of methylene chloride. The combined extracts are evaporated, the residue taken up in 50 ml of warm ethyl acetate and poured onto a silica column and eluted with 2.times.100 ml of ethyl acetate. The combined fractions are evaporated to yield title product mp 203.degree.-204.degree..
EXAMPLE 30
Preparation of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-.alpha.-t-butoxymethyl)-4-isoxazolecarboxanilide (Table F, cpd. no. 412)
To a solution of 1.29 g of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isoxazolecarboxanilide, in 60 ml of THF is syringed in 2 ml of 1.5 molar n-butyl lithium in hexane at -70.degree. C. The mixture is stirred for 10 mins at -70.degree. C. and 0.6 g of t-butylperoxybenzoate, in 10 ml of THF, added over 10 mins. The reaction mixture is stirred at -70.degree. C. for 1 hr and allowed to warm to RT. The mixture is diluted with 300 ml of water and extracted with 2.times.30 ml of toluene. The toluene solution is dried, concentrated and the concentrate flash chromatographed through 300 ml of silica gel, 230-400 mesh, using 1 l of 70/30 hexane/ethyl acetate, 500 ml of 50/50 hexane/ethyl acetate taking 30.times.50 ml fractions. Fractions 11-14 give the title compound as a yellow gum.
EXAMPLE 31
Preparation of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-.alpha.-hydroxymethyl)-4-isoxazolecarboxanilide (Table F, cpd. no. 424)
A mixture of 0.6 g of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-.alpha.-t-butoxymethyl)-4-isoxazolecarboxanilide, and 4 drops of borontrifluoridemethanol complex in 50 ml of toluene is heated at 50.degree.-55.degree. C. for 2 hours, washed with 20 ml of water, 50 ml of 5% sodium bicarbonate solution, dried and concentrated. The concentrate is recrystallized from hexane/methylene dichloride to give a white solid, mp 130.degree.-131.degree. C.
EXAMPLE 32
Preparation of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-4-isoxazolecarboxanilide (Table F, cpd. no. 429)
To a solution of 1.5 ml of oxalyl chloride in 30 ml of methylenedichloride cooled to -60.degree. C. is added a solution of 2 ml of DMSO in 10 ml of methylene dichloride dropwise at -60.degree. C. After 2 mins. a solution of 0.6 g of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinyl-.alpha.-hydroxymethyl)-4-isoxazolecarboxanilide in 10 ml of methylene dichloride is added over 3 mins at -60.degree. C. The mixture is stirred for 15 mins at -60.degree. C. and 1 ml of triethylamine added. The mixture is allowed to warm to RT, washed with water (3.times.30ml), dried and concentrated. The concentrate is flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 l 60/40 hexane/ethyl acetate, 500 ml 50/50 hexane/ethyl acetate taking 25.times.50 ml fractions. Fractions 11-14 give the desired product, a yellow gum.
EXAMPLE 33
Preparation of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-4-isoxazolecarboxanilide (Table F, cpd. no. 429, alternative method)
A solution of 100 mg of N-methyl 3-phenyl-5-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isoxazolecarboxanilide, 20 mg of dicobalt octacarbonyl, and 1 ml of t-butylhydroperoxide, in 60 ml of acetonitrile is refluxed for 48 hours. An additional 1 ml of t-butylhydroperoxide is added after 12 hrs and 24 hrs. Thin layer chromatography after 48 hrs indicates the presence of starting material and the title compound.
EXAMPLE 34
Oxidation of N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-5-trimethylsilyl-4-isothiazolecarboxanilide
A mixture of 2.0 g of N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-5-trimethylsilyl-4-isothiazolecarboxanilide, 1.5 g of manganese (III) triacetate, 20 ml of acetic acid and 30 ml of methylene dichloride is stirred at RT for 48 hours. The resulting suspension is suction filtered through filter aid and the filter cake washed with water and methylene dichloride. The organic layer is separated, dried and concentrated. The concentrate is flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 l 70/30 hexane/ethyl acetate, 500 ml 50/50 hexane/ethyl acetate taking 30.times.50 ml fractions. Fractions 10-15 give a mixture of two components which is heated with boron trifluoride methanol complex (4 drops) in 50 ml of toluene at 80.degree. C. for 2 hrs. The reaction mixture is washed with 30 ml of 15% sodium bicarbonate solution, dried, and concentrated. The concentrate is flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 l 60/40 hexane/ethyl acetate, 500 ml 40/60 hexane/ethyl acetate and 200 ml ethyl acetate taking 34.times.50 ml fractions. Fractions 20-23 give N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isothiazolecarboxanilide, 0.12 g, mp 92.degree.-93.degree. (Table F, cpd. no. 513). Fractions 24-28 give N-methyl 3-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-4-isothiazolecarboxanilide, 0.3 g, mp 140.degree.-142.degree. C. (Table F, cpd. no. 514).
EXAMPLE 35
3-[(4,6-dimethoxy-2-pyrimidinyl)hydroxy methyl]-N-methyl-2-pyridine carboxamide (Table E, cpd. no. 108)
7.2 g of methylamine gas is bubbled into 300 ml of anhydrous methanol over 10 min at 10.degree., 30 g of 5-(4,6-dimethoxy-2-pyridimidinyl)furo[3,4-b]-pyridine-7(5H)-one added and the mixture stirred at RT for 14 hours. The reaction mixture is then filtered and the filtrate concentrated to ca 50 ml. The resulting suspension is cooled to ca 10.degree. and the precipitate filtered to isolate the title compound m.p. 132.degree.-133.degree. C.
EXAMPLE 36
3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-2-pyridinecarboxylic acid (Table E, cpd. no. 64)
30.3 g of KMnO.sub.4 and 32.3 g of NaHCO.sub.3 are suspended in 700 ml of water and 57 g of lithium 3-[(4,6-dimethoxy-2-pyrimidinyl)hydroxymethyl]-2-pyridine carboxylate is added with stirring. The reaction mixture is refluxed for 4 hrs and suction filtered hot. The filtrate is cooled over ice water and audified with conc. HCl (60 ml). The precipitated solid is filtered and dried in vacuo at 50.degree. to give the title compound m.p. 159.degree.-161.degree. C.
EXAMPLE 37
5-chloro-5-(4,6-dimethoxy-2-pyrimidinyl)furo[3-b]pyridine-7(5H)-one (Table B, cpd. no. 68)
45.53 g of 3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-2-pyridinecarboxylic acid are suspended in 700 ml of carbon tetrachloride and 186.4 g of thionyl chloride added with stirring. The suspension is heated to 70.degree. C. for 4 hrs and the reaction mixture then cooled to RT and the excess thionyl chloride and carbon tetrachloride evaporated off to give the title compound as a tan solid m.p. 146.degree.-148.degree. C.
EXAMPLE 38
3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-N,N-dimethyl-2-pyridinecarboxamide (Table E, cpd. no. 385)
15.8 g of anhydrous dimethylamine gas is bubbled into 36 g of 5-chloro-5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4-b]pyridine-7(5H)-one in 350 ml of methylene dichloride cooled in an ice bath and the mixture then stirred overnight at RT. The reaction mixture is then washed with saturated brine solution (3.times.50 ml) passed through phase separating paper and the filtrate concentrated. The concentrate is dissolved in methylene dichloride, charcoal treated at RT for 1 hr and filtered.
The filtrate is concentrated to 60 ml diluted with hexane, digested for 1 hr at 35.degree. and allowed to crystallize overnight at RT. The precipitate is filtered to isolate 35.15 g of the title product m.p. 124.degree.-126.degree. C.
EXAMPLE 39
3-cyano-4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 269)
21.5 g of NaH in oil dispersion are added to 112.75 g of 3-cyano-4,7-dichlorophthalide and 96.7 g of 4,6-dimethoxy-2-methylsulfonyl-pyrimidine. (The hydride is washed with hexane, the hexane removed by suction and the residue covered with DMF and cooled in an ice bath.) The reaction mixture is left to stir overnight at RT and the solution then poured into 3 L of water containing 15 ml of conc. H.sub.2 SO.sub.4 and stirred mechanically until a viscous gum formed around the stirred blade. The water layer is decanted and extracted with 3.times.400 ml of toluene, the first two extracts added to the gum and the mixture stirred until the gum dissolved. The toluene solution is washed 2.times.100 ml of water and 1.times.100 ml of toluene and the combined toluene layers dried over Na.sub.2 SO.sub.4 concentrated to 400 ml and left to stand overnight. The still homogeneous solution is flash-chromatographed over silica gel with toluene (250 ml fraction 5) fractions 5-9 are combined and stripped to give 30 g of the title product m.p. 123.degree.-126.degree. C.
EXAMPLE 40
4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxyphthalide (Table A, cpd. no. 250)
70 g of 3-cyano-4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide are slurried in 100 ml of methanol and 16 g of NaOH pellets with 125 ml of water added. The mixture is stirred and heated to reflux for 30 mins., the solution cooled and the methanol stripped. The aqueous solution was diluted with 400 ml of water, washed with 100 ml of ether and then added dropwise to 400 ml of 1 NH.sub.2 SO.sub.4 to give a solid which is filtered and dried in vacuum for 1 hr at 60.degree.. The solid is triturated with 100 ml of ether and the suspension left overnight at RT and the solid isolated by filtration to give the title product m.p. 161.degree.-175.degree. C.
EXAMPLE 41
3,6-dichloro-2-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]benzoic acid, isopropylammonium salt (Table C, cpd. no. 481)
24.13 g of 4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxyphthalide is slurried in 500 ml of methylene dichloride and 200 ml of methanol and 125 ml of freshly distilled isopropylamine added. The mixture is heated to reflux and the solution filtered, cooled and stripped. The solid is dried in vacuum for 4 hrs at 45.degree. C. to give the title product m.p. 194.degree.-196.degree. C.
EXAMPLE 42
4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hexanoyloxyphthalide (Table A, cpd. no. 265)
52 g of 4,7-dichloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxyphthalide and 500 ml of methylene dichloride are cooled in an ice bath and 23 ml of triethylamine and 1.1 g of DMAP added. The mixture is stirred until most of the solid dissolves, 35.2 g of freshly distilled hexanoic anhydride are added and the mixture is stirred for 48 hrs under N.sub.2 at RT. The solution is washed with 2.times.100 ml 1 NH.sub.2 SO.sub.4, 1.times.100 ml 0.1N NaOH and brine dried over Na.sub.2 SO.sub.4 and concentrated to give 58.2 g of crude product which is triturated with 150 ml of ether and filtered to isolate the title product m.p. 103.degree.-105.degree. C.
The following compounds may be prepared analogously to the preceding examples or as otherwise described herein. Unless otherwise stated alkyl groups are straight chained i.e. in "n"-form.
TABLE A - ##STR36## ##STR37## ##STR38## melting point Cpd No Y.sub.1 Y.sub.2 Y.sub.3 Y W.sub.1 W.sub.2 W.sub.3 W.sub.4 R.sub.1 (.degree.C.) 1 H H H OH N CH COCH.sub.3 N OCH.sub.3 136-138 2 H H H H N CH COCH.sub.3 N OCH.sub.3 102-104 3 H H H OCCH.sub.3 N CBr COCH.sub.3 N OCH.sub.3 215-225 O 4 H H H H N CBr CH N OCH.sub.3 136-138 5 H H 5-Cl H N CH COCH.sub.3 N OCH.sub.3 151-153 6 7-Cl H H H N CH COCH.sub.3 N OCH.sub.3 148-149 7 H 6-Cl H H N CH COCH.sub.3 N OCH.sub.3 138-139 8 H H H H N CH CCl N OCH.sub.3 152-153 9 7-Cl H H H N CH CCl N OCH.sub.3 128-130 10 H H 4-Cl H N CH COCH.sub.3 N OCH.sub.3 98-99 11 7-CH.sub.3 H H H N CH COCH.sub.3 N OCH.sub.3 138-140 12 H H H H N CH CCl N CH.sub.3 133-135 13 7-Cl H H OH N CH COCH.sub.3 N OCH.sub.3 188-190 14 7-Cl H H H N CH COiC.sub.3 H.sub.7 N OCH.sub.3 101-102 15 7-OCH.sub.3 H 4-Br H N CH COCH.sub.3 N OCH.sub.3 126-128 16 7-Cl H H H N CH COCH.sub.2 CF.sub.3 N OCH.sub.3 112-113 17 7-Cl H H H N CH COCH.sub.3 N ##STR39## 136-138 18 7-Cl H H H N CH ##STR40## N OCH.sub.3 115-116 19 7-Cl H H H N CH COCH.sub.3 N ##STR41## 85-88 20 7-Cl H H H N CH COCH.sub.3 N OC.sub.2 H.sub.5 98-100 21 7-Cl H H Cl N CH COCH.sub.3 N OCH.sub.3 163-165 22 7-Cl H H H N CH COCH.sub.2 CCCH.sub.3 N OCH.sub.3 131-133 23 7-Cl H H SCH.sub.3 N CH COCH.sub.2 CCCH.sub.3 N OCH.sub.3 134-136 24 7-Cl H H H N CH COCH.sub.3 N OCH.sub.2 CHCH.sub.2 72-75 25 7-Cl H H H N N COCH.sub.3 N O CH.sub.3 157-160 26 7-OCH.sub.3 H H H N CH COCH.sub.3 N OCH.sub.3 152-154 27 7-Cl H H CN N CH COCH.sub.3 N OCH.sub.3 159-161 28 7-Cl H H CN N N COCH.sub.3 N OCH.sub.3 184-186 29 7-Cl 6-Cl H H N CH COCH.sub.3 N OCH.sub.3 194-195 30 7-Cl H H OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 180-183 31 ##STR42## H H CN N CH COCH.sub.3 N OCH.sub.3 169-171 32 7-OCH.sub.3 6-OCH.sub.3 H ##STR43## N N COCH.sub.3 N OCH.sub.3 134-136 33 7-Cl H H H N CH CCH.sub.3 N CH.sub.3 164-166 34 H H H ##STR44## N CBr CH N OCH.sub.3 163-176 35 H 5-Cl H "H1" N CH COCH.sub.3 N OCH.sub.3 151-153 36 7-Cl H H "H2" N N COCH.sub.3 N OCH.sub.3 126-127 37 H H H OH N CCl COCH.sub.3 N OCH.sub.3 162-165 38 7-F H H CN N CH COCH.sub.3 N OCH.sub.3 132-134 69 7-Cl H H OC.sub.2 H.sub.5 N CH COCH.sub.3 N OCH.sub.3 148-151 72 7-OCH.sub.3 H H CN N CH COCH.sub.3 N OCH.sub.3 159-163 73 H H H CH.sub.3 N CH COCH.sub.3 N OCH.sub.3 87-89 75 H H H "H1" N CH COCH.sub.3 N OCH.sub.3 168-170 88 7-Cl H H H N CH ##STR45## N OCH.sub.3 gum, NMR 98 7-Cl H H H N CH ##STR46## N OCH.sub.3 97-98 101 7-Cl H H H N CH ##STR47## N H 125-127 102 7-Cl H H H N CH ##STR48## N H 83-85 104 ##STR49## H H CN N CH COCH.sub.3 N OCH.sub.3 105-108 105 ##STR50## H H OH N CH COCH.sub.3 N OCH.sub.3 109-110 109 7-F H H OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 172-173.5 113 7-F H H H N CH COCH.sub.3 N OCH.sub.3 138-140 117 7-F H H OH N CH COCH.sub.3 N OCH.sub.3 183.5-185.5 118 7-OH H H CN N CH COCH.sub.3 N OCH.sub.3 121-122 120 ##STR51## H H CN N CH COCH.sub.3 N OCH.sub.3 174-176 125 7-Cl H H acetoxy N CH COCH.sub.3 N OCH.sub.3 213-215 134 7-OH H H OH N CH COCH.sub.3 N OCH.sub.3 138-141 (decomp) 135 7CH.sub.3 SO.sub.2 O H H CN N CH COCH.sub.3 N OCH.sub.3 159-161 137 7-OCON(C.sub.2 H.sub.5).sub.2 H H CN N CH COCH.sub.3 N OCH.sub.3 123-125 138 7propargyloxy H H CN N CH COCH.sub.3 N OCH.sub.3 174-175 139 ##STR52## H H CN N CH COCH.sub.3 N OCH.sub.3 170-171 140 ##STR53## H H CN N CH COCH.sub.3 N OCH.sub.3 169-172 145 ##STR54## H H H N CH COCH.sub.3 N OCH.sub.3 108-110 146 ##STR55## H H H N CH COCH.sub.3 N OCH.sub.3 115-118 147 7-OCH.sub.3 H H OH N CH COCH.sub.3 N OCH.sub.3 174-176 153 7propargyloxy H H H N CH COCH.sub.3 N OCH.sub.3 130-131 154 ##STR56## H H CN N CH COCH.sub.3 N OCH.sub.3 182-185(decomp) 166 7-OCF.sub.3 H H OH N CH COCH.sub.3 N OCH.sub.3 131-132 167 7-OCH.sub.3 H H acetoxy N CH COCH.sub.3 N OCH.sub.3 201-202 180 ##STR57## H H H N CH COCH.sub.3 N OCH.sub.3 133-136 190 7-Oallyl H H H N CH COCH.sub.3 N OCH.sub.3 109-110 195 7-CF.sub.3 O H H acetoxy N CH COCH.sub.3 N OCH.sub.3 165-166 203 7-Cl H H ##STR58## N CH COCH.sub.3 N OCH.sub.3 178-180 204 7-Cl H H ##STR59## N CH COCH.sub.3 N OCH.sub.3 131-133 205 7-Cl H H ##STR60## N CH COCH.sub.3 N OCH.sub.3 177-179 208 7-Cl H H benzoyloxy N CH COCH.sub.3 N OCH.sub.3 192-194 240 7-Cl H H ##STR61## N CH COCH.sub.3 N OCH.sub.3 158-160 250 7-Cl H 4-Cl OH N CH COCH.sub.3 N OCH.sub.3 171-175 253 7-Cl H H cinnamoyloxy N CH COCH.sub.3 N OCH.sub.3 221-224 256 7-Cl H H ##STR62## N CH COCH.sub.3 N OCH.sub.3 102-103 258 7-Cl H H 2-butenoxy N CH COCH.sub.3 N OCH.sub.3 102-103 263 7-Cl H 4-Cl ##STR63## N CH COCH.sub.3 N OCH.sub.3 163-164 265 7-Cl H 4-Cl ##STR64## N CH COCH.sub.3 N OCH.sub.3 87-91 266 7-Cl H 4-Cl ##STR65## N CH COCH.sub.3 N OCH.sub.3 137-138 267 7-Cl H 4-Cl ##STR66## N CH COCH.sub.3 N OCH.sub.3 128-131 268 7-F H 4-F CN N CH COCH.sub.3 N OCH.sub.3 135-136 269 7-Cl H 4-Cl CN N CH COCH.sub.3 N OCH.sub.3 123-126 270 7-Cl H 4-Cl H N CH COCH.sub.3 N OCH.sub.3 156-161 307 4-Cl H H OH N CH COCH.sub.3 N OCH.sub.3 146-150 319 4-Cl H H CN N CH COCH.sub.3 N OCH.sub.3 132-133 320 4-Cl H H OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 168-168.5 326 7-Cl H H ##STR67## N CH COCH.sub.3 N OCH.sub.3 142-143 409 7-Cl H H ##STR68## N CH COCH.sub.3 N OCH.sub.3 162-163 452 7-Cl 4-Cl H OCH.sub.2 CHCH.sub.2 N CH COCH.sub.3 N OCH.sub.3 135-136 459 7-OCH.sub.3 4-Cl H OH N CH COCH.sub.3 N OCH.sub.3 212-213 476 7-Si(CH.sub.3).sub.3 H H OH N CH COCH.sub.3 N OCH.sub.3 103-104 477 7-OCH.sub.3 4-Cl H H N CH COCH.sub.3 N OCH.sub.3 183-185 486 7-Cl 4-Cl H Cl N CH COCH.sub.3 N OCH.sub.3 139-142 526 7-Cl 4-F H OH N CH COCH.sub.3 N OCH.sub.3 178-179 543 7-Cl 4-CH.sub.3 H ##STR69## N CH COCH.sub.3 N OCH.sub.3 95-96 549 7-Cl 4-0CH.sub.3 H ##STR70## N CH COCH.sub.3 N OCH.sub.3 116-117 568 7-Cl 4-Cl H CN N CCl COCH.sub.3 N OCH.sub.3 188.5-189 580 7-CH.sub.3 4-F H ##STR71## N CH COCH.sub.3 N OCH.sub.3 103-104.5 582 7-CH.sub.3 4-F H H N CH COCH.sub.3 N OCH.sub.3 138-140 588 7-SO.sub.2 CH.sub.3 H H ##STR72## N CH COCH.sub.3 N OCH.sub.3 146-148 590 7-Cl 4-Cl H ##STR73## N CH COCH.sub.3 N OCH.sub.3 145-148 591 7-Cl 4-Cl H ##STR74## N CH COCH.sub.3 N OCH.sub.3 130-132 595 7-Cl 4-Cl H ##STR75## N CH COCH.sub.3 N OCH.sub.3 127-129 597 7-Cl 4-NO.sub.2 H CN N CH COCH.sub.3 N OCH.sub.3 151.5-152.5 599 7-Cl 4-Cl H ##STR76## N CH COCH.sub.3 N OCH.sub.3 171-174 605 7-Cl 4-Cl H ##STR77## N CH COCH.sub.3 N OCH.sub.3 81-83 606 7-Cl 4-Cl H ##STR78## N CH COCH.sub.3 N OCH.sub.3 103-108 607 7-Cl 4-Cl H ##STR79## N CH COCH.sub.3 N OCH.sub.3 98-101 608 7-Cl 4-Cl H ##STR80## N CH COCH.sub.3 N OCH.sub.3 83-85 610 7-CH.sub.3 4-Cl H ##STR81## N CH COCH.sub.3 N OCH.sub.3 114-115 611 7-Cl 5-Cl H ##STR82## N CH COCH.sub.3 N OCH.sub.3 206-210 612 7-Cl 4-F H ##STR83## N CH COCH.sub.3 N OCH.sub.3 122-123 615 7-Br H H ##STR84## N CH COCH.sub.3 N OCH.sub.3 142-144 618 7-CN H H ##STR85## N CH COCH.sub.3 N OCH.sub.3 160-162 623 7-Cl 4-Cl H OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 184-185 624 7-Cl 4-CH.sub.3 H OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 178-179
TABLE B__________________________________________________________________________ ##STR86## ##STR87## meltingCpd pointNo W.sub.7 W.sub.8 W.sub.9 W.sub.10 Y W.sub.1 W.sub.2 W.sub.3 W.sub.4 R.sub.1 (.degree.C.)__________________________________________________________________________ 39 CH CH CH N H N CH COCH.sub.3 N OCH.sub.3 149- 151 40 N CH CH CH H N CH COCH.sub.3 N OCH.sub.3 167- 168 41 CH CH N CH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 42 CH N CH CH H N CH COCH.sub.3 N OCH.sub.3 120- 126 43 N CCl CH CH H N CH COCH.sub.3 N OCH.sub.3 166- 169 44 N CH CC.sub.2 H.sub.5 CH H N N COCH.sub.3 N OCH.sub.3 oil NMR 45 N CH CH CH H N N COCH.sub.3 N OCH.sub.3 75-80 46 CH CC.sub.2 H.sub.5 CH N H N CH COCH.sub.3 N OCH.sub.3 oil NMR 47 CH CH CH N CH.sub.3 N CH COCH.sub.3 N OCH.sub.3 98-101 68 N CH CH CH Cl N CH COCH.sub.3 N OCH.sub.3 146- 148 70 N CH CH CH "H1" N CH COCH.sub.3 N OCH.sub.3 173- 176 89 CCH.sub.3 CH CH N H N CH COCH.sub.3 N OCH.sub.3 129- 131 92 N CH CH CH H N CH COCH.sub.2 CF.sub.3 N OCH.sub.3 116- 119 93 N CH CH CH H N CH CCH.sub.3 N CH.sub.3 193- 195 94 N CH CH CH H N CH CCl N OCH.sub.3 147- 149 95 N CH CH CH H N CH ##STR88## N OCH.sub.3 oil NMR 99 N CH CH CH H N CH COC.sub.3 H.sub.7 N OCH.sub.3 140- 142100 N CH CH CH H N CH COC.sub.2 H.sub.5 N OCH.sub.3 133- 135106 N CH CH CH H N CH COallyl N OCH.sub.3 112- 114107 N CH CH CH H N CH COCH.sub.2 CCCH.sub.3 N OCH.sub.3 oil NMR114 CCl N CH CH H N CH COCH.sub.3 N OCH.sub.3 168- 170121 COCH.sub.3 N CH CH H N CH COCH.sub.3 N OCH.sub.3 150- 153 (de- comp)136 N CH CH CH H N CH COCH.sub.3 N H 158- 160141 N CH CH CH * N CH COCHF.sub.2 N OCHF.sub.2 145- 147148 CH CH CH N "H1" N CH COCH.sub.3 N OCH.sub.3 212- 213175 CH CH CH N OH N CH COCH.sub.3 N OCH.sub.3 172- 178260 CCH.sub.3 N CH CH OH N CH COCH.sub.3 N OCH.sub.3 203- 204261 CCOOH N CH CH OH N CH COCH.sub.3 N OCH.sub.3 130- 132 (de- comp)317 N CH CH CH H N CH COCH.sub.3 N CH.sub.3 138- 140408 N CH CH CH N(CH.sub.3)OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 168- 170572 N CH CH COCH.sub.3 CN N CH COCH.sub.3 N OCH.sub.3 177- 179629 N CH CH CH (1) N CH COCH.sub.3 N OCH.sub.3 148- 150630 N CH CH CH (2) N CH COCH.sub.3 N OCH.sub.3 155- 159631 N CH CH CH (3) N CH COCH.sub.3 N OCH.sub.3 199- 200636 N CH CH CH (4) N CH COCH.sub.3 N OCH.sub.3 200- 204637 N CH CH CH (5) N CH COCH.sub.3 N OCH.sub.3 215- 217__________________________________________________________________________ (1) = ##STR89## (2) = ##STR90## (3) = ##STR91## (4) = ##STR92## (5) = ##STR93##
TABLE C - ##STR94## melting point Cpd # Y.sub.1 Y.sub.2 Y.sub.3 R X Y W.sub.1 W.sub.2 W.sub.3 W.sub.4 R.sub.1 (.degree.C.) 48 H H H ##STR95## H H N CH COCH.sub.3 N OCH.sub.3 oil NMR 49 H H H " O N CH COCH.sub.3 N OCH.sub.3 oil NMR 50 H H H ##STR96## H H N CH COCH.sub.3 N OCH.sub.3 150-152 51 H H H COOH NH N CH COCH.sub.3 N OCH.sub.3 225-235 (free acid) 52 2-Cl H H CN H H N CH COCH.sub.3 N OCH.sub.3 94-95 53 2-Cl H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 153-157 (Li.sup.+ salt) 54 2-Cl H H ##STR97## OCH.sub.3 N CH COCH.sub.3 N OCH.sub.3 oil NMR 55 2-Cl H H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 110-111 56 2-Cl H H CONHCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 130-132 57 2-Cl H H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 141-142 58 2-Cl H H COOH O N CH COCH.sub.3 N OCH.sub.3 276-278 (Na.sup.+ salt) 59 2-Cl H H ##STR98## OCH.sub.3 H N CH COCH.sub.3 N OCH.sub.3 148-150 60 H H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 185 (dec.) (Li.sup.+ salt) 61 H H H ##STR99## H H N CH CCl N Cl NMR 62 H H H " Br H N CH COCH.sub.3 N OCH.sub.3 71 H H H COOH OH H1 N CH COCH.sub.3 N OCH.sub.3 74 H H H COOH OH CH.sub.3 N CH COCH.sub.3 N OCH.sub.3 >250 (Li.sup.+ salt) 76 2-Cl H H COOC.sub.2 H.sub.5 O N CH COCH.sub.3 N OCH.sub.3 66-67 77 2Cl H H COOallyl O N CH COCH.sub.3 N OCH.sub.3 81-83 78 2Cl H H COObuten-3-yl O N CH COCH.sub.3 N OCH.sub.3 48-50 79 2Cl H H COObenzyl O N CH COCH.sub.3 N OCH.sub.3 99-101 80 2Cl H H ##STR100## OH N CH COCH.sub.3 N OCH.sub.3 99-101 81 2Cl H H ##STR101## OH N CH COCH.sub.3 N OCH.sub.3 153-154 85 2Cl H H CON(C.sub.2 H.sub.5).sub.2 O N CH COCH.sub.3 N OCH.sub.3 110-111 86 H H H COObenzyl OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 87 2Cl H H ##STR102## OH N CH COCH.sub.3 N OCH.sub.3 161-163 96 2-Cl H H CON(C.sub.2 H.sub.5).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 74-80 103 2-Cl H H CONCH.sub.3 (benzyl) O N CH COCH.sub.3 N OCH.sub.3 105-107 115 2-F H H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 101-104 116 2-F H H COOallyl O N CH COCH.sub.3 N OCH.sub.3 97-99 122 H H H COOallyl O N CH COCH.sub.3 N OCH.sub.3 92-93 123 2-Cl H H COO 2-methyl- O N CH COCH.sub.3 N OCH.sub.3 137-139 allyl 124 2-Cl H H COO-3-methyl- O N CH COCH.sub.3 N OCH.sub.3 54-57 but-2-enyl 126 2-Cl H H COOpropargyl O N CH COCH.sub.3 N OCH.sub.3 138-140 143 2-Cl H H COObut-2-enyl O N CH COCH.sub.3 N OCH.sub.3 61-65 156 2-OCH.sub.3 H H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 142-143 163 2-F H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 220-240 (decomp) 165 2OCH.sub.3 H H COOallyl O N CH COCH.sub.3 N OCH.sub.3 100-101 181 ##STR103## H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt158-159 191 2OCF.sub.3 H H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 80-82 (decomp) 192 3-Cl H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 170-174 (decomp) 194 5-Cl H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 225-227 (decomp) 197 4-Cl H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 195-198 (decomp) 202 2-pro- H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt pargyloxy >200 (decomp) 218 2-Cl H H ##STR104## O N CH COCH.sub.3 N OCH.sub.3 oil NMR 219 2-Cl H H ##STR105## O N CH COCH.sub.3 N OCH.sub.3 127-128 220 2-Cl H H ##STR106## O N CH COCH.sub.3 N OCH.sub.3 154-155 222 2-OC.sub.3 H.sub.7 H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt >273 (decomp) 228 2-Cl 5-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt >210 (decomp) 235 2-Cl 5-Cl H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt >205 (decomp) 239 2-Cl H H COOCH.sub.2 CHCHCl O N CH COCH.sub.3 N OCH.sub.3 86-87 242 2-Cl H H ##STR107## OCH.sub.3 H N CH COCH.sub.3 N OCH.sub.3 112-113 2 43 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt >295 (decomp) 244 2-F H H COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 276 (decomp) 247 2-Cl H H COOC.sub.3 H.sub.7 O N CH COCH.sub.3 N OCH.sub.3 63-65 249 2-Cl 5-Cl H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 130-132 251 2-Cl H H COOCH.sub.2 CHCHCl O N CH COCH.sub.3 N OCH.sub.3 107-108 262 2-Cl 5-Cl H COOallyl O N CH COCH.sub.3 N OCH.sub.3 89-90 264 2-Cl 5-Cl H COOC.sub.12 H.sub.25 O N CH COCH.sub.3 N OCH.sub.3 oil NMR 274 2-F 5-F H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt >295 (decomp) 277 2-Cl H H COOC.sub.4 H.sub.9 O N CH COCH.sub.3 N OCH.sub.3 NMR 281 2-Cl H H COOC.sub.5 H.sub.11 O N CH COCH.sub.3 N OCH.sub.3 NMR 287 2-Cl H H COOC.sub.6 H.sub.13 O N CH COCH.sub.3 N OCH.sub.3 70-71 299 2-Cl H H COOC.sub.7 H.sub.15 O N CH COCH.sub.3 N OCH.sub.3 NMR 300 2-Cl H H COOC.sub.8 H.sub.17 O N CH COCH.sub.3 N OCH.sub.3 NMR 306 5-Cl H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 266-276 (decomp) 308 2-Cl H H COOC.sub.12 H.sub.25 O N CH COCH.sub.3 N OCH.sub.3 NMR 314 2-Cl H H ##STR108## O N CH COCH.sub.3 N OCH.sub.3 92-94 3 15 2-Cl H H CH.sub.2 OH OH H N CH COCH.sub.3 N OCH.sub.3 115-116 316 2-Cl H H COOiC.sub.3 H.sub.7 O N CH COCH.sub.3 N OCH.sub.3 109-110 321 5-Cl H H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 115-116 423 5-Cl H H COOallyl O N CH COCH.sub.3 N OCH.sub.3 117-118 425 2-Cl H H CH.sub.2 O OH N CH COCH.sub.3 N OCH.sub.3 92-94 460 2-OCH.sub.3 5-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 228-230 461 2-OCH.sub.3 5-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 190-201 478 2-OCH.sub.3 5-Cl H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 150-160 479 2-Cl 5-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+ (iC.sub.3 H.sub.7).sub.2 salt 160-162 480 2-Cl 5-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+ (CH.sub.3).sub.2 salt 152-154 481 2-Cl 5-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 184-186 489 2-Cl 5-Cl H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 145-147 502 2-Cl H H COOH O N CH COCH.sub.3 N OCH.sub.3 NH.sub.4 salt 157-160 503 2-Cl H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 136-139 504 2-Cl H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+ (CH.sub.3).sub.2 salt 163-165 527 2-Cl 5-F H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 113-114 528 2-Cl 5-F H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 174-176 (decomp) 531 2-Cl 5-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH.sup.(1) salt 81-83 532 2-Cl H H COOH O N CH COCH.sub.3 N OCH.sub.3 DGA salt gum 533 2-Cl 5-CH.sub.3 H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 156-159 534 2-Cl 5-OCH.sub.3 H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 182-184 535 2-CH.sub.3 5-F H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 161-162 536 2-CH.sub.3 5-Cl H COOH O N CH COCH N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 164-165 537 2-Cl 4-Cl H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 150-151 538 2-SCH.sub.3 H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 205-215 (decomp) 539 2-Cl 5-F H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 216-225 (decomp) 542 2-Cl 5-CH.sub.3 H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 1 28-129 544 2-Cl 5-CH.sub.3 H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 87-88 545 2-Cl 5-Cl H ##STR109## O N CH COCH.sub.3 N OCH.sub.3 102-104 547 2-Cl 5-Cl H ##STR110## O N CH COCH.sub.3 N OCH.sub.3 95-97 548 2-Cl 5-OCH.sub.3 H CON (CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 130-131 550 2-Cl 5-OCH.sub.3 H COOH O N CH COCH N OCH.sub.3 Na.sup.+ salt 225-227 (decomp) 556 2-Cl 5-OCH.sub.3 H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 182-185 (decomp) 557 2-Cl 5-OCH.sub.3 H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 144-145 559 2-CF.sub.3 H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 124-125 560 2-CF.sub.3 H H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 94-95 561 2-CF.sub.3 H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 95-100 (decomp) 563 2-SO.sub.2 CH.sub.3 H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 191-198 (decomp) 566 2-CH.sub.3 H H COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt >260 567 2-CH.sub.3 H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 190-199 570 2-SCH.sub.3 5-Cl H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 183-185 577 2-Cl 5-Cl H ##STR111## O N CH COCH.sub.3 N OCH.sub.3 53-56 578 2-Cl 5-Cl H ##STR112## O N CH COCH.sub.3 N OCH.sub.3 134-136 581 2-CH.sub.3 5-F H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 125-127 583 2-SCH.sub.3 H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 286-289 (decomp) 585 2-NH.sub.2 H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 265-270 (decomp) 586 2-SO.sub.2 CH.sub.3 H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 265-266 587 2-SO.sub.2 CH.sub.3 H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 84-90 (decomp) 589 2-CH.sub.3 5-F H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 176-181 (decomp) 592 2-SO.sub.2 CH.sub.3 5-Cl H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 213-216 (decomp) 593 2-Cl 5-Cl H ##STR113## O N CH COCH.sub.3 N OCH.sub.3 165-166 594 2-Cl 5-Cl H ##STR114## O N CH COCH.sub.3 N OCH.sub.3 123-125 5 96 2-Cl 5-NO.sub.2 H CN CN H N CH COCH.sub.3 N OCH.sub.3 174.5-175.5 600 2-Cl 5-NO.sub.2 H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 168-170 604 2-Cl 5-Cl H ##STR115## O N CH COCH.sub.3 N OCH.sub.3 143-144 613 2-Br H H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 134-135 614 2-Br H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 285-286 616 2-Br H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 166-174 (decomp) 617 2-CN H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 160-162 619 2-CN H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 293-295 (decomp) 620 2-CN H H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 150-151 621 2-CN H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sub.+ salt 118-125 (decomp) 627 2-Cl 5-Cl H CN CN H N CH COCH.sub.3 N OCH.sub.3 134-136 628 2-Cl 3-Cl H CN CN H N CH COCH.sub.3 N OCH.sub.3 122-125 .sup.(1) H.sub.3 N.sup.+ C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH is also know as diglycolamine or DGA
TABLE D__________________________________________________________________________ ##STR116## melting pointCpd No A (anti clockwise)* R X Y W.sub.1 W.sub.2 W.sub.3 W.sub.4 R.sub.1 (.degree.C.)__________________________________________________________________________ 65 SCHCH ##STR117## H N CH COCH.sub.3 N OCH.sub.3 125-127 66 SCHCH ##STR118## H N N COCH.sub.3 N OCH.sub.3 oil NMR 67 CHCHCHN COOH OH CH.sub.3 N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt >283 (decomp)119 ##STR119## CONHCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR142 CHCHCHN COOC.sub.2 H.sub.5 CN H N CH COCH.sub.3 N OCH.sub.3 109-111149 CHCHCHN COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 160-165 (decomp)150 CHCHCHN CONHC.sub.3 H.sub.7 OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR173 CHCHCHN COOH OH H N CH COCH.sub.3 N OCH.sub.3 142-145 (decomp)174 CHCHCHN COOCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR176 CHCHCHN COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 129-131178 ##STR120## COOCH.sub.3 H H N CH COCH.sub.3 N OCH.sub.3 oil NMR179 ##STR121## COOH H H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt >240 (decomp)186 ##STR122## COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 147-149187 ##STR123## COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 235198 ##STR124## COOCH.sub.3 Br H N CH COCH.sub.3 N OCH.sub.3 125-126199 CHCHCHN COOH OH H N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 242 (decomp)206 ##STR125## COOCH.sub.3 acetoxy H N CH COCH.sub.3 N OCH.sub.3 oil NMR216 ##STR126## COOC.sub.2 H.sub.5 H H N CH COCH.sub.3 N OCH.sub.3 oil NMR236 ##STR127## COOC.sub.2 H.sub.5 Br H N CH COCH.sub.3 N OCH.sub.3 oil NMR237 ##STR128## COOC.sub.2 H.sub.5 Br H N CH COCH.sub.3 N OCH.sub.3 oil NMR238 ##STR129## COOC.sub.2 H.sub.5 Br H N CH COCH.sub.3 N OCH.sub.3 oil NMR248 ##STR130## COOC.sub.2 H.sub.5 O N CH COCH.sub.3 N OCH.sub.3 103-104254 ##STR131## COOH O N CH COCH.sub.3 N OCH.sub.3 180-185 (decomp) .301 CHCHCHN CON(C.sub.2 H.sub.5).sub.2 H H N CH COCH.sub.3 N OCH.sub.3 69-72302 CHCHCHN COOH OH H N CH COCH.sub.3 N OCH.sub.3 K.sup.+ salt 220-230 (decomp)330 CHCHCHN CON(C.sub.2 H.sub.5).sub.2 OtC.sub.4 H.sub.9 H N CH COCH.sub.3 N OCH.sub.3 oil NMR414 NCHCHCH ##STR132## OH N CH COCH.sub.3 N OCH.sub.3 136-138415 CHCHCHN ##STR133## O CH CH CH CH CF.sub.3416 CHCHCHN ##STR134## OH H CH CH CH CH CF.sub.3417 CHCHCHN ##STR135## OH H CH CH CH CH CF.sub.3418 CHCHCHN ##STR136## OH H CH CH CH CH CF.sub.3419 NCHCHCH ##STR137## O CH CH CH CH CF.sub.3420 NCHCHCH ##STR138## OH H CH CH CH CH CF.sub.3421 NCHCHCH ##STR139## OH H CH CH CH CH CF.sub.3422 NCHCHCH ##STR140## OH H CH CH CH CH CF.sub.3426 NCHCHCH ##STR141## OH N CH COCH.sub.3 N OCH.sub.3 163-165511 ##STR142## COOCH.sub.3 O(t)C.sub.4 H.sub.9 H N CH COCH.sub.3 N OCH.sub.3 115-117512 ##STR143## CONHC.sub.6 H.sub.13 OH H N CH COCH.sub.3 N OCH.sub.3 94-97518 ##STR144## COOH O N CH COCH.sub.3 N OCH.sub.3 NMR523 ##STR145## COOC.sub.2 H.sub.5 H H N CH COCH.sub.3 N OCH.sub.3 NMR524 ##STR146## COOC.sub.2 H.sub.5 O N CH COCH.sub.3 N OCH.sub.3 98-99525 ##STR147## COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt >280.degree.529 ##STR148## COOC.sub.2 H.sub.5 H H N CH COCH.sub.3 N OCH.sub.3 83-85540 ##STR149## COOC.sub.2 H.sub.5 O N CH COCH.sub.3 N OCH.sub.3 163-165541 ##STR150## COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 275-280551 ##STR151## CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 138-140552 ##STR152## COOC.sub.2 H.sub.5 H H N CH COCH.sub.3 N OCH.sub.3 89-92553 ##STR153## COOC.sub.2 H.sub.5 Br H N CH COCH.sub.3 N OCH.sub.3 NMR554 ##STR154## COOC.sub.2 H.sub.5 O N CH COCH.sub.3 N OCH.sub.3 116-118555 ##STR155## COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt >275__________________________________________________________________________ *Left hand atom attached to Rbearing carbon
TABLE E - ##STR156## C pd # Y.sub.1 Y.sub.2 Y.sub.3 R X Y W.sub.1 W.sub.2 W.sub.3 W.sub.4 R.sub.1 m.p. 63 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 164-166 64 H H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 90-92 82 H H H CONH.sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 135-137 83 H H H CONHbenzyl OH H N CH COCH.sub.3 N OCH.sub.3 NMR 84 H H H CONHallyl OH H N CH COCH.sub.3 N OCH.sub.3 NMR 91 H H H COOCH.sub.3 O N CH COCH.sub.3 N OCH.sub.3 119-121 97 H H H COObenzyl OH H N CH COCH.sub.3 N OCH.sub.3 NMR 108 H H H CONHCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 127-129 110 H H H CONHC.sub.3 H.sub.7 OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 111 H H H CONHC.sub.6 H.sub.13 OH H N CH COCH.sub.3 N OCH.sub.3 67-69 112 H H H CONH(i)C.sub.3 H.sub.7 OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 127 H H H CONHallyl benzoyloxy H N CH COCH.sub.3 N OCH.sub.3 NMR 128 H H H CONHallyl acetoxy H N CH COCH.sub.3 N OCH.sub.3 NMR 129 H H H CONH.sub.2 ethoxy- H N CH COCH.sub.3 N OCH.sub.3 112-114 carbonyloxy 130 H H H CONHC.sub.12 H.sub.25 OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 131 H H H CONHC.sub.2 H.sub.4 OCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 79-80 132 H H H CONH.sub.2 NH.sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 75-78 133 H H H CONHallyl OCONHCH.sub.3 H N CH COCH.sub.3 N OCH.sub.3 NMR 144 H H H CONHpropargyl OH H N CH COCH.sub.3 N OCH.sub.3 102-104 151 H H H ##STR157## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 152 H H H ##STR158## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 155 H H H CONHC.sub.18 H.sub.37 OH H N CH COCH.sub.3 N OCH.sub.3 64-66 157 H H H ##STR159## OH H N CH COCH.sub.3 N OCH.sub.3 102-104 158 H H H CONH.sub.2 benzoyloxy H N CH COCH.sub.3 N OCH.sub.3 115-116 159 H H H CON(benzoyl).sub.2 benzoyloxy H N CH COCH.sub.3 N OCH.sub.3 168-170 160 H H H ##STR160## OH H N CH COCH N OCH.sub.3 88-90 161 H H H CONH.sub.2 ##STR161## H N CH COCH.sub.3 N OCH.sub.3 138-140 162 H H H ##STR162## ##STR163## H N CH COCH.sub.3 N OCH.sub.3 198-200 164 H H H ##STR164## OH N H CH COCH.sub.3 N OCH.sub.3 91-94 168 H H H ##STR165## OH H N CH COCH.sub.3 N OCH.sub.3 103-106 169 H H H ##STR166## H N CH COCH.sub.3 N OCH.sub.3 135-137 170 H H H CONHNH(t)C.sub.4 H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 109-110 171 H H H ##STR167## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 172 H H H ##STR168## OH H N CH COCH.sub.3 N OCH.sub.3 140-142 177 H H H CONHC.sub.2 H.sub.4 N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 182 H H H ##STR169## OH H N CH COCH.sub.3 N OCH.sub.3 117-120 183 H H H ##STR170## OH H N CH COCH.sub.3 N OCH.sub.3 132-133 184 H H H ##STR171## OH H N CH COCH.sub.3 N OCH.sub.3 113-114 185 H H H CONHSO.sub.2 CH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 133-135 188 H H H ##STR172## OH H N CH COCH.sub.3 N OCH.sub.3 115-117 189 H H H CONHCH.sub.2 COOCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 97-99 193 H H H ##STR173## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 196 H H H ##STR174## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 199 H H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 200 H H H ##STR175## OH H N CH COCH.sub.3 N OCH.sub.3 144-146 201 H H H ##STR176## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 207 H H H CONH.sub.2 dichloro- H N CH COCH.sub.3 N OCH.sub.3 118-119 acetoxy 209 H H H ##STR177## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 210 H H H ##STR178## OH H N CH COCH.sub.3 N OCH.sub.3 119-121 211 H H H ##STR179## OH H N CH COCH.sub.3 N OCH.sub.3 125-127 212 H H H ##STR180## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 213 H H H ##STR181## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 214 H H H ##STR182## OH H N CH COCH.sub.3 N OCH.sub.3 oil NMR 215 H H H ##STR183## OH H N CH COCH.sub.3 N OCH.sub.3 119-120 217 H H H ##STR184## OH H N CH COCH.sub.3 N OCH.sub.3 182-183 221 H H H ##STR185## OH H N CH COCH.sub.3 N OCH.sub.3 105-106 223 H H H ##STR186## OH H N CH COCH.sub.3 N OCH.sub.3 130-131 224 H H H ##STR187## OH H N CH COCH.sub.3 N OCH.sub.3 149-150 225 H H H ##STR188## OH H N CH COCH.sub.3 N OCH.sub.3 98-100 226 H H H ##STR189## OH H N CH COCH.sub.3 N OCH.sub.3 40-42 227 H H H ##STR190## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 229 H H H ##STR191## OH H N CH COCH.sub.3 N OCH.sub.3 121-123 230 H H H ##STR192## OH H N CH COCH.sub.3 N OCH.sub.3 130-132 231 H H H ##STR193## OH H N CH COCH.sub.3 N OCH.sub.3 138-140 232 H H H ##STR194## OH H N CH COCH.sub.3 N OCH.sub.3 152-154 233 H H H CONHC.sub.3 H.sub.6 N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 234 H H H CONHC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 241 H H H COOH OH "H1" N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 158-160 245 H H H ##STR195## OH H N CH COCH.sub.3 N OCH.sub.3 150-154 246 H H H ##STR196## OH H N CH COCH.sub.3 N OCH.sub.3 133-134 252 H H H ##STR197## OH H N CH COCH.sub.3 N OCH.sub.3 150-151 255 H H H ##STR198## OH H N CH COCH.sub.3 N OCH.sub.3 52-54 257 H H H ##STR199## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 259 H H H CONHC.sub.8 H.sub.17 OH H N CH COCH.sub.3 N OCH.sub.3 54-56 271 H H H ##STR200## OH N CH COCH.sub.3 N OCH.sub.3 137-138 2 72 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 210 (decomp) 273 H H H ##STR201## O N CH COCH.sub.3 N OCH.sub.3 147-149 275 H H H ##STR202## OH H N CH COCH.sub.3 N OCH.sub.3 158-160 2 76 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 Na.sup.+ salt 195 (decomp) K.sup.+ salt (255 decomp) 278 H H H CONHC.sub.9 H.sub.19 OH H N CH COCH.sub.3 N OCH.sub.3 45-47 279 H H H CONHC.sub.10 H.sub.21 OH H N CH COCH.sub.3 N OCH.sub.3 49-51 280 H H H ##STR203## OH H N CH COCH.sub.3 N OCH.sub.3 58-62 282 H H H CONHCH.sub.2 iPr OH H N CH COCH.sub.3 N OCH.sub.3 103-105 283 H H H CONHCH.sub.2 CH(OCH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 284 H H H CONHC(CH.sub.3).sub.2 CCH OH H N CH COCH.sub.3 N OCH.sub.3 NMR 285 H H H CONHC.sub.4 H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 286 H H H CONHCHCH.sub.2 OCH.sub.3 OH H N CH COCH.sub.3 N OCH.sub.3 NMR CH.sub.3 288 H H H ##STR204## OH H N CH COCH.sub.3 N OCH.sub.3 182-184 289 H H H ##STR205## OH H N CH COCH.sub.3 N OCH.sub.3 181-183 290 H H H ##STR206## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 291 H H H CONHC.sub.6 H.sub.12 N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 292 H H H CONHC.sub.4 H.sub.8 N(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 293 H H H ##STR207## OH H N CH COCH.sub.3 N OCH.sub.3 131-132 294 H H H ##STR208## OH H N CH COCH.sub.3 N OCH.sub.3 124-126 295 H H H ##STR209## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 296 H H H ##STR210## OH H N CH COCH.sub.3 N OCH.sub.3 88-90 297 H H H ##STR211## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 298 H H H ##STR212## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 303 H H H ##STR213## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 304 H H H ##STR214## OH H N CH COCH.sub.3 N OCH.sub.3 54-56 305 H H H ##STR215## OH H N CH COCH.sub.3 N OCH.sub.3 D(+) 64-68L(-) NMR 309 H H H ##STR216## OH H N CH COCH.sub.3 N OCH.sub.3 133-134 310 H H H ##STR217## OH H N CH COCH.sub.3 N OCH.sub.3 102-104 311 H H H ##STR218## OH H N CH COCH.sub.3 N OCH.sub.3 122-123 312 H H H ##STR219## OH H N CH COCH.sub.3 N OCH.sub.3 126-128 313 H H H ##STR220## OH H N CH COCH.sub.3 N OCH 106-108 318 H H H COOH OH H N CH COCH.sub.3 N CH.sub.3 Li.sup.+ salt 185-188 (decomp) 322 H H H COOH OH H N CH CCH.sub.3 N CH.sub.3 Li.sup.+ salt >195 (decomp) 323 H H H COOH OH H N CH COCH.sub.3 N H Li.sup.+ salt >225 (decomp) 324 H H H COOH OH H N CH COCH.sub.3 N OC.sub.2 H.sub.5 Li.sup.+ salt 195 (decomp) 325 H H H COOH OH H N CH COCH.sub.3 N Cl 327 H H H ##STR221## H H N CH COCH.sub.3 N OCH.sub.3 96-98 328 H H H ##STR222## O N CH COCH.sub.3 N OCH.sub.3 114-116 329 H H H ##STR223## O N CH COCH.sub.3 N OCH.sub.3 146-148 379 H H H CON(C.sub.2 H.sub.5).sub.2 O N CH COCH.sub.3 N OCH.sub.3 109-111 380 H H H CON(C.sub.2 H.sub.5).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 381 H H H CON(iC.sub.3 H.sub.7).sub.2 O N CH COCH.sub.3 N OCH.sub.3 146-148 382 H H H CON(iC.sub.3 H.sub.7).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 383 H H H ##STR224## O N CH COCH.sub.3 N OCH.sub.3 384 H H H ##STR225## OH H N CH COCH.sub.3 N OCH.sub.3 3 85 H H H CON(CH.sub.3).sub.2 O N CH COCH.sub.3 N OCH.sub.3 121-123 386 H H H CON(CH.sub.3).sub.2 OH H N CH COCH.sub.3 N OCH.sub.3 387 H H H ##STR226## O N CH COCH.sub.3 N OCH.sub.3 388 H H H ##STR227## OH H N CH COCH.sub.3 N OCH.sub.3 389 H H H ##STR228## O N CH COCH.sub.3 N OCH.sub.3 131-133 390 H H H ##STR229## OH H N CH COCH.sub.3 N OCH.sub.3 391 H H H ##STR230## O N CH COCH.sub.3 N OCH.sub.3 392 H H H ##STR231## OH H N CH COCH.sub.3 N OCH.sub.3 393 H H H ##STR232## O N CH COCH.sub.3 N OCH.sub.3 NMR 394 H H H ##STR233## OH H N CH COCH.sub.3 N OCH.sub.3 395 H H H ##STR234## O N CH COCH.sub.3 N OCH.sub.3 oil NMR 396 H H H ##STR235## OH H N CH COCH.sub.3 N OCH.sub.3 397 H H H ##STR236## O N CH COCH.sub.3 N OCH.sub.3 398 H H H ##STR237## OH H N CH COCH.sub.3 N OCH.sub.3 399 H H H ##STR238## O N CH COCH.sub.3 N OCH.sub.3 400 H H H ##STR239## OH H N CH COCH.sub.3 N OCH.sub.3 401 H H H ##STR240## O N CH COCH.sub.3 N OCH.sub.3 402 H H H ##STR241## OH H N CH COCH.sub.3 N OCH.sub.3 403 H H H ##STR242## O N CH COCH.sub.3 N OCH.sub.3 131-133 404 H H H ##STR243## OH H N CH COCH.sub.3 N OCH.sub.3 405 H H H ##STR244## O N CH COCH.sub.3 N OCH.sub.3 143-145 406 H H H ##STR245## OH H N CH COCH.sub.3 N OCH.sub.3 407 H H H ##STR246## OH H N CH COCH.sub.3 N OCH.sub.3 gum NMR 411 H H H CONHC.sub.2 H.sub.4 S(n)C.sub.4 H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 gum NMR 413 H H H CONCH.sub.2 CCH O N CH COCH.sub.3 N OCH.sub.3 gum NMR CH.sub.3 428 H H H CONHSC.sub.4 H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 NMR (racemate) 432 H H R CONHnC.sub.5 H.sub.11 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 433 H H H CONHC.sub.7 H.sub.15 OH H N CH COCH.sub.3 N OCH.sub.3 NMR 434 H H H ##STR247## OH H N CH COCH.sub.3 N OCH.sub.3 143-145 435 H H H CONHCHC.sub.2 H.sub.5 OH H N CH COCH.sub.3 N OCH.sub.3 NMR COOCH.sub.3 436 H H H CONH(s)C.sub.4 H.sub.9 OH H N CH COCH.sub.3 N OCH.sub.3 NMR (both S(+) and R-(-) forms) 437 H H R CONHCH.sub.2 CCH OH H N CH CCH.sub.3 N OCH.sub.3 NMR 438 H H H ##STR248## OH N CH COCH.sub.3 N OCH.sub.3 139-141 439 H H H ##STR249## OH H N CH COCH.sub.3 N OCH.sub.3 143-144 440 H H H ##STR250## OH H N CH COCH.sub.3 N OCH.sub.3 133-134 441 H H H ##STR251## O N CH COCH.sub.3 N OCH.sub.3 117-120 442 H H H ##STR252## OH H N CH COCH.sub.3 N OCH.sub.3 127-128 443 H H H ##STR253## OH H N CH COCH.sub.3 N OCH.sub.3 138-140 444 H H H ##STR254## OH H H CH COCH.sub.3 N OCH.sub.3 152-153 445 H H H ##STR255## OH H N CH COCH.sub.3 N OCH.sub.3 108-110 446 H H H ##STR256## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 447 H H H ##STR257## OH H N CH COCH.sub.3 N OCH.sub.3 130-131 449 H H H ##STR258## OH H N CH COCH.sub.3 N OCH.sub.3 116-117 450 H H H ##STR259## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 453 H H H ##STR260## OH H N CH COCH.sub.3 N OCH.sub.3 100-102 4 54 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ iC.sub.3 H.sub.7 salt 201-203 455 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+ (CH.sub.3).sub.2 salt 183-185 456 H H H ##STR261## O N CH COCH.sub.3 N OCH.sub.3 115-116 457 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.2 N.sup.+ (iC.sub.3 H.sub.7).sub.2 salt 185-187 458 H H H CON-allyl O N CH COCH.sub.3 N OCH.sub.3 NMR CH.sub.3 462 H H H ##STR262## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 463 H H H ##STR263## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 4 64 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 diCa.sup.++ salt >240 465 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 diMg.sup.++ salt >240 466 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 diAl.sup.++ OH salt >250 467 H H H ##STR264## O N CH COCH.sub.3 N OCH.sub.3 148-150 468 H H H ##STR265## OH H N CH COCH.sub.3 N OCH.sub.3 125-126 469 H H H ##STR266## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 470 H H H ##STR267## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 471 H H H ##STR268## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 472 H H H ##STR269## OH H N CH COCH.sub.3 N OCH.sub.3 137-138 473 H H H ##STR270## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 474 H H H ##STR271## OH H N CH COCH.sub.3 N OCH.sub.3 156-159 475 H H H ##STR272## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 482 H H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 ##STR273## 483 H H H COOH OH H N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ C.sub.6 H.sub.13 salt NMR 484 H H H ##STR274## OH H N CH COCH.sub.3 N OCH.sub.3 113-115 485 H H H ##STR275## OH H N CH COCH.sub.3 N OCH.sub.3 147-148 4 87 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 H.sub.3 N.sup.+ C.sub.6 H.sub.13 salt 165-167 488 H H H COOH O N CH COCH.sub.3 N OCH.sub.3 ##STR276## 490 H H H ##STR277## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 491 H H H ##STR278## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 492 H H H COOH O N OH COCH.sub.3 N OCH.sub.3 Al.sup.+ (OH).sub.2 salt >250 493 H H H COOH O N OH COCH.sub.3 N OCH.sub.3 Al.sup.++ OH/Phe.sup.- salt >250 494 H H H ##STR279## O N CH COCH.sub.3 N OCH.sub.3 59-61 495 H H H ##STR280## OH H N CH COCH.sub.3 N OCH.sub.3 148-150 496 H H H ##STR281## O N CH COCH.sub.3 N OCH.sub.3 NMR 497 H H H ##STR282## O N CH COCH.sub.3 N OCH.sub.3 NMR 498 H H H ##STR283## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 500 H H H ##STR284## O N CH COCH.sub.3 N OCH.sub.3 NMR 501 H H H ##STR285## O N CH COCH.sub.3 N OCH.sub.3 NMR 505 H H H CONHCH.sub.2 CH.sub.2 OH OH H N CH COCH.sub.3 N OCH.sub.3 NMR 506 H H H ##STR286## OH H N CH COCH N OCH.sub.3 NMR 5 07 H H H CON(C.sub.3 H.sub.7).sub.2 O N CH COCH.sub.3 N OCH.sub.3 106-108 508 H H H ##STR287## O N CH COCH.sub.3 N OCH.sub.3 NMR 509 H H H ##STR288## O N CH COCH.sub.3 N OCH.sub.3 NMR 510 H H H ##STR289## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 513 H H H ##STR290## OH H N CH COCH.sub.3 N OCH.sub.3 115-117 514 H H H ##STR291## OH H N CH COCH.sub.3 N OCH.sub.3 94-97 515 H H H ##STR292## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 516 H H H ##STR293## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 517 H H H ##STR294## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 519 H H H ##STR295## OH H N CH COCH.sub.3 N OCH.sub.3 NMR 520 H H H ##STR296## OH H N CH COCH.sub.3 N OCH.sub.3 94-96 521 H H H ##STR297## O N CH COCH.sub.3 N OCH.sub.3 78-79 522 H H H ##STR298## O N CH COCH.sub.3 N OCH.sub.3 94-96 427 H H H ##STR299## O N CH COCH.sub.3 N OCH.sub.3 131-133 499 H H H ##STR300## O N CH COCH.sub.3 N OCH.sub.3 116-118 5 46 H H H CONHC.sub.2 H.sub.5 OH H N CH COCH.sub.3 N OCH.sub.3 48-50 558 H H H ##STR301## OH H N CH COCH.sub.3 N OCH.sub.3 108-110 562 H H 4-CH.sub.3 COOH OH H N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt nmr 569 H H H ##STR302## O N CH COCH.sub.3 N OCH.sub.3 136-138 571 H H H ##STR303## O N CH COCH.sub.3 N OCH.sub.3 NMR 573 H H 4-OCH.sub.3 COOH O N CH COCH.sub.3 N OCH.sub.3 202-204 574 H H 4-OCH.sub.3 COOH O N CH COCH.sub.3 N OCH.sub.3 Li.sup.+ salt 200-210 575 H H H ##STR304## O N CH COCH.sub.3 N OCH.sub.3 122-124 576 H H H ##STR305## O N CH COCH.sub.3 N OCH.sub.3 128-131 579 H H H ##STR306## O N CH COCH.sub.3 N OCH.sub.3 118-121 584 H H H ##STR307## O N CH COCH.sub.3 N OCH.sub.3 168-171 598 H H H ##STR308## O N CH COCH.sub.3 N OCH.sub.3 150-152 602 H H H ##STR309## O N CH COCH.sub.3 N OCH.sub.3 152-154 603 H H H ##STR310## O N CH COCH.sub.3 N OCH.sub.3 90-93 609 H H H ##STR311## O N CH COCH.sub.3 N OCH.sub.3 167-170 622 H H H COOsC.sub.4 H.sub.9 O N CH COCH.sub.3 N OCH.sub.3 NMR 625 H H H COOnC.sub. 4 H.sub.9 O N CH COCH.sub.3 N OCH.sub.3 NMR 626 H H H COOiC.sub.4 H.sub.9 O N CH COCH.sub.3 N OCH.sub.3 111-113 632 H H H ##STR312## OH N CH COCH.sub.3 N OCH.sub.3 122-127 633 H H H ##STR313## OH N CH COCH.sub.3 N OCH.sub.3 142-144 634 H H H ##STR314## OH N CH COCH.sub.3 N OCH.sub.3 156-158 (64: Lithium salt m.p. >250.degree.; sodium salt m.p. >190.degree. (decomp); potassium salt m.p. >230.degree.) (decomp) Phe = Phenalanine anion
TABLE F__________________________________________________________________________ ##STR315##Cpd # AA X Y m.p.__________________________________________________________________________ 90 ##STR316## H H 123-125331 ##STR317## O332 " OH H333 ##STR318## O334 " OH H335 ##STR319## O336 " OH H337 ##STR320## O338 " OH H339 ##STR321## O340 " OH H341 ##STR322## O342 " OH H343 ##STR323## O344 " OH H345 ##STR324## O346 " OH H347 ##STR325## O348 " OH H349 ##STR326## O350 " OH H351 ##STR327## O352 " OH H353 ##STR328## O354 " OH H355 ##STR329## O356 " OH H357 ##STR330## O358 " OH H359 ##STR331## O360 " OH H361 ##STR332## O362 " OH H363 ##STR333## O364 " OH H365 ##STR334## O366 " OH H367 ##STR335## O368 " OH H369 ##STR336## O370 " OH H371 ##STR337## O372 " OH H373 ##STR338## O374 " OH H375 ##STR339## O376 " OH H377 ##STR340## O378 " OH H410 ##STR341## H H 122-123412 " H O(t)C.sub.4 H.sub.9 gum NMR424 " OH H 130-131429 " O NMR430 ##STR342## H O(t)C.sub.4 H.sub.9 NMR431 " OH H NMR448 ##STR343## OH H NMR451 ##STR344## OH H 143-144511 ##STR345## H H NMR512 " H O(t)C.sub.4 H.sub.9 NMR513 ##STR346## H H 92-93514 " O 140-142515 ##STR347## H H 177-179530 ##STR348## H H NMR564 ##STR349## O decompose 270565 ##STR350## CN 155-158601 ##STR351## OH 124-126635 ##STR352## H H 92-94__________________________________________________________________________
Compounds of Table F wherein COOH is replaced by other meanings of R as listed in Tables C, D and E above for R may be prepared analogously.
NMR data [.sup.1 H nmr (CDCl.sub.3)
______________________________________Cpd No______________________________________ 41 .delta.: 3.95(s, 6H, OCH.sub.3), 5.95(s, 1H, pyrimidine H), 6.45(s, 1H, OCH), 7.7-9.1(m, 3H, pyridine H). 44 .delta.: 1.32(t, 3H, CH.sub.3), 2.87(q, 2H, CH.sub.2), 4.05(s, 6H, OCH.sub.3), 6.3(s, 1H, OCH), 7.82(d, 1H, arom.), 8.72(d, 1H, arom.). 46 .delta.: 1.32(t, 3H, CH.sub.3), 2.85(q, 2H, CH.sub.2), 3.87(s, 6H, OCH.sub.3), 5.97(s, 1H, pyrimidine H), 6.32(s, 1H, OCH), 8.08(d, 1H, pyridine H), 8.71(s, 1H, pyridine H). 48 .delta.: 1.25(s, 6H, CH.sub.3), 3.85(s, 6H, OCH.sub.3), 3.95(2H, OCH.sub.3), 4.65(s, 2H, CH.sub.2), 5.85(s, 1H, pyrimidine H), 7.2-8.0(4H, aromatic). 49 .delta.: 1.00(s, 6H, CH.sub.3), 3.65 and 3.75(d of d, 2H, OCH.sub.2), 6.05(s, 1H, pyrimidine H), 7.2-8.1(4H, aromatic H). 54 .delta.: 2.9(s, 3H, CH.sub.3 N), 3.10(s, 3H, CH.sub.3 O), 3.90(s, 6H, OCH.sub.3), 6.10(s, 1H, pyrimidine H), 7.2-7.9(3H, aromatic H). 61 .delta.: 1.24(s, 6H, CH.sub.3), 3.98(s, 2H, CH.sub.2 O), 4.74(s, 2H, CH.sub.2), 7.16(s, 1H, pyrimidine H). 65 .delta.: 3.96(s, 6H, OCH.sub.3), 5.96(s, 1H, pyrimidine H), 6.32(s, 1H, OCH), 7.27(d, 1H, thienyl H), 7.85(d, 1H, thienyl H). 66 .delta.: 408(s, 6H, OCH.sub.3), 6.27(s, 1H, OCH), 7.18(s, 1H, thienyl H), 7.95(d, 1H, thienyl H). 76 .delta.: 1.63(t, 3H, C H.sub.3), 3.91(s, 6H, OCH.sub.3), 4.1(q, 2H, OCH.sub.2), 6.08(s, 1H, pyrimidine H), 7.2-7.8(m, 3H, aromatic H). 83 .delta.: 3.85(s, 6H, OCH.sub.3), 4.58(d, 2H, NCH.sub.3), 5.30(s, 1H, OH), 5.80(s, 1H, pyrimidine H), 6.82(s, 1H, OCH), 7.25(s, 5H, aromatic), 7.40(dd, 1H, pyridine), 7.98(dd, 1H, pyridine), 8.45(dd, 1H, pyridine), 8.70(s, 1H, NH). 84 .delta.: 3.85(s, 6H, OCH.sub.3), 4.05(t, 2H, NCH.sub.2), 5.0-5.45(m, 3H, CH.dbd.CH.sub.2), 5.85(s, 1H, pyrimidine), 6.80(s, 1H, OCH), 7.2-8.6(m, 3H, pyridine). 86 .delta.: 3.85(s, OCH.sub.3), 5.37(s, OCH.sub.2 Ar), 5.85(s, pyrimidine), 6.80(s, OCH), 7.2-8.2(m, aromatic), mixture with cpd. 40. 88 .delta.: 4.00(s, 3H, OCH.sub.3), 5.50(s, 2H, OCH.sub.2), 6.05(s, 1H, pyrimidine H), 6.27(s, 1H, OCH) 7.1-7.7(m, 8H, aromatic H). 95 .delta.: 3.85(s, 6H, OCH.sub.3), 5.42(s, 2H, OCH.sub.2), 6.05(s, 1H, pyrimidine), 6.42(s, 1H, OCH), 7.25(s, 5H, aromatic), 7.30(dd, 1H, pyridine), 7.98(dd, 1H, pyridine), 8.90(dd, 1H, pyridine). 97 .delta.: 3.80(s, 6H, OCH.sub.3), 5.35(s, 2H, OCH.sub.2 Ar), 5.85(s, 1H, pyrimidine), 6.65(s, 1H, OCH), 7.15-8.6(m, 8H, aromatic), mixture with cpd. 40.107 .delta.: 1.92(s, 3H, C.tbd.CCH.sub.3), 3.98(s, 6H, OCH.sub.3), 4.92(s, 2H, OCH.sub.2), 6.07(s, 1H, pyrimidine), 6.58(s, 1H, OCH), 7.71(dd, 1H, pyridine), 8.20 (dd, 1H, pyridine), 8.90(dd, 1H, pyridine).110 .delta.: 0.91(t, 3H, CH.sub.3), 1.53(m, 2H, CH.sub.2) 3.37(m, 2H, CH.sub.2), 3.81(s, 6H, OCH.sub.3), 4.50(m, 3H, OH and NCH.sub.2), 5.82(s, 1H, pyrimidine), 6.72(s, 1H, OCH), 7.37(dd, 1H, pyridine), 7.95(dd, 1H, pyridine), 8.45(dd, 1H, pyridine).112 .delta.: 1.22(d, 6H, CH.sub.3), 3.81(s, 6H, OCH.sub.3), 4.20(m, 1H, NCH), 5.85(s, 1H, pyrimidine), 6.71(s, 1H, OCH), 7.38(dd, 1H, pyridine), 7.92(dd, 1H, pyridine), 8.25(s, 1H, NH), 8.47(dd, 1H, pyridine).119 .delta.: 3.05(d, 3H, NCH.sub.3), 3.94(s, 6H, OCH.sub.3), 5.20(s, 1H, OH), 5.75(s, 1H, pyrimidine), 5.98(s, 1H, OCH), 7.26(d, 1H, pyridine H), 7.82(q, 1H, NH), 8.28(d, 1H, pyridine H).127 .delta.: 3.75(s, 6H, OCH.sub.3), 4.05(t, 2H, NCH.sub.2), 5.05-5.5(m, 3H, CH.dbd.CH.sub.2), 5.85(s, 1H, pyrimidine), 7.2-8.6(m, 9H, phenyl + OCH).128 .delta.: 2.20(s, 3H, CH.sub.3), 3.75(s, 6H, OCH.sub.3), 4.10(t, 2H, NCH.sub.2), 5.0-6.6(m, 3H, CH.dbd.CH.sub.2), 5.85(s, 1H, pyrimidine), 7.2-8.6(m, 5H, pyridine + NH, OCH).130 .delta.: 1.30(m, 15H, aliphatic), 2.26(m, 8H, aliphatic), 3.36(m, 2H, NCH.sub.2), 3.83(s, 6H, OCH.sub.3), 5.82(s, 1H, pyrimidine), 6.81(s, 1H, OCH), 7.38(dd, 1H, pyridine), 8.06(dd, 1H, pyridine), 8.29(s, 1H, NH), 8.46(dd, 1H, pyridine).133 .delta.: 2.85(d, 3H, NCH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.10(t, 2H, NCH.sub.2), 5.0-6.0(m, 3H, CH.dbd.CH.sub.2), 5.85(s, 1H, pyrimidine), 7.2-8.6(m, 4H, pyridine + OCH).150 .delta. 0.96(t, 3H, CH.sub.3), 1.68(m, 2H, CH.sub.2), 3.50(m, 2H, NCH.sub.2), 3.93(s, 6H, OCH.sub.3), 5.92(s, 1H, pyrimidine H), 6.17(d, 1H, OCH), 7.21(d of d, 1H, pyridine H), 8.07(dd, 1H, pyridine H), 8.57(dd, 1H, pyridine H), 8.66(t, 1H, NH).151 .delta.: 1.50(d, 3H, CH.sub.3), 3.82(s, 6H, OCH.sub.3), 5.21(m, 2H, NCH, OH), 5.81(s, 1H, pyrimidine), 6.85(s, 1H, OCH), 7.23(m, 6H, phenyl and pyridine), 7.89(dd, 1H, pyridine), 8.42(dd, 1H, pyridine), 8.62(s, 1H, NH).152 .delta.: 2.18(s, 3H, CH.sub.3), 3.89(s, 6H, OCH.sub.3), 4.42(d, 2H, NCH.sub.2), 5.81(s, 1H, pyrimidine), 6.85(s, 1H, OCH), 7.03(s, 4H, phenyl), 7.21(dd, 1H, pyridine), 7.91(dd, 1H, pyridine), 8.42(dd, 1H, pyridine), 8.51(s, 1H, NH).171 .delta.: 1.24(t, 3H, CH.sub.3), 2.60(q, 2H, CH.sub.2), 3.86(s, 6H, OCH.sub.3), 4.62(d, 2H, NCH.sub.2), 5.86(s, 1H, pyrimidine H), 6.90(d, 1H, OCH), 7.0-8.54(m, 7H, phenyl), 8.60(bs, 1H, NH).174 .delta.: 3.83(s, 3H, OCH.sub.3), 3.90(s, 6H, OCH.sub.3), 5.83(s, 1H, pyrimidine H), 6.60(d, 1H, OCH), 7.30(dd, 1H, pyridine H), 8.23(dd, 1H, pyridine H), 8.70(dd, 1H, pyridine H).177 .delta.: 2.20(s, 6H, CH.sub.3), 2.38(t, 2H, CH.sub.2 N), 3.42(q, 2H, NCH.sub.2), 3.78(s, 6H, OCH.sub.3), 4.88(br, 1H, NH) 5.75(s, 1H, pyrimidine), 6.61(s, 1H, OCH), 7.29(dd, 1H, pyridine), 7.80(dd, 1H, pyridine), 8.34(dd, 1H, pyridine).178 .delta.: 3.85(s, 9H, OCH.sub.3), 3.95(s, 3H, OCH.sub.3), 4.14(s, 2H, CH.sub.2), 5.82(s, 1H, pyrimidine H), 6.90(d, 1H, pyridine H), 8.12(d, 1H, pyridine H).187 .delta.: 3.70(s, 9H, OCH.sub.3), 5.82(s, 1H, pyrimidine H), ;6.80(d, 1H, pyridine H), 8.10(d, 1H, pyridine H).193 .delta.: 1.00(d, 6H, CH.sub.3), 3.78(s, 3H, OCH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.72(q, 1H, CH), 5.50(d, 2H, OH and NCH), 5.82(s, 1H, pyrimidine), 6.88(s, 1H, OCH), 7.40(dd, 1H, pyridine), 7.98(dd, 1H, pyridine), 8.52(dd, 1H, pyridine), 8.78(s, 1H, NH).196 .delta.: 3.78(s, 6H, OCH.sub.3), 4.70(d, 2H, NCH.sub.2), 5.35(s, 1H, OH), 5.81(s, 1H, pyrimidine), 6.28(m, 2H, furfuryl), 6.81(s, 1H, OCH), 7.30(m, 2H, furfuryl; pyridine), 7.98(dd, 1H, pyridine), 8.41(dd, 1H, pyridine), 8.67(s, 1H, NH).201 .delta.: 1.87-2.04(m, 4H, CH.sub.2 and tetrahydrofuran), 3.71-3.92(m, 9H, OCH.sub.3 and tetrahydro- furan), 5.86-5.87(m, 2H, pyrimidine and OH), 6.74(d, 1H, OCH), 7.39(dd, 1H, pyridine), 7.88(dd, 1H, pyridine), 8.48(dd, 1H, pyridine), 8.55(s, 1H, NH).206 .delta.: 2.22(s, 1H, CH.sub.3), 3.85(s, 6H, OCH.sub.3), 3.92(s, 3H, OCH.sub.3), 3.97(s, 3H, OCH.sub.3), 5.86(s, 1H, pyrimdine H), 6.80(s, 1H, OCH), 7.10(d, 1H, pyridine H), 8.16(d, 1H, pyridine H).209 .delta.: 3.63(t, 3H, OCH.sub.3), 3.74(s, 6H, OCH.sub.3), 5.48-5.81(m, 4H, pyrimidine, OH, COCH), 6.88-7.42(m, 8H, phenyl, OCH, pyridine), 7.95(dd, 1H, pyridine), 8.46(dd, 1H, pyridine) 9.25(d, 1H, NH).212 .delta.: 3.85(s, 6H, OCH.sub.3), 4.41-4.52(m, 2H, NCH.sub.2), 5.21-5.72(d, s, 4H, NH.sub.2, pyrimidine, OH), 6.61(s, 1H, OCH), 7.12-7.32(m, 3H, pyridine, benzylsulfon), 7.71-7.80(m, 3H, pyridine, benzylsulfon), 8.3(d, 1H, pyridine), 8.71(m, 1H, NH).213 .delta.: 3.61(s, 6H, OCH.sub.3), 4.60(d, 2H, CH.sub.2, OH), 4.90(s, 1H, OH) 5.72(s, 1H, pyrimidine), 6.72(s, 1H, OCH), 7.16-8.41(m, 7H, pyridine), 9.12(s, 1H, NH).214 .delta.: 3.75(s, 6H, OCH.sub.3), 4.73(d, 2H, NCH.sub.2), 5.84(s, 1H, pyrimidine), 6.86-6.96(m, 3H, OCH, thiophene), 7.15(d, 1H, thiophene), 7.34(dd, Jcb=4.7, Jcd=7.9, 1H, pyridine), 7.96(dd, Jdc=7.9, Jdb=1.5, 1H, pyridine) 8.4(dd, Jbc=4.7, Jbd= 1.5, 1H, pyridine), 8.71(d, 1H, NH).216 .delta.: 1.31(t, 3H, CH.sub.3), 2.62(s, 3H, CH.sub.3), 3.87(s, 6H, OCH.sub.3), 4.21(s, 2H, CH.sub.2), 4.40(q, 2H, OCH.sub.2), 5.83(s, 1H, pyrimidine H), 7.13(d, 1H, pyridine H), 8.44(d, 1H, pyridine H).218 .delta.: 284(3.08)(s, 3H, NCH.sub.3), 3.92(s, 6H, OCH.sub.3), 4.50- 5.03(m, 2H, NCH.sub.2), 6.10(s, 1H, pyrimidine H), 7.10-7.80(m, 7H, aromatic H).227 .delta.: 1.50(m, 6H, CH.sub.2), 2.40(m, 6H, NCH.sub.2), 3.55(q, 2H, NCH.sub.2), 3.80(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine H), 6.70(s, 1H, OCH), 7.15-8.60(m, 4H, 3 pyridine H + NH).233 .delta.: 1.80(q, 2H, CH.sub.2), 2.25(s, 6H, NCH.sub.3), 2.35(q, 2H, NCH.sub.2), 3.45(q, 2H, NCH.sub.2), 3.80(s, 6H, CH.sub.3), 5.80(s, 1H, pyrimidine), 6.65(s, 1H, OCH), 7.15-850(m, 3H, pyridine).234 .delta.: 1.00(t, 6H, CH.sub.3), 2.60(m, 6H, NCH.sub.2), 3.50(q, 2H, NCH.sub.2), 3.92(s, 6H, O)CH.sub.3), 5.80(s, 1H, pyrimidine H), 6.80(s, 1H, OCH), 7.15-8.7(m, 3H, pyridine).236 .delta.: 1.37(t, 3H, CH.sub.3), 2.56(s, 3H, CH.sub.3), 3.87(s, 6H, OCH.sub.3), 4.43(q, 2H, OCH.sub.2), 5.87(s, 1H, pyrimidine H), 6.12(s, 1H, CHBr), 7.90(s, 1H, pyridine H), 8.56(d, 1H, pyridine H).237 .delta.: 1.40(t, 3H, CH.sub.3), 3.87(s, 6H, OCH.sub.3), 4.43(q, 2H, OCH.sub.2), 4.70(s, 2H, CH.sub.2 Br), 5.88(s, 1H, pyrimidine H), 6.23(s, 1H, CHBr), 8.07(d, 1H, pyridine H), 8.65(d, 1H, pyridine H).238 .delta.: 1.37(t, 3H, CH.sub.3), 2.06(s, 3H, CH.sub.3), 3.88(s, 6H, OCH.sub.3), 4.40(q, 2H, OCH.sub.2), 5.28(s, 2H, OCH.sub.2), 5.87(s, 1H, pyrimidine H), 6.23(s, 1H, CHBr), 8.04(d, 1H, pyridine H), 8.64(d, 1H, pyridine H).257 .delta.: 3.82(s, 6H, OCH.sub.3), 4.06(s, 2H, NCH.sub.2), 5.08(s, 1H, OH), 5.43(s, 1H, NH), 5.87(s, 1H, OCH), 6.82(s, 1H, pyrimidine), 7.32-7.38(m, 6H, pyridine; phenyl), 7.88(dd, 1H, pyridine), 8.45(dd, 1H, pyridine), 9.55(s, 1H, NH).264 .delta.: 0.8-1.9(br s, 25H, aliphatic), 3.85-3.90(s, 6H, OCH.sub.3), 6.15(s, 1H, ArH, pyrimidine), 7.4(s, 2H, ArH).277 .delta.: 0.90(t, 3H, CH.sub.3), 1.2-1.7(m, 4H, aliphatic), 3.95(s, 6H, OCH.sub.3), 4.08(t, 2H, OCH.sub.2), 6.15(s, 1H, pyrimidine H), 7.5-7.7(m, 3H, aromatic).281 .delta.: 0.90(t, 3H, CH.sub.3), 1.3(m, 4H, aliphatic), 1.6(m, 2H, aliphatic), 3.95(s, 6H, OCH.sub.3), 4.08(t, 2H, OCH.sub.2), 6.15(s, 1H, pyrimidine H), 7.4-7.7(m, 3H, aromatic).283 .delta.: 3.40(s, 6H, OCH.sub.3), 3.43(m, 2H, NCH.sub.2), 3.82(s, 6H, OCH.sub.3), 4.47(t, 1H, CH), 5.75(s, 1H, OH), 5.86(s, 1H, pyrimidine), 6.77(s, 1H, OCH), 7.41(dd, 1H, pyridine), 7.96(dd, 1H, pyridine), 8.47(m, 2H, NH, pyridine).284 .delta.: 1.75(s, 6H, CH.sub.3), 2.31(s, 1H, C.dbd.CH), 3.85(s, 6H, OCH.sub.3), 5.62(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.85(d, 1H, OCH), 7.45(dd, 1H, pyridine), 7.95(dd, 1H, pyridine), 8.44- 8.45(m, 2H, NH, pyridine).285 .delta.: 0.85(t, 3H, CH.sub.3), 1.48(m, 4H, CH.sub.2), 3.41(m, 2H, NCH.sub.2), 3.82(s, 6H, OCH.sub.3), 5.75(m, 2H, OH, pyrimidine), 6.66(d, 1H, OCH), 7.31(dd, 1H, pyridine), 7.86(d, 1H, pyridine), 8.27(s, 1H, NH), 8.40(dd, 1H, pyridine).286 .delta.: 1.28(t, 3H, CH.sub.3), 3.38-3.58(m, 4H, CH, CH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.18-4,48(m, 2H, CH.sub.2), 5.88(s, 1H, pyrimidine), 6.73(s, 1H, OCH), 7.53- 8.42(m, 4H, pyridine, NH).290 .delta.: 3.74(s, 9H, OCH.sub.3), 5.44(bs, 1H, OH), 5.73(s, 1H, pyrimidine), 6.62(bs, 1H, OCH), 6.9-8.6(m, aromatic, 7H), 10.22(s, 1H, NH).291 .delta.: 1.40(m, 8H, CH.sub.2), 2,28(s, 6H, NCH.sub.3), 2.68(m, 2H, NCH.sub.2), 3.40(m, 2H, NCH.sub.2), 3.80(s, 6H, OCH.sub.3), 5.80(s, 1H, pyrimidine), 6.70(s, 1H, OCH), 7.2-8.6(m, 4H, pyridine H + OH).292 .delta.: 1.60(m, 4H, CH.sub.2), 2.25(s, 6H, NCH.sub.3), 2.25(m, 2H, NCH.sub.2), 3.48(m, 2H, NCH.sub.2), 3.65(s, 6H, OCH.sub.3), 5.80(s, 1H, pyrimidine), 6.65(s, 1H, OCH), 7.2-8.6(m, 4H, pyridine + OH).295 .delta.: 3.74(s, 6H, OCH.sub.3), 3.80(s, 6H, OCH.sub.3), 4.50(s, 2H, NCH.sub.2), 5.84(s, 1H, pyrimidine), 6.5- 8.6(m, 8H, phenyl, OCH, NH).297 .delta.: 3.65(s, 6H, OCH.sub.3), 3.77(s, 6H, OCH.sub.3), 4.50(s, 2H, NCH.sub.2), 5.64(d, 1H, OH), 5.80(s, 1H, pyrimidine), 6.25-6.60(m, 3H, phenyl), 6.8(d, 1H, OCH), 7.2-8.6(m, 3H, pyridine).298 .delta.: 1.21(d, 3H, CH.sub.3), 3.26(m, 1H, CH), 3.61(m, 2H, CH.sub.2), 3.82(s, 6H, OCH.sub.3), 5.86(s, 1H, pyrimidine), 6.7(s, 1H, CH), 7.38(dd, 1H, pyridine), 7.90(dd, 1H, pyridine), 8.43(dd, 1H, pyridine), 8.61(br, 1H, NH).299 .delta.: 0.85(t, 3H, CH.sub.3), 1.2(m, 8H, aliphatic), 1.6(m, 2H, aliphatic), 3.95(s, 6H, OCH.sub.3), 4.08(t, 2H, OCH.sub.2), 6.15(s, 1H, pyrimidine H), 7.4-7.7 (m, 3H, aromatic).300 .delta.: 0.90(t, 3H, CH.sub.3), 1.2(m, 10H, aliphatic), 1.6(m, 2H, aliphatic), 3.95(s, 6H, OCH.sub.3), 4.08(t, 2H, OCH.sub.3), 4.08(t, 2H, OCH.sub.2), 6.15(s, 1H, pyrimidine H), 7.4-7.7(m, 3H, phenyl).303 .delta.: 3.80(s, 6H, OCH.sub.3), 3.90(d, 6H, OCH.sub.3), 5.45(d, 1H, OH), 5.80(s, 1H, pyrimidine), 6.85(s, 1H, OCH), 7.0-8.6(m, 6H, phenyl), 10.2(s, 1H, NH).305L(-) .delta.: 1.60(d, 3H, CH.sub.3), 3.75(2s, 6H, OCH.sub.3), 5.25(m, 1H, OH), 5.75(s, 1H, pyrimidine), 6.75(d, 1H, OCH), 7.2-8.6(m, 8H, aromatic).308 .delta.: 0.88(t, 3H, CH.sub.3), 1.25(bs, 18H, aliphatic), 1.6(m, 2H, aliphatic), 3.95(s, 6H, OCH.sub.3), 4.07(t, 2H, O--CH.sub.2), 6.15(s, 1H, pyrimidine H), 7.55-7.7(m, 3H, aromatic).330 .delta.: 1.05(m, 6H, NCH.sub.2 CH.sub.3), 1.27(s, 9H, C(CH.sub.3).sub.2), 2.3(m, 4H, NCH.sub.2), 3.8(s, 6H, OCH.sub.3), 5.8(s, 1H, pyrimidine H), 5.9(s, 1H, CH--Ot-Bu), 7.18(d of d, 1H, pyridine H), 7.45(d of d, 1H, pyridine H), 8.6(d of d, 1H, pyridine H).393 .delta.: 0.86(d, 3H, CH.sub.3), 1.12-1.26(m, 8H, CH.sub.2), 3.15(s, 3H, NCH.sub.3), 3.32(m, 2H, CH.sub.2), 3.93(s, 6H, OCH.sub.3), 6.14(s, 1H, pyrimidine), 7.46(dd, Jca=4.8, Jcb=7.8, 1H, pyridine), 8.12(dd, Jba=1.3, Jbc=7.8, 1H, pyridine), 8.68(dd, Jab= 1.2, Jac=4.8).395 .delta.: 3.10(s, 3H, N--CH.sub.3), 3.86(s, 6H, OCH.sub.3), 4.58(s, 2H, CH.sub.2), 6.06(s, 1H, pyrimidine), 7.18-8.69(m, 8H, pyridine, phenyl).407 .delta.: 3.18(m, 2H, CH.sub.2 S0, 3.65(m, 2H, CH.sub.2 N), 3.95(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.80(s, 1H, OCH), 7.0-8.7(m, 8H, aromatic).411 .delta.: 1.90(t, 3H, CH.sub.3), 1.55(m, 4H, CH.sub.2), 2.65(m, 4H, CH.sub.2 S), 3.62(m, 2H, CH.sub.2 N), 3.82(s, 6H, CH.sub.3 O), 5.90(s, 1H, pyrimidine), 6.75(s, OCH), 7.2-8.65(m, 3H, pyridine).412 .delta.: 1.37(s, 9H, tBuO), 3.30(s, 3H, CH.sub.3 N), 3.90(s, 6H, CH.sub.3), 5.95(s, 1H, pyridimidine), 5.97(s, 1H, OCH), 6.5-6.7(m, 10H, aromatic).413 .delta.: 2.23(s, 1H, C.tbd.CH), 3.12-3.23(d, 3H, N--CH.sub.3), 3.93(s, 8H, OCH.sub.3, N--CH.sub.2 C.dbd.), 6.15(s, 1H, pyrimidine), 7.47-7.52(m, 1H, pyridine), 8.14-8.17(m, 1H, pyridine), 8.69-8.71(t, 1H, pyridine).4.28 .delta.: 0.71-1.80(m, 8H, alphatic), 3.02(s, 6H, OCH.sub.3), 3.92-4.20(m, 1H, NCH), 5.82(s, 1H, pyrimidine), 6.67(s, 1H, OCH), 7.20-8.50(m, 4H, pyridine + NH).429 .delta.: 3.38(s, 3H, NCH.sub.3), 4.02(s, 6H, OCH.sub.3), 6.20(s, 1H, pyrimidine), 6.63-7.90(m, 10H, aromatic).430 .delta.: 1.3(s, 9H, t-Bu), 3.4(s, 3H, N--CH.sub.3), 3.9(s, 6H, OCH.sub.3), 5.9(s, H, pyrimidine H0, 6.57(m, 2H, CH--O + thiophene H), 7.05(m, 6H, thiophene H, phenyl).431 .delta.: 3.46(s, 3H, N--CH.sub.3), 3.97(s, 6H, OCH.sub.3), 5.2(d, 1H, OH), 5.87(s, 1H, pyrimidine H), 6.1(d, 1H, CH--O), 6.32(d, 1H, thiophene H), 6.75(d, 1H, thiophene H), 7.05(m, 5H, phenyl).432 .delta.: 0.92(t, 3H, CH.sub.3), 1.42(m, 6H, CH.sub.2), 3.42(m, 2H, NCH.sub.2), 3.85(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.72(d, 1H, OCH), 7.22-8.60(m, 4H, pyridine + NH).433 .delta.: 0.90(t, 3H, CH.sub.3), 1.32(m, 10H, CH), 3.45(m, 2H, NCH.sub.2), 3.92(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.75(s, 1H, OCH), 7.2-8.6(m, 4H, pyridine + NH).435 .delta.: 0.96(t, 3H, CH.sub.3), 1.92(m, 2H, CH.sub.2), 3.78(s, 3H, OCH.sub.3), 3.86(s, 6H, OCH.sub.3), 4.60(m, 1H, NCH), 5.86(s, 1H, pyrimidine), 6.86(d, 1H, OCH), 7.2- 8.9(m, 4H, pyridine + NH).436 (S)-(+)-amine .delta.: 0.76-1.74(m, 8H, CH.sub.3, CH.sub.2), 3.86(s, 6H, OCH.sub.3), 4.06(m, 1H, NCH), 5.86(s, 1H, pyrimidine), 6.70(d, 1H, OCH), 7.60-8.60(m, 4H, pyridine NH).436 (R)-(-)-amine .delta.: 0.70-1.85(m, 8H, CH.sub.3, CH.sub.2), 3.90(s, 6H, OCH.sub.3), 4.05(m, 1H, NCH), 5.85(s, 1H, pyrimidine), 6.65(s, 1H, OCH), 7.20-8.60 (m, 4H, pyridine, NH).437 .delta.: 2.25(m, 1H, .dbd.CH), 2.45(s, 3H, CH.sub.3), 3.80(s, 3H, OCH.sub.3), 4.25(m, 2H, NCH.sub.2), 6.38(s, 1H, pyrimidine), 6.95(s, 1H, OCH), 7.25-8.65(m, 4H, pyrimidine, NH).446 .delta.: 1.45(t, 3H, CH.sub.3), 3.82(s, 6H, OCH.sub.3), 4.12(q, 2H, OCH.sub.2), 5.42(d, 1H, OH), 5.88(s, 1H, pyrimidine), 6.72(m, 1H, OCH), 7.00-8.65(m, 7H, phenyl, pyridine), 10.32(s, 1H, NH).448 .delta.: 3.45(s, 3H, NCH.sub.3), 3.95(s, 6H, OCH.sub.3), 5.35(s, 1H, OH), 5.95(s, 1H, pyrimidine), 6.15(s, 1H, OCH), 6.90- 7.40(m, 5H, phenyl), 7.94(s, 1H, isothiazole).450 .delta.: 3.38(s, 3H, NCH.sub.3), 3.72(s, 6H, OCH.sub.3), 4.47(s, 2H, CH.sub.2), 5.38(s, 1H, OH), 6.94-8.62(m, 8H, OCH, benzene, pyridine), 10.64(s, 1H, NH).458 .delta.: 3.10(s, 3H, N--CH.sub.3), 3.95(m, 8H, CH.sub.2, OCH.sub.3), 5.19(m, 1H, .dbd.CH), 6.17(s, 1H, pyrimidine), 7.49(dd, 1H pyridine), 8.16(dd, 1H, pyridine), 8.69(dd, 1H, pyridine).462 .delta.: 3.40(s, 3H OCH.sub.3), 3.82(s, 6H, OCH.sub.3), 4.48(s, 2H, CH.sub.3), 4.63(s, 2H, NCH.sub.2), 5.73(s, 1H, OH), 5.88(s, 1H, pyrimidine), 6.80(s, 1H, OCH), 7.28- 8.80(m, 8H, benzene, pyridine, NH).463 .delta.: 3.83(s, 6H, OCH.sub.3), 4.43(d, 1H, OH), 5.75(s, 1H, pyrimidine), 6.75(s, 1H, OCH), 7.10-8.45(m, 7H, phenyl, pyridine), 8.70(t, 1H, NH).469 .delta.: 3.80(s, 6H, OCH.sub.3), 3.90(d, 6H, OCH.sub.3), 5.60(s, 1H, OH), 5.85(s, 1H, pyrimidine), 6.35-8.70(m, 7H, OCH, pyridine, phenyl), 10.30(s, 1H, NH).470 .delta.: 1.10(t, 6H, CH.sub.3), 2.53(q, 4H, CH.sub.2), 3.75(s, 6H, OCH.sub.3), 5.80(s, 1H, pyrimidine), 5.90(d, 1H, OH), 6.45(d, 1H, OCH), 7.00-8.60(m, 6H, phenyl, pyridine), 9.78(s, 1H, NH).471 .delta.: 3.34(s, 3H, OCH.sub.3), 3.37(s, 6H, OCH.sub.3), 4.42(s, 2H, OCH.sub.2), 4.63(d, 2H, NCH.sub.2), 5.74(d, 1H, OH), 5.80(s, 1H, pyrimidine), 6.80(d, 1H, OCH), 7.22-8.50(M, 7H, phenyl, pyrimidine), 8.65(t, 1H, NH).473 .delta.: 3.35(s, 3H, N--CH.sub.3), 3.95(s, 6H, OCH.sub.3), 6.27(s, 1H, CH), 6.66(s, 1H, pyrimidine), 6.93-8.93(d, 8H, phenyl, pyridine).475 .delta.: 3.40(s, 3H, OCH.sub.3), 3.75(s, 6H, OCH.sub.3), 4.52(s, 2H, CH.sub.2), 4.66(d, 2H, NCH.sub.2), 5.82(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.76(d, 1H, OCH), 7.20-8.60(m, 7H, phenyl, pyridine), 8.85(t, 1H, NH).482 .delta.: 2.20-2.70(m, 10H, NCH.sub.2, CH.sub.2), 3.40-3.80(m, 4H, OCH.sub.2), 3.85(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.20(s, 1H, OCH), 7.15-8.70(m, 3H, pyridine).483 .delta.: 0.60-1.80(m, 11H, CH.sub.2, CH.sub.3), 2.60-3.00(m, 2H, NCH.sub.2), 3.88(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.20(s, 1H, OCH), 7.00-8.70(m, 3H, pyridine).490 .delta.: 2.55(t, 1H, .dbd.CH), 3.82(s, 6H, OCH.sub.3), 4.68(d, 1H, OCH.sub.2), 5.45(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.90(d, 1H, OCH), 6.90-8.70(m, 7H, phenyl, pyridine), 10.25(s, 1H, NH).491 .delta.: 2.55(t, 1H, .dbd.CH), 3.80(s, 6H, OCH.sub.3), 5.42(d, 1H, OH), 5.84(s, 1H, pyrimidine), 6.80(m, 1H, OCH), 6.80- 8.70(m, 7H, phenyl, pyridine), 10.40(s, 1H, NH).496 .delta. 3.19(s, 3H, N--CH.sub.3), 3.69(t, 2H, CH.sub.2), 3.82(m, 2H, CH.sub.2), 3.94(s, 6H, OCH.sub.3), 6.17(s, 1H, pyrimidine), 7.55(dd, 1H, pyridine), 8.19 (dd, 1H, pyridine), 8.61(dd, 1H, pyridine).497 .delta.: 0.89(t, 3H, CH.sub.3), 1.26(m, 4H, CH.sub.2), 3.14(s, 3H, --NCH.sub.3), 3.34(m, 2H, CH.sub.2), 3.93(s, 6H, OCH.sub.3), 6.15(s, 1H, pyrimidine), 7.46(dd, 1H, pyridine), 8.13(dd, 1H, pyridine), 8.68(dd, 1H, pyridine).498 .delta.: 0.70-1.70(m, 10H, CH.sub.2 CH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.20(m, 1H, NCH), 5.85(s, 1H, pyrimidine), 5.95(d, 1H, OH), 6.68(d, 1H, OCH), 7.25-8.65(m, 4H, pyridine, NH).500 .delta.: 2.30(s, 6H, N(CH.sub.3).sub.2), 3.19(s, 3H, N--CH.sub.3), 3.54(m, 4H, CH.sub.2), 3.94(s, 6H, OCH.sub.3), 6.16(s, 1H, pyrimidine), 7.48(dd, Jca=2.8, Jcb=4.8, 1H, pyridine), 8.15(dd, Jbc=4.8, Jba=1.5, 1H, pyridine), 8.69(dd, Jca=2.8, Jab=1.5, 1H, pyridine).501 .delta.: 3.16(s, 3H, NCH.sub.3), 3.19-3.27(m, 9H, OCH.sub.3, CH.sub.2, CH), 3.71(s, 6H, OCH.sub.3), 5.96(s, 1H, pyrimidine), 7.27-7.31(d, 1H, pyridine), 7.93- 7.96(d, 1H, pyridine), 8.46-8.50(d, 1H, pyridine).505 .delta.: 3.35-4.10(m, 6H, NCH.sub.2, OCH.sub.2, NH, OH), 3.80(s, 6H, OCH.sub.3), 5.75(d, 1H, OH), 5.80(s, 1H, pyrimidine), 6.70(d, 1H, OCH), 7.20-8.30(m, 3H, pyridine), 8.60(m, 1H, NH).506 .delta.: 1.00(m, 6H, CH.sub.3), 1.60(m, 3H, CH.sub.2, CH), 3.75- 4.38(m, 6H, NH, NCH, CH.sub.2 OH), 3.88(s, 6H, OCH.sub.3), 5.90(s, 1H, pyrimidine), 6.76(s, 1H, OCH), 7.28-7.72(m, 4H, pyridine, NH).508 .delta.: 3.27(s, 3H, NCH.sub.3), 3.53(d, 2H, CH.sub.2), 3.61(t, 1H, CH), 3.82(m, 4H, CH), 3.87(s, 6H, OCH.sub.3), 6.16(s, 1H, pyrimidine), 7.48(dd, 1H, pyridine), 8.14(dd, 1H, pyridine), 8.69(dd, 1H, pyridine).509 .delta.: 3.25(s, 3H, NCH.sub.3), 3.67(t, 2H, CH.sub.2), 3.71(t, 2H, CH.sub.2), 3.94(s, 6H, OCH.sub.3), 6.19(s, 1H, pyrimidine), 7.50(dd, Jca=4.8, Jcb=7.8, 1H, pyridine), 8.18(dd, Jba=1.5, Jbc=7.8, 1H, pyridine), 8.72(dd, Jab=1.5, Jac=4.8, 1H, pyridine).510 .delta.: 1.77(s, 3H, CH.sub.3), 3.80(s, 6H, OCH.sub.3), 3.98(d, 2H, N--CH.sub.2), 4.90(s, 2H, .dbd.CH.sub.2), 5.70(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.8(d, 1H, OCH), 7.2- 7.5(m, 1H, pyridine), 7.8-8.05(d, 1H, pyridine), 8.4- 8.6(d, 1H, pyridine).511 .delta.: 0.18(s, 9H, Si(CH.sub.3).sub.3), 3.47(s, 3H, N--CH.sub.3), 3.90(s, 6H, OCH.sub.3), 4.20(s, 2H, CH.sub.2), 5.88(s, 1H, pyrimidine C--H), 7.04(s, 1H, thiophene C--H), 7.17(s, 5H, phenyl).512 .delta.: 0.12(s, 9H, Si(CH.sub.3).sub.2), 1.24(s, 9H, O-t-Bu), 3.38(s, 3H, N--CH.sub.3), 3.84(s, 6H, OCH.sub.3), 5.83(s, 1H, pyrimidine C--H), 6.20(s, 1H, CH--O), 7.05(s, 5H, phenyl), 7.37(s, 1H, thiophene C--H).513 .delta.: 0.75-1.15(t, 3H, CH.sub.3), 1.15-1.70(m, 6H, CH.sub.2), 2.25-2.70(m, 2H, OCH, OH), 3.45-4.00(m, 2H, NCH.sub.2), 3.85(s, 6H, OCH.sub.3), 5.85(s, 1H, pyrimidine), 6.80(s, 1H, OCH), 7.30-8.80(m, 4H, pyridine, NH).514 .delta.: 0.90(t, 3H, CH.sub.3), 1.10-1.67(m, 9H, CH.sub.2, CH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.10(m, 1H, NCH), 5.90(s, 1H, pyrimidine), 5.94(d, 1H, OH), 6.80(d, 1H, OCH), 7.28-8.66(m, 4H, pyridine, NH).515 .delta.: 1.06(m, 3H, CH.sub.3), 2.30(m, 1H, .dbd.CH), 3.90(s, 6H, OCH.sub.3), 3.92(m, 1H, NCH), 5.85(s, 1H, pyrimidine), 5.95(s, 1H, OH), 6.95(s, 1H, OCH), 7.20-8.70(m, 4H, pyridine, NH).516 .delta.: 0.95(t, 3H, CH.sub.3), 1.50(q, 2H, CH.sub.2), 3.62(m, 2H, NCH.sub.2), 3.85(s, 6H, OCH.sub.3), 3.87(m, 1H, OCH), 5.35(d, 1H, OH), 5.85(s, 1H, pyrimidine), 6.75(d, 1H, OCH), 7.30-8.80(m, 4H, pyridine, NH).517 .delta.: 1.00-2.25(m, 10H, CH.sub.2), 3.85(s, 6H, OCH.sub.3), 3.98(m, 1H, NCH), 5.85(s, 1H, pyrimidine), 5.88(d, 1H, OH), 6.68(d, 1H, OCH), 7.20-8.60(m, 4H, pyridine, NH).518 .delta.: 3.78(s, 6H, OCH.sub.3), 6.40(s, 1H, pyrimidine), 7.78(dd, Jca=4.7, Jcb=7.7, 1H, pyridine), 8.17(dd, Jbc= 7.6, Jba=1.5, 1H, pyridine), 8.91(dd, Jac=4.7, Jab=1.5, 1H, pyridine).519 .delta.: 2.12(m, 2H, CH.sub.2), 3.44(m, 2H, NCH.sub.2), 3.84(s, 6H, OCH.sub.3), 4.00(m, 2H, NCH.sub.2), 4.87(s, 1H, OH), 5.85(s, 1H, pyrimidine), 6.77(s, 1H, OCH), 6.90-8.68(m, 7H, pyridine, imidazole, NH).523 .delta.: 1.33(t, 3H, CH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.14(s, 2H, CH.sub.2), 4.40(q, 2H, OCH.sub.2), 5.87(s, 1H, pyrimidine H), 7.35(d, 1H, pyridine H), 8.33(d, 1H, pyridine H).530 .delta.: 0.50(s, 9H, Si(CH.sub.3).sub.3), 3.40(s, 3H, NCH.sub.3), 3.85(s, 6H, OCH.sub.3), 4.10(s, 2H, CH.sub.2), 5.83(s, 1H, pyrimidine), 7.00-7.40(m, 5H, benzene).532 .delta.: 3.01-3.50(m, 2H, CH.sub.2 OH), 3.59-3.61(m, 4H, OCH.sub.2), 3.71-3.73(m, 2H, CH.sub.2 N), 3.99(s, 6H, OCH.sub.3), 5.76(br s, 3H, NH), 6.08(s, 1H, pyrimidine), 7.27-7.31(m, 1H, aromatic), 7.45- 7.51(m, 2H, aromatic).553 .delta.: 1.41-1.46(t, 3H, CH.sub.3), 3.89(s, 6H, OCH.sub.3), 4.47-4.52(q, 2H, OCH.sub.2), 5.93(s, 1H, CHBr), 6.52(s, 1H, pyrimidine), 8.35(d, 1H, J=5.25 Hz, pyridine), 8.83(s, 1H, J=5.25 Hz, pyridine).562 .delta.: 2.5(s, 3H, CH.sub.3), 3.9(s, 6H, OCH.sub.3), 5.9(s, 1H, C HOH), 6.2(s, 1H, pyrimidine), 7.3(d, 1H, J=12 Hz, pyridine), 8.3(d, 1H, J=12 Hz, pyridine).571 .delta.: 1.26(t, 3H, CH.sub.3), 3.33(s, 3H, NCH.sub.3), 3.94(s, 6H, OCH.sub.3), 4.11(s, 2H, NCH.sub.2), 4.25(q, 2H, OCH.sub.2), 6.15(s, 1H, pyrimidine), 7.51(dd, Jca=4.8, ;Jcb=7.6, 1H, pyridine), 8.10(dd, Jbc=7.7, Jab=1.6, 1H, pyridine), 8.65(dd, Jac=4.8, Jab=1.6, 1H, pyridine).622 .delta.: 0.84(t, 3H, CH.sub.3), 1.08(d, 3H, CH.sub.3), 1.56(m, 2H, CH.sub.2), 3.89(s, 6H, OCH.sub.3), 4.78(m, 1H, CH), 6.13(s, 1H, pyrimidine), 7.62(dd, Jca=4.8, Jcb=7.6, 1H, pyridine), 7.94(dd, Jba=1.6, Jbc=7.6, 1H, pyridine), 8.85(dd, Jab=1.6, Jac=4.8, 1H, pyridine).625 .delta.: 0.87(t, 3H, CH.sub.3), 1.28(m, 2H, CH.sub.2), 1.54(m, 2H, CH.sub.2), 3.89(s, 6H, OCH.sub.3), 4.09(t, 2H, OCH.sub.2), 6.13(s, 1H, pyrimidine), 7.62(dd, Jca=4.7, Jcb=7.7, 1H, pyridine), 7.99(dd, Jba=1.5, Jbc=7.7, 1H, pyridine), 8.84(dd, Jab=1.5, Jac=4.17, 1H, pyridine).______________________________________

Number	Name	Date
3133066	Hemingway et al.	May 1964
3654204	Kim et al.	Apr 1972
3927214	Barth	Dec 1975
4923501	Saito et al.	May 1990
5015285	Rheinheimer et al.	May 1991
5137564	Jones	Aug 1992
5185026	Drewes et al.	Feb 1993
5317005	Jones	May 1994

Number	Date	Country
249708	Dec 1987	EPX
4026177	Feb 1992	DEX
1301668	Dec 1989	JPX
9216511	Oct 1992	WOX

	Number	Date	Country
Parent	201150	Feb 1994
Parent	36006	Mar 1993

	Number	Date
Parent	804150	Dec 1991
Parent	633592	Dec 1990
Parent	534794	Jun 1990

Substituted phthalides and heterocyclic phthalides

Information

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Inventors

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CPC

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Abstract

Description

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Parent Case Info

US Referenced Citations (8)

Foreign Referenced Citations (4)

Continuations (2)

Continuation in Parts (3)