Phenyl-substituted sulfonamides

BACKGROUND OF THE INVENTION
This invention relates to 1,2-benzothiaxinesulfonamides, 2,1-benzothiazinesulfonamides, 1,2-benzisothiazolesulfonamides, 2,1-benzisothiazolesulfonamides, 1,2-benzoxathiinsulfonamides, 2,1-benzoxathiinsulfonamides, 1,2-benzoxathiolesulfonamides, 2,21-benzoxathiolesulfonamides, 2-quinolonesulfonamides, 1-isoquinolonesulfonamides, 2-oxindolesulfonamides, 1-oxisoindolesulfonamides, benzo[b]pyran-2-onesulfonamides, benzo[c]pyran-1-onesulfonamides, benzo[c]pyran-3-onesulfonamides, benzo[c]thiopyran-1-onesulfonamides, benzo[b]furan-2-onesulfonamides, benzo[c]furan-1-onesulfonamides, benzo[c]thiopen-1-onesulfonamides, 1-tetralonesulfonamides, 2-tetralonesulfonamides, 1-indanonesulfonamides, 2-indanonesulfonamides, benzo[b]furan-3-onesulfonamides, benzo[b]pyran-4-onesulfonamides, 1,2-benzothiazepinesulfonamides, 2,1-benzothiazepinesulfonamides, 2-benzoxepin-1[5H]-onesulfonamides, 1-benzoxepin-2[3H]-onesulfonamides, 3-benzoxepin-2[1H]-onesulfonamides, 2-benzothiepin-1[5H]-onesulfonamides, 2-benzazepine-1-onesulfonamides, 1-benzazepine-2-onesulfonamides, 2,1-benzoxathiepinsulfonamides, 1,2-benzoxathiepinsulfonamides, benzocyclohepten-5-onesulfonamides, benzocyclohepten-6-onesulfonamides and 1-benzoxepin-5[4H]-onesulfonamides, which are useful as agricultural chemicals and in particular as growth regulants or herbicides.
U.S. Pat. No. 4,127,405 teaches compounds which are useful for controlling weeds in wheat having the formula: ##STR1## wherein R.sub.1 is ##STR2## R.sub.3 and R.sub.6 are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH.sub.3 S(O).sub.n --or CH.sub.3 CH.sub.2 S(O).sub.n --;
R.sub.4 is hydrogen, fluorine, chlorine, bromine or methyl;
R.sub.5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;
R.sub.7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alkoxy of 1-2 carbon atom;
R.sub.8 is hydrogen, methyl, chlorine or bromine;
R.sub.9 and R.sub.10 are independently hydrogen, methyl, chlorine or broment;
W and Q are independently oxygen or sulfur;
n is 0, 1 or 2;
X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbon atoms, trifluoromethyl, Ch.sub.3 S--or CH.sub.3 OCH.sub.2 --; and
Y is methyl or methoxy; or their agriculturally suitable salts; provided that:
(a) when R.sub.5 is other than hydrogen, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 is other than hydrogen and at least two of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be hydrogen;
(b) when R.sub.5 is hydrogen and all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 are other than hydrogen, then all of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 must be either chlorine or methyl; and
(c) when R.sub.3 and R.sub.7 are both hydrogen, at least one of R.sub.4, R.sub.5 or R.sub.6 must be hydrogen.
French Pat. No. 1,468,747 discloses the following para-substituted phenylsulfonamides, useful as antidiabetic agents: ##STR3## wherein R=H, halogen, CF.sub.3 or alkyl.
Logemann et al., Chem. Ab., 53, 18052g (1959), disclose a number of sulfonamides, including uracil derivatives and those having the formula: ##STR4## wherein R is butyl, phenyl or ##STR5## and R.sub.1 is hydrogen or methyl.
When tested for hypoglycemic effect in rats (oral 35 doses of 25 mg/100 g), the compounds in which R is butyl and phenyl were most potent. The others were of low potency or inactive.
Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 59 1633 e] describes the synthesis of N-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide: ##STR6## Based upon similarity to a known compound, the author predicted hypoglycemic activity for the foregoing compound.
Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches the preparation of compounds of Formula (i), and their use as general of selective herbicides, ##STR7## wherein R.sub.1 and R.sub.2 may independently be alkyl of 1-4 carbon atoms; and
R.sub.3 and R.sub.4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
Compounds of Formula (ii), and their use as antidiabetic agents, are reported in J. Drug. Res. 6, 123 (1974), ##STR8## wherein R is pyridyl.
The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food needs, such as soybeans, barley, wheat, and the like. The current population explosion and concomitant world food shortage demand improvements in the efficiency of producing these crops. Prevention or minimizing the loss of a portion of valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.
A wide variety of materials useful for filling, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need exists, however, for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.
SUMMARY OF THE INVENTION
this invention relates to novel compounds of Formula I, agriculturally suitable compositions containing them, and their method-of-use as pre-emergent or post-emergent herbicides or plant growth regulants. ##STR9## wherein J is ##STR10## n is 0, 1 or 2; W is O or S;
w.sub.1 is O or S;
R is H or CH.sub.3 ;
R.sub.1 is H, F, Cl, Br, CH.sub.3, OCH.sub.3, CF.sub.3, SCH.sub.3 or OCF.sub.2 H;
R.sub.2 is H or C.sub.1 -C.sub.4 alkyl;
R.sub.3 and R.sub.4 are independently H, C.sub.1 -C.sub.4 alkyl, Cl or Br;
R.sub.5 is H or CH.sub.3 ;
R.sub.6 is H or CH.sub.3 ;
R.sub.7 is H or CH.sub.3 ;
A is ##STR11## X is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, Cl, F, Br, OCF.sub.2 H, CH.sub.2 F or CF.sub.3 ;
Y is H, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, C.sub.2 H.sub.5, CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 c.tbd.CH, OCH.sub.2 CF.sub.3, CN, N.sub.3, OCH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 SCH.sub.3, CR.sub.6 (QCH.sub.3).sub.2, ##STR12## CR.sub.6 (QCH.sub.2 CH.sub.3).sub.2 or QCF.sub.2 T where Q is O or S and T is H, CHClF, CHBrF or CHFCF.sub.3 ;
Z is CH, N, CCH.sub.3, CC.sub.2 H.sub.5, CCl or CBr;
Y.sub.1 is O or CH.sub.2 ;
X.sub.1 is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5 or OCF.sub.2 H;
X.sub.2 is CH.sub.3, c.sub.2 H.sub.5 or CH.sub.2 CF.sub.3 ;
Y.sub.2 is OCH.sub.3, OC.sub.2 H.sub.5, SCH.sub.3, SC.sub.2 H.sub.5, CH.sub.3 or CH.sub.2 CH.sub.3 ;
X.sub.3 is CH.sub.3 or OCH.sub.3 ;
provided that
(a) when W is S, then R is H,
a is ##STR13## Z is CH or N, and Y is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, C.sub.2 H.sub.5, CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 c.tbd.CH, OCH.sub.2 CF.sub.3, OCH.sub.2 CH.sub.2 OCH.sub.3, CH(OCH.sub.3).sub.2 or ##STR14## (b) the totalnumber of carbon atoms in R.sub.3 and R.sub.4 is less than or equal to 4;
(c) when X is Cl, F or Br, then Z is CH and Y is OCH.sub.3, OC.sub.2 H.sub.5, NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2 or OCF.sub.2 H;
(d) when R.sub.5 is CH.sub.3, then n is 0;
(e) when J is J.sub.24, then R.sub.4 and R.sub.5 are not both H and R.sub.4 is not Cl or Br;
and their agriculturally suitable salts.
Preferred for reasons of their higher herbicidal activity, greater plant growth regulant activity or more favorable ease of synthesis are:
(1) Compounds of Formula I where W is O, R.sub.2 is H or C.sub.1 -C.sub.3 alkyl, R.sub.3 and R.sub.4 are independently H or C.sub.1 -C.sub.3 alkyl and R.sub.1 is bonded to the ortho or meta position of the ring relative to the sulfonylurea moiety.
(2) Compounds of Preferred 1 where R.sub.1 is H, F, Cl, Br, CH.sub.3, OCH.sub.3, CF.sub.3 or SCH.sub.3 ; Y is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, C.sub.2 H.sub.5, CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 C.tbd.CH, OCH.sub.2 CF.sub.3, OCH.sub.2 CH.sub.2 OCH.sub.3, CR.sub.6 (OCH.sub.3).sub.2, ##STR15## CR.sub.6 (OCH.sub.2 CH.sub.3).sub.2 or OCF.sub.2 H; and Z is CH or N.
(3) Compounds of Preferred 2 where R.sub.1 is H, R.sub.5 is H, A is ##STR16## X is CH.sub.3, OCH.sub.3, Cl, Br, CH.sub.2 F or OCF.sub.2 H; and Y is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, CF.sub.3, OCH.sub.2 CF.sub.3, CH(OCH.sub.3).sub.2, ##STR17## CH(OCH.sub.2 CH.sub.3).sub.2 or OCF.sub.2 H.
(4) Compounds of Preferred 3 where R is H, Y is CH.sub.3 or OCH.sub.3 and X is CH.sub.3, OCH.sub.3, Cl or Br.
(5) Compounds of Preferred 4 where J is J.sub.1.
(6) Compounds of Preferred 4 where J is J.sub.2.
(7) Compounds of Preferred 4 where J is J.sub.3.
(8) Compounds of Preferred 4 where J is J.sub.4.
(9) Compounds of Preferred 4 where J is J.sub.5.
(10) Compounds of Preferred 4 where J is J.sub.6.
(11) Compounds of Preferred 4 where J is J.sub.7.
(12) Compounds of Preferred 4 where J is J.sub.8.
(13) Compounds of Preferred 4 where J is J.sub.9.
(14) Compounds of Preferred 4 where J is J.sub.10.
(15) Compounds of Preferred 4 where J is J.sub.11.
(16) Compounds of Preferred 4 where J is J.sub.12.
(17) Compounds of Preferred 4 where J is J.sub.13.
(18) Compounds of Preferred 4 where J is J.sub.14.
(19) Compounds of Preferred 4 where J is J.sub.15.
(20) Compounds of Preferred 4 where J is J.sub.16.
(21) Compounds of Preferred 4 where J is J.sub.17.
(22) Compounds of Preferred 4 where J is J.sub.18.
(23) Compounds of Preferred 4 where J is J.sub.19.
(24) Compounds of Preferred 4 where J is J.sub.20.
(25) Compounds of Preferred 4 where J is J.sub.21.
(26) Compounds of Preferred 4 where J is J.sub.22.
(27) Compounds of Preferred 4 where J is J.sub.23.
(28) Compounds of Preferred 4 where J is J.sub.24.
(29) Compounds of Preferred 4 where J is J.sub.25.
(30) Compounds of Preferred 4 where J is J.sub.26.
Specifically preferred for reasons of their highest herbicidal activity, greatest plant growth regulant activity and/or most favorable ease of synthesis are:
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-1, 2-benzisothiaxole-7-sulfonamide, 1,1-dioxide, m.p. 218-221.degree. C.;
N-[(4-methoxy-6-methyl-1,2,5-triazin-2-yl)aminocarbonyl]-2, 3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfonamide, 1,1-dioxide, m.p. 210-212.degree. C.;
N-[(4-methoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]-2, 3-dihydro-2-methyl-1,2-benzisothiaxole-7-sulfonamide, 1,1-dioxide, m.p. 169-171.degree. C.;
N-[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-2, 3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfonamide, 1,1-dioxide, m.p. 206-208.degree. C.;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2, 3-dihydro-2-(1-methylethyl)-1,2-benzisothiaxole-7-sulfonamide, 1,1-dioxide, m.p. 234-236.degree. C.;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2, 3-dihydro-2-(1-methylethyl)-1,2-benzisothiazole-7-sulfonamide, 1,1-dioxide, m.p. 186-188.degree. C.;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2, 3-dihydro-2-propyl-1,2-benzisothiaxole-7-sulfonamide, 1,1-dioxide, m.p. 197-199.degree. C.;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2, 3-dihydro-2ethyl-1,2-benzisothiaxole-7-sulfonamide, 1,1-dioxide, m.p. 169-171.degree. C.;
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2, 3-dihydro-2-methyl-2H-1,2-benzisothiazole-8-sulfonamide, 1,1-dioxide, m.p. 258-266.degree. C.;
N-[(4,6-dimethoxypyrimidin-2yl)aminocarbonyl]-1,3-dihydro-3-oxoisobenzofuran-4-sulfonamide, m.p. 218-220.degree. C.;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1, 3-dihydro-2-methyl-1-oxo-1H-isoindole-7-sulfonamide, m.p. 215-217.degree. C.; and
N-[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-2, 3-dihydro-2-methyl-1,2-benzisothiaxole-7-sulfonamide, 1,1-dioxide, m.p. 219-221.degree. C.

DETAILED DESCRIPTION OF THE INVENTION
Synthesis
the compounds of Formula I can be prepared by one or more of the methods described below in Equations 1, 2, 3 and 4.
As shown in Equation 1, compounds of Formula I whee J is other than J.sub.6, J.sub.12, J.sub.22 and J.sub.23, can be prepared by reacting a sulfonylisocyanate (W=0) or a sulfonylisothiocyanate (W=S) of Formula II with an appropriate heterocyclic amine of Formula III. R, A and W are as previously defined. ##STR18##
the reaction is carried out at 25.degree. to 100.degree. C. in an inert, aprotic solvent such as methylene chloride or xylene for 0.5 to 24 hours as taught in U.s. Pat. No. 4,127,405.
Compounds of Formula I, where W is S and R is H, (Ia) can be prepared by reacting the appropriate sulfonamide of Formula IV with a heterocyclic isothiocyanate of Formula V, as shown in Equation 2. ##STR19##
The reaction is carried out at 25.degree. to 80.degree. C. in an inert, aprotic solvent such as acetone or acetonitrile in the presence of a base such as potassium carbonate for 0.5 to 24 hours. The required heterocyclicisothiocyanates V are prepared from the corresponding amines III as taught in EPO Publication 35893.
Compounds of Formula I, where W is O (Ib) and J is other than J.sub.4, J.sub.5, J.sub.10, J.sub.11, J.sub.16, J.sub.17, J.sub.21, J.sub.24 and J.sub.25, can be prepared by reacting the sulfonamides of Formula IV with an appropriate methylcarbamate of Formula VI in the presence of an equimolar amount of trimethylaluminum, as shown in Equation 3. ##STR20##
The reaction is carried out at 25.degree. to 40.degree. C. in a solvent such as methylene chloride for 10 to 96 hours under an inert atmosphere astaught in EPO No. 84,244 (7/27/84). The required carbamates VI are preparedby reacting the corresponding amines III with dimethylcarbonate or methyl chloroformate in the presence of a strong base.
Alternatively, compounds of Formula Ib, can be prepared by reacting a sulfonylcarbamate of Formula VII with an appropriate amine of Formula III,as shown in Equation 4. ##STR21##
The reaction is carried out at 50.degree. to 100.degree. C. in a solvent such as dioxane for 0.5 to 24 hours as taught in EPO publication No. 44807. The required carbamates VII are prepared by reacting the corresponding sulbonamides IV with diphenylcarbonate in the presence of a strong base.
The intermediate sulfonylisocyanates (W=O) and sulfonylisothiocyanates (W=S) of Formula II from Equation 1 can be prepared as shown in Equations 5, 6 and 7.
As shown in Equation 5, sulfonylisocyanates of Formula IIa where J is otherthan J.sub.6, J.sub.12, J.sub.22 and J.sub.23 can be prepared by the reaction of sulfonamides of Formula IV with phosgene, in the presence of n-butylisocyanate and a tertiary amine catalyst, at reflux in a solvent such as xylene by the method of U.S. Pat. No. 4,238,621. ##STR22##
The sulfonylisocyanates can also be prepared from the sulfonamides by a twostep procedure involving (a) reacting the sulfonamides with n-butylisocyanate in the presence of a base such as K.sub.2 CO.sub.3 at reflux in an inert solvent such as 2-butanone forming a n-butylsuflonylurea; and (b) reacting this compound with phosgene and a tertiary amine catalyst at reflux in xylene solvent. The method is similarto a procedure taught by Ulrich and Sayigh, Newer Methods of Preparative Organic Chemistry, Vol. VI, p. 223-241, Academic Press, New York and London, W. Foerst Ed.
Alternatively, as shown in Equation 6, the sulfonylisocyanates of Formula IIa can be prepared by reacting the corresponding sulfonyl chlorides VIII with cyanic acid salts. ##STR23##
The reaction is carried out at 25.degree. to 100.degree. C. in an enert aprotic solvent such as acetonitrile for 0.5-24 hours in the presence of phosphorus pentoxide and an alkali metal salt such as lithium iodide according to the teachings of Japanese Patent No. 76/26,816 ((Chem. Abst.,85:77892e (1976)).
The sulfonylisothiocyanates of Formula IIb where J is other than J.sub.6, J.sub.12, J.sub.22 and J.sub.23 can be prepared, as shown in Equation 7, by contacting the sulfonamides of Formula IV with carbon disulfide in the presence of two equivalents of a strong base. The resulting salt is then reacted with phosgene according to the teachings of K. Hartke, Arch. Pharm., 299, 174 (1966). ##STR24##
The sulfonamides of Formula IV of Equations 2, 3, 4, 5 and 7 are important intermediates for the preparation of the compounds of this invention. The syntheses of the required sulfonamide intermediates are described in Equations 8 and 9.
As shown in Equation 8, sulfonamides of Formula IV can be prepared from thecorresponding sulfonyl chlorides of Formula VIII by contacting with either anhydrous or aqueous ammonia. ##STR25##
The preparation of sulfonamides from sulfonyl chlorides is widely reported in the literature, for reviews see: F. Hawking and J. S. Lawrence, "The Sulfonamides," H. K. Lewis and Co., London, 1950 and E. H. Northey, "The Sulfonamides and Allied Compounds," Reinhold Publishing Corp., New York, 1948.
The unsaturated sulfonamides of Formula IVa can also be prepared from the corresponding saturated sulfonamides of Formula IVb by the two step procedure shown in Equation 9. G.sub.1 --G.sub.2 is SO.sub.2 --NR.sub.2, SO.sub.2 --O, CO--NR.sub.2, CO--O, CO--S, NR.sub.2 --SO.sub.2, O--SO.sub.2, NR.sub.2 --CO and O--CO, R.sub.1 and R.sub.2 are as previously defined. ##STR26##
The first step involves benzylic bromination by N-bromosuccinimide to give a monobromide which is subsequently dehydrobrominated in a second step by reaction with a suitable base such as triethyl amine or potassium-t-butoxide in an inert solvent such as THF. This method has beenused to prepare isocoumarins from 3,4-dihydroisocoumarins, see R. Barry, Chem. Rev., 64, 229 (1964). In cases where R.sub.1 is a methyl function, competitive bromination at this site may occur resulting in a mixture. Thedesired bromide may be separated at this stage, or after treatment with thebase, by standard methods. A similar method may be used to prepare sulfonamides where J is J=hd 23 from sulfonamides where J is J=hd 22 (n=1).
The sulfonyl chlorides of Formula VIII of Equation 6 and 8 can be prepared from the corresponding amines IX by the method shown in Equation 10. ##STR27##
The reaction involves diazotization of the amine IX with sodium nitrite in HCl, followed by reaction of the diaxonium salt with sulfur dioxide and cupric chloride in acetic acid analogous to the teachings of Yale and Sowinski, J. Org. Chem., 25, 1924 (1960).
Alternatively, sulfonyl chlorides of Formula VIII can be prepared by a modification of the above procedure whereby the diazotization reaction is carried out in dilute sulfuric acid and the resulting diazonium salt is reacted with sulfur dioxide, HCl and cupric chloride in a cosolvent mixture consisting of acetic acid-water (1:1) and in immiscible, inert solvent such as 1-chlorobutane or methylene chloride at 0.degree.-40.degree. C. for 1 to 24 hours.
Some of the sulfonyl chlorides of Formula VIII may best be prepared by direct chlorosulfonation depending on the substitution pattern on the ringand the nature of the substituent as will be known to one skilled in the art.
The sulfonyl chlorides of Formula VIIIa can also be prepared from the chloro compounds X by the two step sequence shown in Equation 11. R.sub.1,R.sub.2 and n are as previously defined, except that R.sub.1 is not halogenwhen it is para to the sulfonyl group or SCH.sub.3. R' is C.sub.1 -C.sub.4 alkyl or benzyl. ##STR28##
The first step involves nucleophilic displacement of the chlorine atom withan alkyl or benzyl mercaptide to give an intermediate sulfide. The reactioncan be carried out at 25.degree. to 80.degree. C. in a polar solvent such as DMF for 0.5-24 hours. The sulfide is then oxidatively chlorinated to the desired sulfonyl chloride VIIIa by the addition of molecular chlorine or a chlorine equivalent to the sulfide in the presence of water at 15.degree. to 80.degree. C. in an aliphatic carboxylic acid solvent such as acetic acid or an inert organic solvent such as dichloroethane for 1 to24 hours.
Many of the chloro compounds of Formula X in Equation 11, where n=0, can beprepared by the reaction sequence shown in Equation 12. When R.sub.1 is para to the sulfonyl group, then it is H, OCH.sub.3 or CF.sub.3. when R.sub.1 is meta to the sulfonyl group, then it is F, Cl, Ch.sub.3, OCH.sub.3 or CF.sub.3. R.sub.2 and R.sub.5 are as previously defined. ##STR29##
The sequence begins by contacting an appropriately substituted N-t-butylbenzenesulfonamide XIa with two equivalents of butyl lithium at 0.degree. to 25.degree. C. in an inert solvent such as THF for 2 to 10 hours to give a dianion according to the teachings of J. Lombardino, J. Org. Chem., 36, 1843 (1971). The dianion can then be trapped with an esteror, when R.sub.5 is H, with dimethylformamide at -78.degree. to 25.degree. C. to produce, upon aqueous acid workup, the hemiaminal XII. The hemiaminal XII can be de-t-butylated and dehydrated by a catalytic amount of acid such as p-toluenesulfonic acid in a solvent such as benzene or toluene at reflux. The resulting benzisothiazole XIII can be reduced with a reagent such as sodium borohydride in a suitable solvent such as ethanolto produce a 2,3-dihydrobenzisothiazole which is N-aklylated to give Xa by Standard methods known to one skilled in the art.
Many of the chloro compounds of Formula X in Equation 11, where n=1, can beprepared by the reaction sequence shown in Equation 13. R.sub.1 and R.sub.2are as defined for Equation 12. ##STR30##
As in Equation 12, the N-substituted-benzenesulfonamides XI is contacted with 2 equivalents of butyl lithium to form a dianion, which is now trapped with ethylene oxide to produce alcohol XIV. The alcohol can be mesylated by treatment of XIV with mesyl chloride in the presence of an equivalent of a tertiary amine at 0.degree. to 25.degree. C. for 1 to 24 hours in a solvent such as methylene chloride. The resulting mesylate is cyclized by heating with a base such as potassium carbonate in a solvent such as DMF to produce the desired compounds Xb.
Many of the sulfonyl chlorides of Formula VIIIb can also be prepared from the thioether compounds A as shown in Equation 13a. R.sub.1 is not Br, SCH.sub.2 or OCF.sub.2 H. R.sub.4 and R.sub.5 are as previously defined. ##STR31##
As in Equation 13a, the N-methyl carboxamide A is contacted with 2 equivalents of butyl lithium to form a dianion, which is trapped with 2 equivalents of the appropriate epoxide to produce B. Hydrolysis of the amide to its corresponding carboxylic acid followed by acid catalyzed cyclization gives the lactone C. Oxidative chlorination of C as described previously in Equation 11 produces the desired sulfonyl chloride VIIIb.
The amines of Formula IX in Equation 10, can be prepared by reduction of the corresponding nitro compounds of Formula XV, as shown in Equation 14. ##STR32##
The reduction of nitro compounds to amines can be carried out by any of several known methods as described in Preparative Organic Chemistry, 4 Ed., p. 557-563, John Wiley and Sons, New York and London, G. Hilgetag andA. Martini Ed.
The nitro compounds of Formula XV in Equation 14 can be prepared by the procedures outlined in Equations 15 to 41.
As shown in Equation 15, nitro compounds of Formula XV, where J is J.sub.1 (XVa) can be prepared starting from the appropriately substituted nitrobenzenes of Formula XVI. R' is H or CH.sub.2 Cl, R.sub.1, R.sub.2, R.sub.5 and n are as previously defined. ##STR33##
The nitrobenzenes XVI are first reduced to their corresponding amines and nitrated by standard methods to produce, in part, compounds of Formula XVII. In some instances, it may be desirable to first protect the amino group as its acetate prior to nitration as is known to one skilled in the art. The desired nitro compound XVII can be isolated by either fractional crystallization or chromatographic procedures and converted to sulfonyl chlorides XVIII by the method previously discussed in Equation 10. The intermediate sulfonyl chlorides XVIII can be converted into their corresponding sulfonamides by reaction with an appropriate amine (see Equation 8 for references) and subsequently cyclized a) when R' is CH.sub.2 Cl, to the nitro-1, 2-benzothiazines XVa, where n is 1, by heating in the presence of a base such as potassium carbonate or b) when R' is H, by contacting the sulfonamide with NBS in a solvent such as carbon tetrachloride to give sulfonamides where R' is Br, followed by contacting this product with a base to give the nitro benzisothiaxoles XVawhere n is 0. (Note discussion of Equation 9 for NBS brominations when R.sub.1 is methyl.)
the procedure of Equation 15 is similar to the method taught by E. Sianesi et al., Chem. Ber., 104, 1880 (1971) for the preparation of substituted 1,2-benzothiazine-1, 1-dioxides. The starting nitrobenzenes XVI can be prepared by standard methods known to one skilled int he art.
Alternatively, as shown in Equation 16, the nitro compounds of Formula XVa where n is 1 can be prepared, in part, by contacting the nitro acetamides XIX with fuming sulfuric acid according to the method taught by H. Zenno and T. Mizutani, Japanese Patent No. 44/32,404 (1969) (Chem. Abst.: 72:79122 (1970)) for the preparation of 7-nitro-1,2-benzothiazine-1,1-dioxide. The resulting benzothiazines can beisolated and subsequently alkylated by standard methods known to one skilled in the art. ##STR34##
The nitro compounds of Formula XVa where n is 0 can also be prepared from the corresponding 1,2-benzisothiazoles XX as shown in Equation 17. R.sub.1, R.sub.2 and R.sub.5 are as previously defined. ##STR35##
Nitration of XX gives, inpart, the 7-nitro derivative which is isolated by standard methods. The derivative is converted to its 1,1-dioxide by treatment with hydrogen peroxide. Reduction of the carbon-nitrogen double bond with NaBH.sub.4 followed by alkylation of the resulting sulfonamide gives compounds SVa where n is 0. The above reactions are characteristic of 1,2-benzisothiazoles XX. For reviews of their systhesis and reactions, see L. L. Bambas, "The Chemistry of Heterocyclic Compounds," Vol. 4, part III, 1952, p. 223-378, and M. Davis, Adv. Heterocyclic Chem., Vol. 14 (1972) p. 43-98. 1,2-Benzothiaxines are also well known in the literature,for a review of their chemistry and alternate methods of their preparation see J. G. Lombardino, D. E. Kuhla, Adv. Heterocyclic Chem., Vol. 28 (1981)p. 73-126.
As shown in Equation 18, nitro compounds of Formula XVb where J=J.sub.2 canbe prepared from the appropriately substituted nitro sulfonyl chlorides XVIII. R' is H or CH.sub.2 Cl, R.sub.1, R.sub.5 and n are as previously defined. ##STR36##
The nitro sulfonyl chlorides XVIII, previously described inEquation 15, canbe (a) cyclized to the nitro benzoxathiins XVb (N=1) by heating in water at50.degree. to 100.degree. C. for 0.1 to 1 hour when R' is CH.sub.2 Cl or (b) cyclized to the nitro benzoxathioles XVb (n=0) by brominating with NBSor bromine (see discussion of Equation 9 for brominations when R.sub.1 is methyl) followed by heating in water as described above. This is similar to the method taught by Clemo and Turnbull, J. Chem. Soc., 124 (1947) for the preparation of substituted 22,1-benzoxathiins.
2,1-Benzoxathiins and 2,1-benzoxathioles are well known in the literature, for a review of their synthesis and reactions see Chemistry of Heterocyclic Compounts, Vol. 21, John Wiley and Sons, New York, 1966, part2 and part 1, respectively.
As shown in Equation 19, nitro compounds of Formula XV where J=J.sub.4 (XVd) can be prepared from the appropriately substituted amines XVII. R' is H or Ch.sub.2 Cl, R.sub.1, R.sub.5 and n are as previously defined. ##STR37##
the nitro amines XVII, previously described in Equation 15, can be converted into the corresponding cyano compounds XXI by the "Sandmeyer Reaction" (T. Sandmeyer, Chem. Bar., 17, 1633, 2650 (1884)). The cyano function is hydrolyzed to a carboxylic acid by methods known to one skilled in the art, and the carboxylic acids or their corresponding esterscan be (a) cyclized to the nitro isocoumarins XVd (n=1) by heating in the presence of base when R' is CH.sub.2 Cl, or (b) cyclized to the nitro phthalides XVd (n=0) when R' is H by first brominating with NBS or bromine(note discussion of Equation 9 for brominations when R.sub.1 is methyl) followed by heating in a solvent such as aqueous dioxane. The latter method is that taught by J. A. Houbion et al., Org. Prep. and Procedures Int., 11, 27 (1979) for the preparation of 7-nitrophthalide (XVd, n=0, R.sub.1 =H).
the procedure of Equation 19 is similar to the method of P. Banejce and D. Chaudhury, J. Org. Chem., 26, 4344 (1961) for the preparation of substituted isocoumarins; similar methods can be utilized for the preparation of isocoumarins of the J.sub.24 type. Isocoumarins are well known in the literature, for a review of their synthesis and reactions seeR. Barry, Chem. Rev., 64, 229-260 (1964).
the nitro compounds of Formula XVd, where n=0 can also be prepared by reduction of the corresponding 3-nitrophthalic anhydrides with either sodium borohydride or lithium aluminum hydride in tetrahydrofuran as taught by M. Kayser and P. Morand, Can. J. Chem., 48, 2484 (1980) for the preparation of 7-nitrophthalide (XVd; n=0, R.sub.1 =H). Phthalides and phthalic anhydrides are well iknown in the art, for a review of their systhesis and reactions see, S. Wawzonek, Heterocyclic Compounds, Vol. 2, John Wiley and Sons, Inc., New York, 1951.
As shown in Equation 20, nitro compounds of Formula XV where J is J.sub.5 (XVe) can be prepared from the appropriately substituted cyano compounds XXI. R' is H or CH.sub.2 Cl, R.sub.1, R.sub.5 and n are as previously defined. ##STR38##
The nitrobenzonitriles XXI, previously described in Equation 15, can be converted into mercaptans XXII by reacting compounds XXI where R' is Br orCh.sub.2 Cl with an alkali metal salt of hydrogen sulfide in a polar solvent such as ethanol or DMF according to the teachings of S. Gabriel and E. Leupold, Chem. Ber., 31, 2646 (1898). The cyano mercaptans are cyclized to the thiol ethers by heating in aqueous acid as taught by M. Renson and R. Collienne, Bull. Soc. Chem. Belges, 73, 491 (1964) for the preparation of 2-thiophthalide.
Alternatively, as shown in Equation 21, the nitro compounds of Formula XVe can be prepared from the lactones of Formula XVd by reaction with potassium t-butyl mercaptide ina solvent such as DMF at 0.degree. to 100.degree. C. for 0.5 to 24 hours to give the carboxylic acids XXIII, which are then heated in the presence of a catalytic amount of an acid such as p-toluenesulfonic acid in a solvent such as xylene at 100.degree. to 140.degree. C. for 2 to 24 hours. ##STR39##
2-Thiophthalides are widely reported in the literature, for a review of their synthesis and reactions see, B. Iddon, Adv. Heterocyclic. Chem., Vol. 14 (1972) pp. 368-381.
As shown in Equation 22, nitro compounds of Formula XV, where J is J.sub.3 (XVc) can be prepared from the appropriately substituted benzonitriles XXI. R' is H or CH.sub.2 Cl, R.sub.1, R.sub.2, R.sub.5 and n are as previously defined. ##STR40##
The benzonitriles XXI, previously described in Equation 19, are hydrolyzed to carboxylic acids, converted to their corresponding acid chlorides by contacting with a reagent such as thionyl chloride and subsequently reacted with the appropriate amine, by standard methods, to give the amides XXIV. The intermediate amides XXIV can be cyclized to the nitro compounds XVc by the procedures previously described n Equation 15 for converting sulfonamides of XVIII into nitro compounds XVa.
Alternatively, the nitro compounds of Formula XVc can be prepared from the nitro compounds of Formula XVd as shown in Equation 23. R.sub.1, R.sub.2, R.sub.5 and n are as previously defined. ##STR41##
The reactions of phthalides with amines to produce phthalimidines as well known, see C. Hollins, The Synthesis of Nitrogen Ring Compounds, ernest Benn Limited, London, 1924. In these reactions, heating the phthalides (XVd, n=0) with an amine produces the phthalimidines (XVc, n=0) directly, the intermediate alcohols XXV (n=0) are not isolated. With the 3,4-dihydrocoumarins (XVd, n=1) the intermediate amide alcohols XXV (n=1) are formed (see P. Maitte, Colloq. Intern. Centre Natl. Rech. Sci. (Paris), 64, 197 (1955), Chem. Abst., 55:10426 (1961)) and can be converted to the dihydroisoquinolines XVc (n=1) by first conversion to thecorresponding mesylate followed by heating with a base as described above in Equation 13 for the preparation of compounds Xb from the sulfonamide alcohols XIV. For a comprehensive review of the synthesis and reactions ofdihydroisoquinolones see N. J. McCorkindale, The Chemistry of Heterocyclic Compounds, Vol. 38, part III, John Wiley and Sons, New York, in press.
As shown in Equation 24, nitro compounds of Formula XV, where J is J.sub.6 (XVf) can be prepared, in part, by cyclization of the appropriate arylproprionic (n=0) or arylbutyric (n=1) acids XXVI. R.sub.1, R.sub.3, R.sub.4, R.sub.5 and n are as previously defined. ##STR42##
The reaction is carried out by heating the acid with a suitable condensing agent such as polyphosphoric acid, hydrofluoric acid, sulfuric acid or stannic chloride or the acid may be converted to its chloride and heated with a typical Friedel-Crafts reagent such as aluminum chloride or stannicchloride. For a comprehensive review of this and related reactions, see "Friedel-Crafts and Related Reactions", Vols. 1-4, Interscience, New York and London, G. A. Olah, Ed. This procedure has been used to prepare a number of substituted -7-nitro-1-indanones (XVf, n=0), see: H. Jones and T. Y. Shen, German Patent No. 2,337,120 (1974) and Y. Takahi and Y. Yura, Japanes Patent 78/12,421 (1978) Chem. Abst., 89:101857c.
alternatively, the nitro compounds of Formula XVf can be prepared by benzylic oxidation of the corresponding nitroindanes or nitrotetralines astaught by D. Biggs, et al., J. Med. Chem., 19, 472 (1976) for the preparation of 8-nitrotetralone (XVf, n=1, R.sub.1, R.sub.3, R.sub.4 and R.sub.5 =H). Nitroindanes and nitrotetralines are well known in the literature and can be prepared by methods known to one skilled in the art.
Additionally, ketones of Formula XVf where R.sub.3 and/or R.sub.4 are otherthan hydrogen can be prepared from ketones XVF where R.sub.3 and/or R.sub.4are hydrogen by standard ketone alkylation and halogenation methods. For a review, see: H. House, Modern Synthetic Reactions, 2nd Edition, W. A. Benjamin, Inc., Menlo Park, California, 1972, p. 542-570 and 459-478, respectively.
As shown in Equation 25, nitro compounds of Formula XV where J is J.sub.7 (XVg) can be prepared from the appropriately substituted nitrobenzenes XVI. R' is Br or CH.sub.2 Br, R.sub.1, R.sub.2, R.sub.5 and n are as previously defined. ##STR43##
The nitrobenzenes XVI, previously described in Equation 15hare heated with thiourea in a suitable solvent such as ethanol to give thiouronium salts which are oxidatively chlorinated in aqueous acetic acid to give the sulfonyl chlorides XXVII (see also discussion of Equation 11). the sulfonyl chlorides XXVII are dissolved in 10% aqueous sodium hydroxide solution and the nitro groups are catalytically hydrogenated to give intermediate amino sulfonate salts. The salts are cyclized with phosphorous pentachloride and acetyl chloride to give the sultams XXVIII according to the teachings of B. Loev and M. F. Kormendy, J. Org. Chem., 30, 3163 (1965) for the preparation of 3,4-dihydro-2,10-benzothiazine-2,2-dioxide (XXVIII, N=1, R.sub.1, R.sub.5 =H).
Alternatively, the sulfonyl chlorides XXVII can be converted to their corresponding sulfonamides by the methods discussed in Equation 8. Reduction of the nitro group according to procedures of Equation 14 gives the corresponding amino sulfonamides which are cyclized to sultams XXVIII by heating, in the presence of HCl, according to the teachings of E. Sianesi, et al., Chem. Ber., 104, 1880 (1971) for the preparation of 3,4-dihydro-2,1-benzothiazine-2,2-dioxide (XXVIII, n=1, R.sub.1, R.sub.5 =H).
The sultams XXVIII can be nitrated, in part, ortho to the ring nitrogen by standard methods known to one skilled in the art. Isolation by either fractional crystallization or chromatographic methods followed by alkylation of the ring nitrogen under standard conditions gives the nitrosultams XVg as taught by E. Sianesi loc. cit. for the preparation of 1-methyl-8-nitro-3,4-dihydro-2,1-benzothiazine-2,2-dioxide (XVg, n=1, R.sub.1, R.sub.5 =H, R.sub.2 =CH.sub.3).
The sultams of Formula XXVIII of Equation 25 where n=1, can also be prepared from anilines XXIX as shown in Equation 26. R.sub.1 is as previously defined. ##STR44##
The substituted anilines XXIX are reacted with methyl chlorosulfonylacetatein the presence of an acid scavenger to give methyl sulfamoyl acetate intermediates which are hydrolized with dilute sodium hydroxide solution to the corresponding carboxylic acids XXX. The carboxylic acids XXX can becyclized (note discussion of Equation 24) by heating with polyphosphoric acid to give the 4-benzothiazinones XXXI as taught by B. Loev et al., J. Org. Chem., 31,3531 (1966) for the preparation of 4-keto-3,4-dihydro-2,1-benzothiazine-2, 2-dioxide (XXXI, R.sub.1 =H). WhenR.sub.1 is meta to nitrogen, cyclization may produce an isomeric mixture. The desired compounds XXXI can be isolated by either fractional crystallization or chromatographic methods known to one skilled in the art. The benzothiazines XXVIII (N=1) are prepared by reducing the tosylhydrazone derivative of ketones XXX*I with catecholborane in a solvent such as chloroform for 2 to 24 hours at ambient temperatures according to the teachings of G. Kabalka and J. Chandler, Synthetic Comm.,9, 275 (1979).
The synthesis and chemistry of 2,1-benzothiazines has been reviewed, see J.G. Lombardino and D. E. Kuhla, Adv. Heterocyclic Chem., Vol. 28 (1981) p. 73-126. Additionally, for a review of the synthesis and chemistry of benzothiazinone dioxides, see P. Catsoulacos and Ch. Camoutsis, J. Heterocyclic Chem., 16, 1503 (1979).
As shown in Equation 27, nitro compounds of Formula XV where J is J.sub.8 (XVh) can be prepared from the appropriately substituted nitrophenols XXXII. R' is Br or CH.sub.2 Cl, R.sub.1, R.sub.5 and n are as previously defined. ##STR45##
The nitrophenols XXXII, prepared by methods known to one skilled in the art, are heated with aqueous sodium sulfite to give the sulfonic acids XXXIII which are then cyclized by heating with phosphorous oxychloride.
The method is similar to those taught by Marckwald and Frahne, Chem. Ber. 31, 1854 (1898) for the preparation of 1,2-benzoxathiole, and Truce and Hoerger, J. Amer. Chem. Soc., 76, 5357 (1954) and 77 2496 (1955) for the preparation of 1,2-benzoxathiin.
Alternatively, compounds of Formula XVh where n=0 can be prepared from nitrophenols XXXIV by the three step sequence shown in Equation 28. This is the method taught by Shearing and Smiles, J. Chem. Soc., 1348 (1937) for the preparation of 5-methyl-1,2-benzoxathiole. For a review of this and alternate methods of synthesis of 1,2-benzoxathioles, see Chemistry ofHeterocyclis Compounds, Vol. 21, part 1 (1966). ##STR46##
Compounds of Formula XVh where n=1 can be prepared from nitrophenols XXXII where R'=R.sub.5 =H by the three step sequence shown in Equation 29. ##STR47##
The phenol is brominated with NBS in a solvent such as carbontetrachloride and the hydroxy group is then converted to its methanesulfonate ester by treatment with mesyl chloride in the presence of an acid scavenger such astriethylamine in a solvent such as methylene chloride. The methanesulfonateester is then cyclized by reacting with a strong base such as sodium hydride or potassium t-butoxide in a polar solvent such as DMF at 0.degree. to 80.degree. C. for 0.5 to 24 hours. For alternative methods ofsynthesis and the reactions of 1,2-benzoxathiins, see Chemistry of Heterocyclic Compounds, Vol. 21, part 2, (1966).
As shown in Equation 30, nitro compounds of Formula XV where J is J.sub.9 (XVi) can be prepared from the appropriately substituted nitrobenzenes XVI. R' is Br or CH.sub.2 Br, R.sub.1, R.sub.2, R.sub.5 and n are as previously defined. ##STR48##
The nitrobenzenes XVI, previously discussed in Equation 15, are reacted with potassium cyanide in a solvent such as acetone to give nitrile intermediates which are hydrolized to the corresponding carboxylic acids XXXV by standard methods known to one skilled in the art. The nitro carboxylic acids XXXV, when reduced by standard methods (see discussion ofEquation 14), spontaneously cyclize to give the lactams XXXVI. For a discussion of this reaction when n is 0, see W. Sumpter and F. Miller, TheChemistry of Heterocyclic Compounds, Vol. 8, Interscience Publishers, Inc.,New York, 1954, P. 134-135, and references cited therein. For a discussion of this reaction when n is 1, see G. Jones, The Chemistry of Heterocyclic Compounds, Vol. 32, John Wiley and Sons, New York, 1977, p. 216-217, and references cited therein. The nitro lactams XVi are prepared from lactams XXXVI by the nitration, alkylation sequence described earlier for the preparation of nitro sultams XVg in Equation 25.
Alternatively, lactams XXXVI of Equation 30 can be prepared from the substituted anilines XXIX of Equation 26, as shown in Equation 31. R.sub.1and n are as previously defined. ##STR49##
The substituted anilines XXVII are reacted with either a chloroacetyl chloride (n=0) of .beta.-chloropropionyl chloride (n=1, R.sub.5 =H) in thepresence of an acid scavenger to give the chloro amides XXXVII. The amides XXXVII are cyclized by heating in the presence of a suitable Friedel-Crafts reagent such as AlCl.sub.3 (see discussion of Equation 24) to give the lactams XXXVI. The method of Equation 31 has been widely used for the preparation of oxindoles (XXXVI, n=0; see W. Sumpter and F. Miller, loc. cit., p. 135-136 for discussion and references) and for the preparation of 3,4-dihydro-2-quinolones (XXXVI, n=1; see G. Jones, loc. cit., p. 164-168 for discussion and references). For a general review of oxindole chemistry see W. Sumpter and F. Miller, loc. cit., p. 134-153.
As shown in Equation 32, nitro compounds of Formula XV where J is J.sub.10 (XVj) can be prepared from the appropriately substituted phenols XXXII. R'is Br or CH.sub.2 Cl, R.sub.1, R.sub.5 and n are as previously defined. ##STR50##
The nitrophenols XXXII, prepared by methods known to one skilled in the art, are reacted with potassium cyanide in a solvent such as DMF at 0.degree. to 80.degree. C. for 0.5 to 24 hours to give the cyanophenols XXXVIII. The cyano function is hydrolyzed to its corresponding carboxylic acid by methods known in the art. For n=0, the carboxylic acids cyclize spontaneously. For n=1, the carboxylic acid is cyclized by heating with a reagent such as thionyl chloride as taught by Wakselman et al. Tetrahedron, 30 4069 (1974) for the preparation of substituted dihydrocoumarins and 2-benzofuranones.
Alternatively, as shown i Equation 33, nitro compounds of Formula XVj wheren=1 can be prepared by reducing the corresponding coumarins XVp, which are readily prepared from nitrosalicaldehydes XXXIX by heating with, for example where R.sub.3 is H, potassium acetate in acetic anhydride according to the teachings of Gqola, et al., Fort. Hare Pap., 6, 197 (1975) (Chem. Abst. 84:150452X (1975)) for the preparation of 8-nitrocoumarin (XVp, R.sub.1 =H). Coumarins are well known in the literature, for a review see Comprehensive Organic Chemistry, Vol. 4, Pergamon Press 1979. ##STR51##
As shown in Equation 34, nitro compounds of Formula XV where J is J.sub.11 and n is 0 (XVk) can be prepared from the appropriately substituted nitro phenols XXXX. R.sub.6 and R.sub.7 are H, R.sub.1 is as previously defined. ##STR52##
This method is parrallel to that previously discussed for the preparation of Formula XVj in Equation 32. The 2-benzofuranones XVk, where R.sub.6 and/or R.sub.7 are other than hydrogen, can be prepared from the 2-benzofuranones XVk where R.sub.6 and/or R.sub.7 are hydrogen by standardalkylation methods known in the art. For a review see: H. House, Modern Synthetic Reactions, 2nd Edition, W. A. Benjamin, Inc., Menlo Park, California 1972, p. 542-570.
As shown in Equation 35, nitro compounds of Formula XV where J is J.sub.11 and n is 1 (XVl) can be prepared from the appropriately substituted nitrophenylacetic acids XXXXI. R.sub.1, R.sub.6 and R.sub.7 are as previously defined. ##STR53##
The nitrophenylacetic acids, prepared by methods known to one skilled in the art, are treated with formaldehyde in the presence of a strong acid such as HCl in a solvent such as acetic acid at 25.degree. to 200.degree. C. for 2 to 48 hours. This method has been used to prepare substituted benzo[c]pyran-3-ones, see U.S. Pat. No. 3,480,634 (Chem. Abst. 72:43486s (1970)).
Alternatively, as shown in Equation 36, benzo[c]pyran-3-ones XVl can be prepared from the appropriately substituted nitrotoluic acids XXXXII. R.sub.6 and R.sub.7 are H, R.sub.1 is a previously defined. ##STR54##
The nitrotoluic acids, prepared by methods known to one skilled in the art,are heated with dimethylformamide dimethylacetal in DMF to produce, in part, the nitroisocoumarins XXXXIII. The isocoumarins are reduced by lithium aluminum hydride to gove a hemiacetal which is then separated and oxidized with pyridinium chlorochromate (PCC) to give the desired benzo[c]pyran-3-ones. This is the method taught by Somei and Shoda, Heterocycles, 17, 417 (1982) for the preparation of 1,4-dihydro-5-nitrobenzo[c]pyran-3-one (Xvl, R.sub.1, R.sub.6 and R.sub.7 =H).
The benzo[c]pyran-3-ones XVl where R.sub.6 and/or R.sub.7 are other than hydrogen can be prepared by the standard alkylation methods discussed for Equation 34.
additionally, benzo[c]pyran-3-ones XVl, where R.sub.1 is other than SCH.sub.3, can be prepared by the Baeyer-Villiger oxidation of 2-indanonesXVm (n=0) (vide infra). The Baeyer-Villiger oxidation of ketones to esters is well known in the literature, for a review see: Organic Reactions, Vol.9, John wiley and sons, New york, 1957, p. 73 to 107. For application of this reaction to 2-indanones see G. Swan J. Chem. Soc., 1720 (1949).
As shown in Equation 37, nitro compounds of Formula XV, where J is J.sub.12(XVm), can be prepared from the appropriately substituted indenes and dihydronaphthalenes of Formula XXXXIV. R.sub.7 is H, R.sub.1, R.sub.6 and n are as previously defined. ##STR55##
The nitroolefins XXXXIV can be converted to their corresponding epoxides XXXXV by either direct oxidation with a peracid such as m-chloroperbenzoicacid or via hydrobromination followed by treatment with a base as known to one skilled in the art. The epoxides XXXXV are rearranged to the desired 2-indanones (XVm, n=0) or tetralones (XVm, n=1) by reaction with either a protonic acid such as sulfuric acid as taught by Rosen et al., J. Org. Chem., 29, 1723 (1964) or a Lewis Acid such as BF.sub.3 -etherate as taught by Bondinell and Pendleton, U.S. Pat. No. 4,192,888 (1980).
The starting nitroindenes (XXXXIV, n=0) and nitrodihydronaphthalenes (XXXXIV, n=1) are well known in the literature and can be prepared by methods known to one skilled in the art.
Alternatively, as shown in Equation 38, 2-tetralones of Formula XVm (n=1) can be prepared from the appropriately substituted nitrophenylacetic acidsXXXXI discussed previously in Equation 35 by reaction with ethylene under Friedel-Crafts conditions. For a review of this and alternate syntheses of2-tetralones see Shner and Przhiyaglovskaya, Russian Chemical Reviews, 35, 523 (1966). ##STR56##
Additionally, the 2indanones (XVm, n=0) and 2-tetralones (XVm, n=1) can be prepared from the corresponding 1indanones *XVf, n=0) and 1-tetralones (XVf, n=1), respectively, via a 1,2-carbonyl transposition, as shown in Equation 39. R.sub.1, R.sub.6 and n are as previously defined. ##STR57##
1,2-Carbonyl transpositions are well known in the literature and can be performed by a wide variety of methods, for a recent review, see: D. G. Morris, Chem. Soc. ReviewsII, 397-434 (1983). For application of this method to indanones, see U.S. Pat. No. 4,192,888. For application of the method to tetralones, see Shner and Przhiyaglovskaya loc. cit.
As shown in Equation 40, nitro compounds of Formula XV, where J is J.sub.22(XVn), can be prepared from the appropriately substituted nitrophenols XXXXVI. R.sub.1, R.sub.3, R.sub.4 and n are as previously defined. ##STR58##
the reaction of the nitrophenol XXXXVI with the halo-acid salts produces the nitro ethers XXXXVII which are subsequently cyclized, in part, to giveXVn (R.sub.3, R=H) by heating the acid with a suitable condensing agent such as polyphosphoric acid, hydrofluoric acid, sulfuric acid or stannic chloride, or the acid may be converted to its chloride and heated with a typical Friedel-Crafts reagent such as aluminum chloride or stannic chloride. The ketones of Formula XVn where R.sub.3 and/or R.sub.3 are other than hydrogen can be prepared from detones XVn where R.sub.3 and/or R.sub.4 are hydrogen by standard ketone alkylation and halogenation methods as described previously for compounds of Equation 24.
Alternatively, as shown in Equation 41, compounds of Formula XVn where n=0 can be prepared from nitrobenzoates of Formula XXXXVIII. R.sub.1, R.sub.3 and R.sub.4 are as previously defined. ##STR59##
The phenol XXXXVIII is first alkylated with ethyl chloroacetate in the presence of an acid scavenger followed by reaction with a base to effect cyclization to the ketoester XXXXIX. The ketoester is than saponafied and decarboxylated by heating with acid to give the 3-ketobenzofurans XVn (n=0). 3-Ketobenzofurans are well known in the art, for a review of their synthesis and chemistry see Chemistry of Heterocyclic Compounds, Vol. 29, Interscience Publishers, Inc., New York, 1974, p. 210-296.
Benzopyran-4-ones are also well known in the art, for a review see Chemistry of Heterocyclic Compounds, Vol. 31, Interscience Publishers, Inc., New York, 1977. For a review of the synthesis and chemistry of benzoxepin-5-ones see Chemistry of Heterocyclic Compounds, Vol. 26, Interscience Publishers, Inc., New York, 1972.
The nitro compounds of Formula XV in Equation 14, where J is J.sub.13, J.sub.14, J.sub.15, J.sub.16 J.sub.17, J.sub.18, J.sub.19, J.sub.20, J.sub.21, or J.sub.23 can be prepared from the nitro compounds of FormulaXV where J is J.sub.1, J.sub.2, J.sub.3, J.sub.4, (J.sub.24), J.sub.5, J.sub.7, J.sub.8, J.sub.9, J.sub.10, or J.sub.22, respectively, (n=1) by the bromination/dehydrobromination sequence described above for sulfonamides IV in Equation 9.
Alternately, nitro compounds of Formula XV in Equation 14 where J is J.sub.15 can be prepared from nitro compounds of Formula XV where J is J.sub.16 by treatment with the appropriate amines R.sub.2 NH.sub.2 as taught by J. Jones and A. Pinder, J. Chem. Soc., 2612 (1958). Additionally, the nitro compounds of Formula XV where J is J.sub.21 can beprepared as discussed in Equation 33.
The nitro compounds of Formula XV in Equation 14 where J is J.sub.18 can also be prepared from ketones XXXI by base treatment of its tosylhydrazonederivative as taught by B. Loev, et al., J. Org. Chem., 31, 3531 (1966).
The preparation of compounds of Formula I where J is J.sub.1 to J.sub.12 and J.sub.22 and n=2 can be prepared using the procedures outlined above for the analogous compounds where n=1.
The amines of Formula III in Equations 1 and 4 are also important intermediates for the preparation of the compounds of this invention and are described below.
The pyrimidines and triazines of Formula (IIIa) to (IIId) below are either known or can be prepared by obvious methods by one skilled in the art. ##STR60##
For a review of the synthesis and reactions of 2-aminopyrimidines (IIIa, Z.dbd.CR') see The Chemistry of Heterocyclic Compounds, Vol. 16, John Wiley and Sons, New York (1962). For a review of the synthesis and reactions of 2-amino-s-triazines (IIIa, Z.dbd.N) see The Chemistry of Heterocyclic Compounds, Vol. 13, John Wiley, New York (1959), F. C. Schaefer, U.S. Pat. No. 3,154,547 and F. C. Schaefer and K. R. Huffman, J.Org. Chem., 28, 1812 (1963). The synthesis of the bicyclic amines IIIb and IIIc is taught in European patent application No. 803,005,05.7. The synthesis of bicyclic amines IIId is taught in European Patent Publication46,677.
The amines of Formula III where X is OCF.sub.2 H, OCH.sub.2 F, OCF.sub.3 orCF.sub.3 ; or X.sub.1 is OCF.sub.2 H and/or Y is OCH.sub.2 F, OCF.sub.3, SCH.sub.2 F, SCF.sub.3 or GCF.sub.2 T wherein G is O or S and T is H, CHClF, CHBrF or CHFCF.sub.3 can be prepared by methods taught in South African patent application No. 825,045, or by suitable modifications that would be obvious to one skilled in the art.
The pyrimidines of Formula IIIa (Z.dbd.CH) where ##STR61##can be prepared according to the methods taught in European patent application No. 82-306,492.8 or suitable modifications thereof known to one skilled in the art.
The triazine amines of Formula IIIe where X.sub.3 is CH.sub.3 or OCH.sub.3 and R is H or CH.sub.3 can be prepared according to the teachings of U.S. Ser. No. 472,879, filed Mar. 14, 1983. ##STR62##
Preparations of 3- amino-1,2,4-triazoles of Formula (IIIf) are known in theart and 1,2,4-triazoles are reviewed in The Chemistry of Heterocyclic Compounds "Triazoles 1,2,4" (John Wiley and Sons, New York, 1981). Commonly used starting materials containing nitrogen are N-aminoguanidine,hydrazine, alkylhydraxines, cyanamide, ethyl cyanoacetimidate, dimethyl cyanodithioimidocarbonate, dimethyl cyanoimidocarbonate, ethoxymethylenecyanamide, and acylhydrazines. Some literature synthesis are illustrated below. Using these techniques or suitable modifications that would be apparent to one skilled in the art, the 3-amino-1,2,4- triazole intermediates can be readily prepared.
Heating equimolar amounts of ethyl propionimidate hydrochloride and N-aminoguanidine nitrate in pyridine gives 3-amino-5-ethyltriazole; GermanPatent 1,073,499 (1966); Berichte, 96, 1064 (1963). ##STR63##Condensation of hydrazine with ethyl N-cyanoacetimidate yields 3-amino-5-methyltriazole; Journal of Organic Chemistry, 28, 1816 (1963). ##STR64##U.S. Pat. No. 2,835,581 (1958) teaches the preparation of 3 -amino-5-(hydroxymethyl)triazole from N-aminoguanidine and glycolic acid and British Patent 736,568 (1955) describes the synthesis of 3-amino-5-mercaptotriazole. Condensing hydrazine with dimethyl cyanodithioimidocarbonate in acetonitrile gives 3-amino-5-methylthio-1,2,4-triazole while reaction of hydrazine with dimethyl N-cyanoimidocarbonate produces 3-amino-5-methosy-1,2,4-triazole; Journal of Organic Chemistry, 39, 1522 (1974). ##STR65##
Reaction of substituted hydrazines with N-cyanothioimidocarbonates (prepared according to the procedure given in D. M. Wieland, Ph.D. Thesis,1971, pp. 123-124) yields disubstituted aminotraizoles as shown below. ##STR66##
Many of the aminoheterocyclic intermediates of Formula (III) where R is methyl may be prepared by a two-step procedure as described for IIIi in Equation 42. X, Y and Z are as previously defined. ##STR67##
A solution of the amine L in concentrated hydrochloric acid is treated withsodium nitrite solution and the chloro compound LI is isolated in the usualmanner by filtration of the acidic solution. A representative procedure is described by Bee and Rose in J. Chem. Soc. C, 2031 (1966), for the case inwhich Z=CH, and X=Y=OCH.sub.3. Displacement of the chlorine of LI may be accomplished by heating with an excess of methylamine in water to obtain the methylamino heterocycle (IIIg).
Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by contacting compounds of Formula I witha solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonate or hydride). Quaternary amine salts can be made by similar techniques.
Salts of compounds of Formula I can also be prepared by exchange of one cation for another. Cationic exchange can be effected by direct contactingof an aqueous solution of a salt of a compound of Formula I (e.g., alkali metal or quaternary amine salt) with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water, e.g., a copper salt, and can be separated by filtration.
Exchange may also be effected by passing an aqueous solution of a salt of acompound of Formula I (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cationto be exchanged. In this method, the cation of the resin is exchanged for that of the original salt and the desired product is eluted from the column. This method is particularly useful when the desired salt is water-soluble, e.g., a potassium, sodium or calcium salt.
Acid addition salts, useful in this invention, can be obtained by reacting a compound of Formula I with a suitable acid, e.g., p-toluenesulfonic acid, trichloroacetic acid or the like.
EXAMPLE 1
2-t-Butyl-3-hydroxy-7-chloro-2,3-dihydro-1,2-benzisothiazole-1,1-dioxide
To a solution of 49.5 g of N-t-butyl-2-chlorobenzenesulfonamide in 875 mls of dry THF was added 262 ml of a 1.6M hexane solution of n-butyl lithium at -20.degree. to -5.degree. C. under an inert atmosphere. The mixture wasstirred at 0.degree. C. for 1 hour, room temperature for 2 hours, recooled to -78.degree. C. and contacted with 38 mls of dry dimethylformamide. The mixture was allowed to warm to room temperature overnight, poured into water, acidified to a ph of .about.3 and ether extracted. The extract was washed with water and brine, dried over MgSO.sub.4 and concentrated to give a yellow oil. The oil was dissolved in 50% ether in hexane solution and allowed to stand, giving, after filtration, 38 g of the title compoundas colorless crystals, m.p. 139-141.degree. C.
90 MHz (CDCl.sub.3).delta.: 7.7-7.2 (m 3H, arom); 6.9 (br. d, J=11 Hz, 1H, CH or OH); 4.2 (br. d, J=11 Hz, 1H, OH or CH); and 1.5 (s, 9H, CH.sub.3 's).
IR (nujol) 3440 cm-.sup.1.
EXAMPLE 2
7-Chloro-1,2-benzisothiazole-1,1-dioxide
A solution of 37 g of 2t-butyl-3-hydroxy-7-chloro-2,3-dihydro-1,2-benzisothiazole-1,1-dioxide and 0.2 g of tosic acid in 370 mls of benzene was refluxed through a Dean-Stark water separator for 16 hours, cooled in ice and filtered to give 18.9 g of the title compound as colorless crystals, m.p. 162.degree.-164.degree. C.
90 MHz NMR (CDCl.sub.3).delta.: 9.15 (s, 1H, CH); and 8.0-7.7 (m, 3H, arom).
IR (nujol) 1445, 1320, 1170 cm-1.
EXAMPLE 3
7-Chloro-2,3-dihydro-1,2-benzisothiazole-1,1-dioxide
A suspension of 17.9 g of 7-chloro-1,2-benzisothiazole-1,1-dioxide in 180 ml of absolute ethanol was cooled to 0.degree. C. and treated with 3.33 g of sodium borohydride at such a rate that the temperature remained below 5.degree. C. The mixture was warmed to room temperature for 30 minutes, recooled to 0.degree. C. and treated with glacial acetic acid to destroy excess hydride. The mixture was concentrated to dryness, the resulting solid suspended in water, filtered, washed with water and dried in vacuo at 50.degree. C. for 16 hours to give 17.6 g of the title compound as a white powder, m.p. 159.degree.-161.degree.0 C.
90 MHz NMR (CDCl.sub.3 /DMSO).delta.: 7.9-7.2 (m, 3H, arom); 6.9 (br, 1H, NH); and 4.4 (s, 2H, CH.sub.2).
IR (nujol) 3220 cm-.sup.1
EXAMPLE 4
2-Methyl-7-chloro-2,3-dihydro-1,2-benzisothiazole-1,1-dioxide
A solution of 16.6 g of 7-chloro-2,3-dihydro-1,2-benzisothiazole-1,1-dioxide in 85 mls of dry dimethylformamide was cooled and treated with 10 g of potassium t-butoxideat such a rate that the temperature remained below 6.degree. C. The resulting suspension was stirred at 5.degree. to 10.degree. C. for 30 minutes, treated with 6.1 mls of methyl iodide at 10.degree. to 15.degree.C. and stirred at room temperature for 16 hours. The mixture was poured into ice water and the resulting solid was filtered, washed with water anddried in vacuo at 50.degree. C. for 1.5 hours to give 15.4 g of the title compound as a pinkish solid, m.p. 95.degree.-97.degree. C.
90 MHz NMR (CDCl.sub.3).delta.: 7.8-7.2 (m, 3H, arom); 4.4 (s, 2H, CH.sub.2); and 3.0 (s, 3H, CH.sub.3).
IR (nujol) 1460, 1300, 1165, 1152 cm-.sup.1.
EXAMPLE 5
2-Methyl-7-(phenylmethylthio)-2,3-dihydro-1,2-benzisothiazole-1,1-dioxide
To a solution of 12 g of potassium-t-butoxide in 100 ml of dry dimethylformamide was added 12.9 mls of benzyl mercaptan at -5.degree. to 0.degree. C. under an inert atmosphere followed by 12.2 g of 2-methyl-7-chloro-2,3-dihydro-1,2-benzisothiazole-1,1-dioxide. The mixturewas stirred at room temperature for 16 hours and poured into water to give a gummy solid. The water was decanted and extracted with ethyl acetate. The gummy solid was slurried in ethyl acetate and filtered to give 5.9 g of the title compound as a light orange solid, m.p. 119.degree.-122.degree. C. The combined ethyl acetate extract and filtratewere washed with water and brine, dried over MgSO.sub.4 and concentrated toa solid which was slurried in either and filtered to give an additional 7.6g of product, m.p. 121.degree.-124.degree. C. Total yield was 13.5 g.
90 MHz NMR (CDCl.sub.3).delta.: 7.5-7.3 (m, 8H, arom); 4.3 (br. s, 4H, CH.sub.2 's); and 2.9 (s, 3H, CH.sub.3).
IR (nujol) 1455, 1290, 1155, cm-.sup.1.
EXAMPLE 6
2-Methyl-2,3-dihydro-1,2-benzisothiazole-7-sulfonamide-1,1-dioxide
To a solution of 9.8 g of 2-methyl-7-(phenylmethylthio)-2.3-dihydro-1,2-benzisothiazole-1,1-dioxide and 1.44 mls of water in 200 mls of 1,2-dichloroethane was added a solution of 12.9 mls of sulfuryl chloride in 50 mls of 1,2-dichloroethane,dropwise, at 65.degree. to 70.degree. C. The mixture was heated at 70.degree. to 75.degree. C. for 2 hours, cooled to room temperature and concentrated. The residue was dissolved in 100 ml of methylene chloride and added to a solution of 4.0 ml of liquified ammonia in 200 mls of methylene chloride at -78.degree. to -40.degree. C. The mixture was warmedto room temperature, stirred for 16 hours, concentrated and the resulting white solid was suspended in 150 mls of 1N HCl, filtered, washed with water and ether and dried in vacuo at 70.degree. C. to 5.0 g of the title compound as a white powder, m.p. 195.degree.-197.degree. C. (a similar preparation had m.p. 203.degree.-205.degree. C.
90 MHz NMR (CDCl.sub.3 /DMSO).delta.: 8.2-7.7 (m, 3H, arom); 7.5 (b, 2H, NH.sub.2); 4.4 (s, 2H, CH.sub.2); and 2.9 (s, 3H, CH.sub.3).
IR (nujol) 3330, 3230, cm-.sup.1.
EXAMPLE 7
N-(Butylaminocarbonyl)-2-methyl-2,3-dihydro-1,2-benzisothiazole-7-sulfonamide-1,1-dioxide
A suspension of 13.0 g of 2-methyl-2,3-dihydro-1,2-benzisothiazole-7-sulfonamide-1,1-dioxide, 11.2 ml of butyl isocyanate and 13.8 g of potassium carbonate in 200 ml of dry methyl ethyl ketone was heated at reflux for 2 hours. 13.8 g of potassium carbonate was added and heating was continued for an additional 16 hours. The mixture was cooled, the solvent was decanted from the solids, concentrated in vacuo, the residue dissolved in ethyl acetate and washed with saturated aq. NaHCO.sub.3. The aqueous wash was added to the originalsolids diluted with water and acidified to pH .about.3 with dilute HCl. Themixture was extracted with methylene chloride, the extract was washed with water and brine, dried and concentrated in vacuo leaving a solid which wasslurried in ether and filtered to give 13.24 g of the title compound as a white powder, m.p. 162.degree.-164.degree. C.
90 MHz NMR (CDCl.sub.3).delta.: 8.4-7.5 (m, 3H, arom); 6.4 (b, t, 1H, NH); 5.8 (b, 1H, NH); 4.4 (s, 2H, CH.sub.2); 3.1 (m, 2H, CH.sub.2); 3.0 (s, 3H,CH.sub.3); and 1.7-0.7 (m, 7H, alkyl).
IR (nujol) 3350, 3240, 1680 cm-.sup.1.
EXAMPLE 8
N-((4.6-Dimethoxypyrimidin-2-yl)aminocarbonyl)-2-methyl-2,3-dihydro-1,2-benzisothiazole-7-sulfonamide-1,1-dioxide
A mixture of 13.2 g N-(butylaminocarbonyl)-2-methyl-2,3-dihydro-1,2-benzisothiazole-7-sulfonamide-1,1-dioxide, 3.7 ml of butyl isocyanate and 0.1 g of DABCO was treated with 3.5 ml of phosgene at 135.degree.-138.degree. C. for 2 hours, purged with N.sub.2 and cooled to 0.degree. C. depositing a solid which was filtered under nitrogen to give 5.5 g of 2-methyl-2,3-dihydro-1,2-benzisothiazole-7-sulfonyl isocyanate-1,1-dioxideas a cream colored solid, m.p. 176.degree.-180.degree. C., IR (nujol) 2220 cm.sup.-1.
To a solution of 0.69 g of the isocyanate in 10 ml of dry methylene chloride was added 0.31 g of 2-amino-4,6-dimethoxypyrimidine. The mixture was heated to reflux for 1 minute and stirred at 25.degree. C. for 16 hours. The resulting solid was filtered, washed with methylene chloride and ether to give 0.81 g of the title compound as a white powder, m.p. 229.degree.-231.degree. C.
90 MHz NMR (TFA-d).delta.: 8.7-7.9 (m, 3H, aromatic); 6.3 (s, 1H, CH); 4.6 (s, 2H, CH.sub.2); 4.2 (s, 6H, OCH.sub.3); and 3.15 (s, 3H, CH.sub.3).
IR (nujol) 1710, cm.sup.-1.
EXAMPLE 9
N-((4.6-Dimethoxypyrimidin-2-yl)aminocarbonyl)benzo[c]furan-1-one-7-sulfonamide
A slurry of 0.8 g of crude phthalide-7-sulfonylisocyanate in 10 ml of dry acetonitrile was combined with 0.53 g of 2-amino-4,6-dimethoxypyrimidine and the mixture stirred at ambient temperature for 18 hours. The mixture was then diluted with 15 ml of acetonitrile, heated to a boil, filtered hot, the filtrate concentrated to 10 ml, allowed to cool, the crystals collected and washed with acetonitrile. Yield 0.69 g, m.p. 210.degree.-215.degree. C. (dec.). Recrystallization from acetonitrile improved the m.p. to 219.degree.-221.degree. C.(d).
NMR (CDCl.sub.3): .delta.4.06 (s, 6H, OCH.sub.3 's); 5.40 (s, 2H, CH.sub.2); 5.84 (s, 1H, pyrimidine C.sub.5 -H); 7.2 (broad s, 1H, NH); 7.8-8.1 (m, 2H); 8.5 (broad d, J=8, 1H); and 13.0 (broad s, 1H, NH).
IR (nujol) 3430 cm.sup..times.1 (NH); 1765 (lactone); and 1728, 1708 sulfonylurea).
The following compounds can be prepared according to the procedures of Examples 1-9 and Equations 1-42.
TABLE 1a__________________________________________________________________________ ##STR68##W n R R.sub.1 R.sub.2 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CH 227-229O 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CH 235-237O 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 229-231O 0 H H CH.sub.3 H Cl OCH.sub.3 CH 206-208O 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 N 210-212O 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 N 207-209O 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH 215-217O 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CH 221-222O 0 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 219-221O 0 H H CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CH 224-226O 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 N 169-171O 0 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 N 180-183O 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 OCH.sub.3 CH 234-236O 0 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 CH 237-239O 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH 206-210O 0 H H CH(CH.sub.3).sub.2 H Cl OCH.sub.3 CH 239-241O 0 H H CH(CH.sub.3).sub.2 H F OCH.sub.3 CH 221-223O 0 H H CH(CH.sub. 3).sub.2 H CH.sub.3 OCH.sub.3 N 186-188O 0 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 N 199-201O 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 CH(OCH.sub.3).sub.2 CH 170-175O 0 CH.sub.3 H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 CH 200-204O 0 CH.sub.3 H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 N 192-195O 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 230-235O 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 N >215O 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 N 258-266O 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 199- 200O 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NS 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHS 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 N 182-188O 0 H -o-F CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-Br CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-OCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub. 3 H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 NH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 NHCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CCH CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CF.sub.3 CH 193-195O 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 1 H H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CHO 1 H H CH(CH.sub.3).sub.2 H OCH.sub.3 CH.sub.3 CHO 1 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 CH 211-214O 1 H H CH(CH.sub.3).sub.2 H Cl OCH.sub.3 CHO 1 H H CH(CH.sub.3).sub.2 H OCH.sub.3 CH.sub.3 NO 1 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H CH.sub.3 ##STR69## CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CH 169-171O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CClO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CBrO 1 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH 195-198O 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CH 197-199O 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 206-208O 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CH 199-201O 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 N 187-190O 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 N 185-187O 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH 193-195O 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CH 167-170O 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 214-216O 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CH 195-197O 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub. 3 N 165-168O 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H F OCH.sub.3 CH 224-226O 0 H H CH.sub.3 H Br OCH.sub.3 CH 219-221O 0 H H CH.sub.3 H CH.sub.2 F OCH.sub.3 CHO 0 H H CH.sub.3 H OCF.sub.2 H CH.sub.3 CH 228-230O 0 H H CH.sub.3 H CF.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCF.sub.2 H OCH.sub.3 CH 185-189O 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCF.sub.2 H OCF.sub.2 H CH 207-210O 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H Br OCH.sub.3 CH 190-192O 0 H H CH(CH.sub.3)CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH(CH.sub.3)CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH(CH.sub.3)CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 220-222O 0 H H CH(CH.sub.3)CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CH 221-224O 0 H H CH(CH.sub.3)CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 N 151-153O 0 H H CH(CH.sub.3)CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 N 139-142O 0 H H CH.sub.3 H CH.sub.3 ##STR70## CHO 0 H H CH.sub.3 H CH.sub.3 ##STR71## CHO 0 H H CH.sub.3 H CH.sub.3 H CHO 0 H H CH.sub.3 H CH.sub.3 CN CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H Cl OCH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 CH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 192-194O 0 H H CH.sub.3 H OCH.sub.3 CH(OCH.sub.3).sub.2 CH 167-168O 0 H H CH.sub.3 H OCH.sub.2 CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 H OCH.sub.3 N.sub.3 CH__________________________________________________________________________
TABLE 2a__________________________________________________________________________ ##STR72##W n R R.sub.1 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.3 CHO 0 H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 NO 0 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub. 3 CHO 1 H H H CH.sub.3 OCH.sub.3 CHO 1 H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 NO 1 H H H CH.sub.3 OCH.sub.3 NO 1 H H H OCH.sub.3 OCH.sub.3 NS 0 H H H OCH.sub.3 OCH.sub.3 CHS 1 H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 0 H -o-F H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H OCH.sub.3 OCH.sub.3 CHO 0 H -o-Br H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H Cl OCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H CH.sub. 3 NH.sub.2 CHO 0 H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 CF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H CH.sub.3 ##STR73## CHO 0 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CClO 0 H H H CH.sub.3 CH.sub.3 CBrO 1 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H Cl OCH.sub.3 CHO 0 H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H F OCH.sub.3 CHO 0 H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H CF.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR74## CHO 0 H H H Br OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR75## CHO 0 H H H CH.sub.3 H CHO 0 H H H CH.sub.3 CN CHO 0 H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H CH.sub.3 OCF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H CH.sub.3 SCF.sub.3 CHO 0 H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H H CH.sub.3 CH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 CHO 2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H Cl OCH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 NO 2 H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 3a__________________________________________________________________________ ##STR76##W n R R.sub.1 R.sub.2 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CH 215-216O 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CH 215-217O 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 202-204O 0 H H CH.sub.3 H Cl OCH.sub.3 CH 211-213O 0 H H CH.sub.3 H CH.sub. 3 OCH.sub.3 N 192-193O 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 N 198-200O 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH 150-153O 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 OCH.sub.3 CH 195-197O 0 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 CH 199-203O 0 H H CH(CH.sub.3).sub.2 H Cl OCH.sub.3 CH 180-183O 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 OCH.sub.3 N 181-183O 0 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 N 203-206O 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 NO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NS 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHS 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H -o-F CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-Br CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-OCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 NH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 NHCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CCH CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 ##STR77## CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CClO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CBrO 1 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub. 2 CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H Cl OCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H F OCH.sub.3 CHO 0 H H CH.sub.3 H Br OCH.sub.3 CHO 0 H H CH.sub. 3 H CH.sub.2 F OCH.sub.3 CHO 0 H H CH.sub.3 H OCF.sub.2 H OCH.sub.3 CHO 0 H H CH.sub.3 H OCF.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H CF.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 ##STR78## CHO 0 H H CH.sub.3 H CH.sub.3 ##STR79## CHO 0 H H CH.sub.3 H CH.sub.3 H CHO 0 H H CH.sub.3 H CH.sub.3 CN CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHFCF.sub.3O 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H Cl OCH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 4a__________________________________________________________________________ ##STR80##W n R R.sub.1 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H CH.sub.3 CH.sub.3 CH 185-200O 0 H H H CH.sub.3 OCH.sub.3 CH 209-211O 0 H H H OCH.sub.3 OCH.sub.3 CH 219-221O 0 H H H CH.sub.3 CH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 N 194-196O 0 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub.3 CH 218-220O 1 H H H CH.sub.3 OCH.sub.3 CH 219-222O 1 H H H OCH.sub.3 OCH.sub.3 CH 210-214O 1 H H H CH.sub.3 CH.sub.3 N 202-204O 1 H H H CH.sub.3 OCH.sub.3 N 190-197O 1 H H H OCH.sub.3 OCH.sub.3 N 204-207S 0 H H H OCH.sub.3 OCH.sub.3 CHS 1 H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H OCH.sub.3 OCH.sub.3 N 198-220O 0 H .sub.-o-F H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-Br H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H Cl OCH.sub.3 CH 210-213O 0 H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 NH.sub.2 CHO 0 H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 CF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.3 CHO 0 H H H OCH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H OCH.sub.3 OCH.sub.2 CCH CHO 0 H H H OCH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH(OCH.sub.3).sub.2 CH 149-151O 0 H H H CH.sub.3 ##STR81## CHO 0 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CClO 0 H H H CH.sub.3 CH.sub.3 CBrO 1 H H H Cl OCH.sub.3 CH 175-182O 1 H H H Br OCH.sub.3 CH 182-190O 0 H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H H OCH.sub.3 OCH.sub.3 CHO 0 H H F OCH.sub.3 CHO 0 H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H OCF.sub.2 H OCH.sub.3 CH 230O 0 H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H CF.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR82## CHO 0 H H H Br OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR83## CHO 0 H H H CH.sub.3 H CHO 0 H H H CH.sub.3 CN CHO 0 H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H CH.sub.3 OCF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H CH.sub.3 SCF.sub.3 CHO 0 H H H CH.sub.3 OCF.sub.2 H CH 208-209O 0 H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H H CH.sub.3 CH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 CHO 2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H Cl OCH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 NO 2 H H H OCH.sub.3 OCH.sub.3 NO 0 CH.sub.3 H H OCH.sub.3 OCH.sub.3 CH 230-232O 0 H H H OCH.sub.3 CH(OCH.sub.3).sub.2 CH 143-145O 0 H H H OCF.sub.2 H OCF.sub.2 H CHO 1 CH.sub.3 H H CH.sub.3 OCH.sub.3 CH 203-209__________________________________________________________________________
TABLE 5a__________________________________________________________________________ ##STR84##W n R R.sub.1 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.3 CH 210-212O 0 H H H OCH.sub.3 OCH.sub.3 CH 232-233O 0 H H H CH.sub.3 CH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 N 193-195O 0 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub.3 CHO 1 H H H CH.sub.3 OCH.sub.3 CHO 1 H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 NO 1 H H H CH.sub.3 OCH.sub.3 NO 1 H H H OCH.sub.3 OCH.sub.3 NS 0 H H H OCH.sub.3 OCH.sub.3 CHS 1 H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 0 H .sub.-o-F H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-Br H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H Cl OCH.sub.3 CH 218-219O 0 H H H CH.sub.3 OCH.sub. 2 CH.sub.3 CHO 0 H H H CH.sub.3 NH.sub.2 CHO 0 H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 CF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H CH.sub.3 ##STR85## CHO 0 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H H CH.sub. 3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CClO 0 H H H CH.sub.3 CH.sub.3 CBrO 1 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H Cl OCH.sub.3 CHO 0 H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H F OCH.sub.3 CHO 0 H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H CF.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR86## CHO 0 H H H Br OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR87## CHO 0 H H H CH.sub.3 H CHO 0 H H H CH.sub.3 CN CHO 0 H H H CH.sub.3 CH(OCH.sub.2 CH.sub. 3).sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H CH.sub.3 OCF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H CH.sub.3 SCF.sub.3 CHO 0 H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H H CH.sub.3 CH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 CHO 2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H Cl OCH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 NO 2 H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 6a__________________________________________________________________________ ##STR88##W n R R.sub.1 R.sub.3 R.sub.4 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H H Cl OCH.sub.3 CHO 0 H H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 1 H H H H H CH.sub.3 CH.sub.3 CHO 1 H H H H H CH.sub.3 OCH.sub.3 CHO 1 H H H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H H H Cl CH.sub.3 CHO 1 H H H H H CH.sub.3 OCH.sub.3 NO 1 H H H H H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H H Cl CH.sub.3 CHO 1 H H CH.sub.3 H H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 H Cl CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 NS 0 H H H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H H H OCH.sub.3 OCH.sub.3 NO 0 H .sub.-o-F H H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-Br H H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-OCH.sub.3 H H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H H CH.sub.3 CH.sub.3 NO 0 H H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H H H CH.sub.3 NH.sub.2 CHO 0 H H H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H H H CH.sub.3 CF.sub.3 CHO 0 H H H H H CH.sub.3 SCH.sub.3 CHO 0 H H H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H H H CH.sub.3 ##STR89## CHO 0 H H H H H OCH.sub.3 OCH.sub.3 CCH.sub.3O 0 H H H H H OCH.sub.3 OCH.sub.3 CC.sub.2 H.sub.5O 0 H H H H H OCH.sub.3 OCH.sub.3 CClO 0 H H H H H OCH.sub.3 OCH.sub.3 CBrO 0 H H H H H F OCH.sub.3 CHO 0 H H H H H Br OCH.sub.3 CHO 0 H H H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H H H CF.sub.3 OCH.sub.3 CHO 0 H H H H H CH.sub.3 ##STR90## CHO 0 H H H H H CH.sub.3 ##STR91## CHO 0 H H H H H CH.sub.3 H CHO 0 H H H H H CH.sub.3 CN CHO 0 H H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H H H CH.sub.3 OCF.sub.3 CHO 0 H H H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H H H CH.sub.3 SCF.sub.3 CHO 0 H H H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H H H CH.sub. 3 SCF.sub.2 CHFCF.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-CF.sub.2 H H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H H CH.sub.3 CH.sub.3 CHO 2 H H H H H CH.sub.3 OCH.sub.3 CHO 2 H H H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H H Cl OCH.sub.3 CHO 2 H H H H H CH.sub.3 OCH.sub.3 NO 2 H H H H H OCH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H H CH.sub.3 CH.sub.3 CHO 2 H H CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H H Cl OCH.sub.3 CHO 2 H H CH.sub.3 H H CH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 0 H H Cl Cl H CH.sub.3 CH.sub.3 CH 197-199O 0 H H Cl Cl H CH.sub.3 OCH.sub.3 CH 198-201O 0 H H Cl Cl H OCH.sub.3 OCH.sub.3 CH 154-166O 0 H H Br Br H OCH.sub.3 OCH.sub.3 CHO 0 H H Cl Cl H OCH.sub.3 CH.sub.3 N 178-182__________________________________________________________________________
TABLE 7a__________________________________________________________________________ ##STR92##W n R R.sub.1 R.sub.2 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 OCH.sub.3 CHO 0 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 NO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NS 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHS 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H -o-F CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-Br CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-OCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 NH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 NHCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CCH CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 ##STR93## CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CClO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CBrO 1 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub. 3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H Cl OCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H F OCH.sub.3 CHO 0 H H CH.sub.3 H Br OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.2 F OCH.sub.3 CHO 0 H H CH.sub.3 H OCF.sub.2 H OCH.sub.3 CHO 0 H H CH.sub.3 H OCF.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H CF.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 ##STR94## CHO 0 H H CH.sub.3 H CH.sub.3 ##STR95## CHO 0 H H CH.sub.3 H CH.sub.3 H CHO 0 H H CH.sub.3 H CH.sub.3 CN CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H Cl OCH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 8a__________________________________________________________________________ ##STR96##W n R R.sub.1 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.3 CHO 0 H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 NO 0 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub.3 CHO 1 H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 NO 1 H H H CH.sub.3 OCH.sub.3 NO 1 H H H OCH.sub.3 OCH.sub.3 NS 0 H H H OCH.sub.3 OCH.sub.3 CHS 1 H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 0 H -o-F H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H OCH.sub.3 OCH.sub.3 CHO 0 H -o-Br H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H Cl OCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 NH.sub.2 CHO 0 H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 CF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H CH.sub.3 ##STR97## CHO 0 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CClO 0 H H H CH.sub.3 CH.sub.3 CBrO 1 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H Cl OCH.sub.3 CHO 0 H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H F OCH.sub.3 CHO 0 H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H CF.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR98## CHO 0 H H H Br OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR99## CHO 0 H H H CH.sub.3 H CHO 0 H H H CH.sub.3 CN CHO 0 H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H CH.sub.3 OCF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H CH.sub.3 SCF.sub.3 CHO 0 H H H CH.sub.3 OCF.sub.2 F CHO 0 H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H H CH.sub.3 CH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 CHO 2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H Cl OCH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 NO 2 H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 9a__________________________________________________________________________ ##STR100##W n R R.sub.1 R.sub.2 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH(CH.sub.3).sub.2 H CH.sub.3 OCH.sub.3 CHO 0 H H CH(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 NO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NS 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHS 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H -o-F CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-Br CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H -o-OCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 NH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 NHCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CCH CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 ##STR101## CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3O 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CClO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CBrO 1 H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H Cl OCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 F CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H F OCH.sub.3 CHO 0 H H CH.sub.3 H Br OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.2 F OCH.sub.3 CHO 0 H H CH.sub.3 H OCF.sub.2 H OCH.sub.3 CHO 0 H H CH.sub.3 H OCF.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H CF.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 ##STR102## CHO 0 H H CH.sub.3 H CH.sub.3 ##STR103## CHO 0 H H CH.sub.3 H CH.sub.3 H CHO 0 H H CH.sub.3 H CH.sub.3 CN CHO 0 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCH.sub.2 F CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub. 2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 H CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H Cl OCH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 10a__________________________________________________________________________ ##STR104##W n R R.sub.1 R.sub.5 X Y Z m.p.(.degree.C.)__________________________________________________________________________O 0 H H H CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.3 CHO 0 H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 NO 0 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub.3 CHO 1 H H H CH.sub.3 OCH.sub.3 CHO 1 H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 NO 1 H H H CH.sub.3 OCH.sub.3 NO 1 H H H OCH.sub.3 OCH.sub.3 NS 0 H H H OCH.sub.3 OCH.sub.3 CHS 1 H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 0 H .sub.-o-F H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-Br H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H Cl OCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 NH.sub.2 CHO 0 H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 CF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H CH.sub.3 ##STR105## CHO 0 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CClO 0 H H H CH.sub.3 CH.sub.3 CBrO 1 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H Cl OCH.sub.3 CHO 0 H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H F OCH.sub.3 CHO 0 H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H CF.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR106## CHO 0 H H H Br OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR107## CHO 0 H H H CH.sub.3 H CHO 0 H H H CH.sub.3 CN CHO 0 H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H CH.sub.3 OCF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H CH.sub.3 SCF.sub.3 CHO 0 H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H H CH.sub.3 CH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 CHO 2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H Cl OCH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 NO 2 H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 10b__________________________________________________________________________ ##STR108##W n R R.sub.1 R.sub.5 X Y Z m.p.(.degree.C.)__________________________________________________________________________O 0 H H H CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.3 CHO 0 H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 NO 0 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub.3 CHO 1 H H H CH.sub.3 OCH.sub.3 CHO 1 H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 NO 1 H H H CH.sub.3 OCH.sub.3 NO 1 H H H OCH.sub.3 OCH.sub.3 NS 0 H H H OCH.sub.3 OCH.sub.3 CHS 1 H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO 0 H .sub.-o-F H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-Br H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H Cl OCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 NH.sub. 2 CHO 0 H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H CH.sub.3 CF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H CH.sub.3 ##STR109## CHO 0 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CCH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CCH.sub.2 CH.sub.3O 0 H H H CH.sub.3 CH.sub.3 CClO 0 H H H CH.sub.3 CH.sub.3 CBrO 1 H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H Cl OCH.sub.3 CHO 0 H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-OCF.sub.2 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H F OCH.sub.3 CHO 0 H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H CF.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR110## CHO 0 H H H Br OCH.sub.3 CHO 0 H H H CH.sub.3 ##STR111## CHO 0 H H H CH.sub.3 H CHO 0 H H H CH.sub.3 CN CHO 0 H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H CH.sub.3 OCF.sub.3 CHO 0 H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H CH.sub.3 SCF.sub.3 CHO 0 H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 2 H H H CH.sub.3 CH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 CHO 2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H Cl OCH.sub.3 CHO 2 H H H CH.sub.3 OCH.sub.3 NO 2 H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 11a__________________________________________________________________________ ##STR112##W n R R.sub.1 R.sub.6 R.sub.7 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H Cl OCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H OCH.sub. 3 OCH.sub.3 NO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H .sub.--m-F H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H .sub.-o-Cl H H CH.sub.3 NH.sub.2 CHO 0 H .sub.--m-Br H H CH.sub.3 NHCH.sub.3 CHO 0 H .sub.-o-CH.sub.3 H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H .sub.--m-OCH.sub.3 H H CH.sub.3 C.sub.2 H.sub.5 CHO 0 H .sub.-o-CF.sub.3 H H CH.sub.3 CF.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H H CH.sub.3 SCH.sub.3 CHO 0 H .sub.-o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H .sub.-o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 ##STR113## CHO 0 H H H H CH.sub.3 ##STR114## CHO 0 H H H H CH.sub.3 ##STR115## CHO 0 H H H H CH.sub.3 H CHO 0 H H H H CH.sub.3 CN CHO 0 H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H H CH.sub.3 OCF.sub.3 CHO 0 H H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H H CH.sub.3 SCF.sub.3 CHO 0 H H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 0 H H H H CH.sub.2 F CH.sub.3 CHO 0 H H H H F OCH.sub.3 CHO 0 H H H H Br OCH.sub.3 CHO 0 H H H H OCF.sub.2 H CH.sub.3 CHO 0 H H H H OCF.sub.3 CH.sub.3 CHO 0 H H H H CF.sub.3 CH.sub.3 CHS 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H H CH.sub.3 CH.sub.3 CHO 1 H H H H CH.sub.3 OCH.sub.3 CHO 1 H H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H H Cl OCH.sub.3 CHO 1 H H H H CH.sub.3 OCH.sub.3 NO 1 H H H H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 Cl OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 2 H H H H CH.sub.3 CH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 CHO 2 H H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H Cl OCH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 NO 2 H H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 11b__________________________________________________________________________ ##STR116##W n R R.sub.1 R.sub.6 R.sub.7 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H Cl OCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H OCH.sub. 3 OCH.sub.3 NO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H .sub.--m-F H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H .sub.-o-Cl H H CH.sub.3 NH.sub.2 CHO 0 H .sub.--m-Br H H CH.sub.3 NHCH.sub.3 CHO 0 H .sub.-o-CH.sub.3 H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H .sub.--m-OCH.sub.3 H H CH.sub.3 C.sub.2 H.sub.5 CHO 0 H .sub.-o-CF.sub.3 H H CH.sub.3 CF.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H H CH.sub.3 SCH.sub.3 CHO 0 H .sub.-o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H .sub.-o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 ##STR117## CHO 0 H H H H CH.sub.3 ##STR118## CHO 0 H H H H CH.sub.3 ##STR119## CHO 0 H H H H CH.sub.3 H CHO 0 H H H H CH.sub.3 CN CHO 0 H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H H CH.sub.3 OCF.sub.3 CHO 0 H H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H H CH.sub.3 SCF.sub.3 CHO 0 H H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 0 H H H H CH.sub.2 F CH.sub.3 CHO 0 H H H H F OCH.sub.3 CHO 0 H H H H Br OCH.sub.3 CHO 0 H H H H OCF.sub.2 H CH.sub.3 CHO 0 H H H H OCF.sub.3 CH.sub.3 CHO 0 H H H H CF.sub.3 CH.sub.3 CHS 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 NO 1 H H H H CH.sub.3 CH.sub.3 CHO 1 H H H H CH.sub.3 OCH.sub.3 CHO 1 H H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H H Cl OCH.sub.3 CHO 1 H H H H CH.sub.3 OCH.sub.3 NO 1 H H H H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 Cl OCH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 2 H H H H CH.sub.3 CH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 CHO 2 H H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H Cl OCH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 NO 2 H H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 12a__________________________________________________________________________ ##STR120##W n R R.sub.1 R.sub.5 R.sub.6 R.sub.7 X Y Z m.p. (.degree. C.)__________________________________________________________________________O 0 H H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H H Cl OCH.sub.3 CHO 0 H H H H H CH.sub.3 OCH.sub. 3 NO 0 H H H H H OCH.sub.3 OCH.sub.3 NO 0 H H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H H CH.sub.3 Cl OCH.sub.3 CHO 0 H H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO 0 H H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO 0 H H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 0 H H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H .sub.--m-F H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H -o-Cl H H H CH.sub.3 NH.sub.2 CHO 0 H .sub.--m-Br H H H CH.sub.3 NHCH.sub.3 CHO 0 H -o-CH.sub.3 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H .sub.--m-OCH.sub.3 H H H CH.sub.3 C.sub.2 H.sub.5 CHO 0 H -o-CF.sub.3 H H H CH.sub.3 CF.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H H H CH.sub.3 SCH.sub.3 CHO 0 H -o-OCF.sub.2 H H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H -o-OCF.sub.2 H H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H H H CH.sub.3 ##STR121## CHO 0 H H H H H CH.sub.3 ##STR122## CHO 0 H H H H H CH.sub.3 ##STR123## CHO 0 H H H H H CH.sub.3 H CHO 0 H H H H H CH.sub.3 CN CHO 0 H H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H H H CH.sub.3 OCF.sub.3 CHO 0 H H H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H H H CH.sub.3 SCF.sub.3 CHO 0 H H H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 0 H H H H H CH.sub.2 F CH.sub.3 CHO 0 H H H H H F OCH.sub.3 CHO 0 H H H H H Br OCH.sub.3 CHO 0 H H H H H OCF.sub.2 H CH.sub.3 CHO 0 H H H H H OCF.sub.3 CH.sub.3 CHO 0 H H H H H CF.sub.3 CH.sub.3 CHS 0 H H H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H H H OCH.sub.3 OCH.sub.3 NO 1 H H H H H CH.sub.3 CH.sub.3 CHO 1 H H H H H CH.sub.3 OCH.sub.3 CHO 1 H H H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H H H Cl OCH.sub.3 CHO 1 H H H H H CH.sub.3 OCH.sub.3 NO 1 H H H H H OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H H H CH.sub.3 Cl OCH.sub.3 CHO 1 H H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 1 H H H CH.sub.3 CH.sub.3 Cl OCH.sub. 3 CHO 1 H H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 1 H H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 2 H H H H H CH.sub.3 CH.sub.3 CHO 2 H H H H H CH.sub.3 OCH.sub.3 CHO 2 H H H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H H Cl OCH.sub.3 CHO 2 H H H H H CH.sub.3 OCH.sub.3 NO 2 H H H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 13a__________________________________________________________________________ ##STR124##W R R.sub.1 R.sub.2 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 NH.sub.2 CHO H H CH.sub.3 CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 ##STR125## CHO H H CH.sub.3 CH.sub.3 ##STR126## CHO H H CH.sub.3 CH.sub.3 ##STR127## CHO H H CH.sub.3 CH.sub.3 H CHO H H CH.sub.3 CH.sub.3 CN CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CClO H H CH.sub.3 CH.sub.3 OCH.sub.3 CBrO H H CH.sub.3 F OCH.sub.3 CHO H H CH.sub.3 Br OCH.sub.3 CHO H H CH.sub.3 CH.sub.2 F OCH.sub.3 CHO H H CH.sub.3 OCF.sub.2 H OCH.sub.3 CHO H H CH.sub.3 OCF.sub.3 OCH.sub.3 CHO H H CH.sub.3 CF.sub.3 OCH.sub.3 CHO H .sub.--m-F CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-Cl CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H CH.sub.3 CH.sub.3 OCH.sub.3 CHO CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 OCH.sub. 3 CHO H H H OCH.sub.3 OCH.sub.3 CHO H H H Cl OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 NO H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 OCH.sub.3 OCH.sub.3 CH 205-210O H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 14a______________________________________ ##STR128## m.p.W R R.sub.1 X Y Z (.degree.C.)______________________________________S H H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 NH.sub.2 CHO H H CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub.3 CF.sub.3 CHO H H CH.sub.3 SCH.sub.3 CHO H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 ##STR129## CHO H H CH.sub.3 ##STR130## CHO H H CH.sub.3 ##STR131## CHO H H CH.sub.3 H CHO H H CH.sub.3 CN CHO H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H CH.sub.3 OCH.sub.3 CClO H H CH.sub.3 OCH.sub.3 CBrO H H F OCH.sub.3 CHO H H Br OCH.sub.3 CHO H H CH.sub.2 F OCH.sub.3 CHO H H OCF.sub.2 H OCH.sub.3 CHO H H OCF.sub.3 OCH.sub.3 CHO H H CF.sub.3 OCH.sub.3 CHO H .sub.--m-F CH.sub.3 OCH.sub.3 CHO H -o-Cl CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H CH.sub.3 OCH.sub.3 CHO CH.sub.3 H CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CHO H H CH.sub.3 OCH.sub.3 CHO H H OCH.sub.3 OCH.sub.3 CHO H H Cl OCH.sub.3 CHO H H CH.sub.3 OCH.sub.3 NO H H OCH.sub.3 OCH.sub.3 N______________________________________
TABLE 15a__________________________________________________________________________ ##STR132##W R R.sub.1 R.sub.2 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 NH.sub.2 CHO H H CH.sub.3 CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 ##STR133## CHO H H CH.sub.3 CH.sub.3 ##STR134## CHO H H CH.sub.3 CH.sub.3 ##STR135## CHO H H CH.sub.3 CH.sub.3 H CHO H H CH.sub.3 CH.sub.3 CN CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CClO H H CH.sub.3 CH.sub.3 OCH.sub.3 CBrO H H CH.sub.3 F OCH.sub.3 CHO H H CH.sub. 3 Br OCH.sub.3 CHO H H CH.sub.3 CH.sub.2 F OCH.sub.3 CHO H H CH.sub.3 OCF.sub.2 H OCH.sub.3 CHO H H CH.sub.3 OCF.sub.3 OCH.sub.3 CHO H H CH.sub.3 CF.sub.3 OCH.sub.3 CHO H .sub.--m-F CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-Cl CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H CH.sub.3 CH.sub.3 OCH.sub.3 CHO CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CHO H H H OCH.sub.3 OCH.sub.3 CHO H H H Cl OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 NO H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 16a__________________________________________________________________________ ##STR136##W R R.sub.1 R.sub.4 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H H OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H H CH.sub.3 NH.sub.2 CHO H H H CH.sub.3 NHCH.sub.3 CHO H H H CH.sub.3 N(CH.sub.2).sub.2 CHO H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO H H H CH.sub.3 CF.sub.3 CHO H H H CH.sub.3 SCH.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H H CH.sub.3 OCH.sub.2 CCH CHO H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H H CH.sub.3 ##STR137## CHO H H H CH.sub.3 ##STR138## CHO H H H CH.sub.3 ##STR139## CHO H H H CH.sub.3 H CHO H H H CH.sub.3 CN CHO H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H H CH.sub. 3 OCH.sub.2 F CHO H H H CH.sub.3 OCF.sub.3 CHO H H H CH.sub.3 SCH.sub.2 F CHO H H H CH.sub.3 SCF.sub.3 CHO H H H CH.sub.3 OCF.sub.2 H CHO H H H CH.sub.3 OCF.sub.2 CHClF CHO H H H CH.sub.3 OCF.sub.2 CHBrF CHO H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H H CH.sub.3 SCF.sub.2 H CHO H H H CH.sub.3 SCF.sub.2 CHClF CHO H H H CH.sub.3 SCF.sub.2 CHBrF CHO H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CCH.sub.3O H H H CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H H CH.sub.3 OCH.sub.3 CClO H H H CH.sub.3 OCH.sub.3 CBrO H H H F OCH.sub.3 CHO H H H Br OCH.sub.3 CHO H H H CH.sub.2 F OCH.sub.3 CHO H H H OCF.sub.2 F OCH.sub.3 CHO H H H OCF.sub.3 OCH.sub.3 CHO H H H CF.sub.3 OCH.sub.3 CHO H .sub.--m-F H CH.sub.3 OCH.sub.3 CHO H -o-Cl H CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br H CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 H OCH.sub.3 CHO H .sub.--m-CF.sub.3 H CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 H CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H H CH.sub.3 OCH.sub.3 CHO CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CHO H H H OCH.sub.3 OCH.sub.3 CH 226-236.degree.O H H H Cl OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 NO H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 17a__________________________________________________________________________ ##STR140##W R R.sub.1 X Y Z m.p (.degree.C.)__________________________________________________________________________S H H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 NH.sub.2 CHO H H CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub.3 CF.sub.3 CHO H H CH.sub.3 SCH.sub.3 CHO H H CH.sub.3 OCH.sub.2 CHCH.sub. 2 CHO H H CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 ##STR141## CHO H H CH.sub.3 ##STR142## CHO H H CH.sub.3 ##STR143## CHO H H CH.sub.3 H CHO H H CH.sub.3 CN CHO H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H CH.sub.3 OCH.sub.3 CClO H H CH.sub.3 OCH.sub.3 CBrO H H F OCH.sub.3 CHO H H Br OCH.sub.3 CHO H H CH.sub.2 F OCH.sub.3 CHO H H OCF.sub.2 H OCH.sub.3 CHO H H OCF.sub.3 OCH.sub.3 CHO H H CF.sub.3 OCH.sub.3 CHO H .sub.--m-F CH.sub.3 OCH.sub.3 CHO H -o-Cl CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H CH.sub.3 OCH.sub.3 CHO CH.sub.3 H CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CHO H H CH.sub.3 OCH.sub.3 CHO H H OCH.sub.3 OCH.sub.3 CHO H H Cl OCH.sub.3 CHO H H CH.sub.3 OCH.sub.3 NO H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 18a__________________________________________________________________________ ##STR144##W R R.sub.1 R.sub.2 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 NH.sub.2 CHO H H CH.sub.3 CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 ##STR145## CHO H H CH.sub.3 CH.sub.3 ##STR146## CHO H H CH.sub.3 CH.sub.3 ##STR147## CHO H H CH.sub.3 CH.sub.3 H CHO H H CH.sub.3 CH.sub.3 CN CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CClO H H CH.sub.3 CH.sub.3 OCH.sub.3 CBrO H H CH.sub.3 F OCH.sub.3 CHO H H CH.sub.3 Br OCH.sub.3 CHO H H CH.sub.3 CH.sub.2 F OCH.sub.3 CHO H H CH.sub.3 OCF.sub.2 H OCH.sub.3 CHO H H CH.sub.3 OCF.sub.3 OCH.sub.3 CHO H H CH.sub.3 CF.sub.3 OCH.sub.3 CHO H .sub.--m-F CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-Cl CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H CH.sub.3 CH.sub.3 OCH.sub.3 CHO CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CHO H H H OCH.sub.3 OCH.sub.3 CHO H H H Cl OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 NO H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 19a__________________________________________________________________________ ##STR148##W R R.sub.1 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 NH.sub.2 CHO H H CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub.3 CF.sub.3 CHO H H CH.sub.3 SCH.sub.3 CHO H H CH.sub. 3 OCH.sub.2 CHCH.sub.2 CHO H H CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 ##STR149## CHO H H CH.sub.3 ##STR150## CHO H H CH.sub.3 ##STR151## CHO H H CH.sub.3 H CHO H H CH.sub.3 CN CHO H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H CH.sub.3 OCH.sub.3 CClO H H CH.sub.3 OCH.sub.3 CBrO H H F OCH.sub.3 CHO H H Br OCH.sub.3 CHO H H CH.sub.2 F OCH.sub.3 CHO H H OCF.sub.2 H OCH.sub.3 CHO H H OCF.sub.3 OCH.sub.3 CHO H H CF.sub.3 OCH.sub.3 CHO H .sub.--m-F CH.sub.3 OCH.sub.3 CHO H -o-Cl CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H CH.sub.3 OCH.sub.3 CHO CH.sub.3 H CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CHO H H CH.sub.3 OCH.sub.3 CHO H H OCH.sub.3 OCH.sub.3 CHO H H Cl OCH.sub.3 CHO H H CH.sub.3 OCH.sub.3 NO H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 20a__________________________________________________________________________ ##STR152##W R R.sub.1 R.sub.2 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 NH.sub.2 CHO H H CH.sub.3 CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub. 3 CH.sub.3 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 ##STR153## CHO H H CH.sub.3 CH.sub.3 ##STR154## CHO H H CH.sub.3 CH.sub.3 ##STR155## CHO H H CH.sub.3 CH.sub.3 H CHO H H CH.sub.3 CH.sub.3 CN CHO H H CH.sub.3 CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H CH.sub.3 CH.sub.3 OCH.sub.3 CClO H H CH.sub.3 CH.sub.3 OCH.sub.3 CBrO H H CH.sub.3 F OCH.sub.3 CHO H H CH.sub.3 Br OCH.sub.3 CHO H H CH.sub.3 CH.sub.2 F OCH.sub.3 CHO H H CH.sub.3 OCF.sub.2 H OCH.sub.3 CHO H H CH.sub.3 OCF.sub.3 OCH.sub.3 CHO H H CH.sub.3 CF.sub.3 OCH.sub.3 CHO H .sub.--m-F CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-Cl CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-SCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H -o-OCF.sub.2 H CH.sub.3 CH.sub.3 OCH.sub.3 CHO CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CHO H H H OCH.sub.3 OCH.sub.3 CHO H H H Cl OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 NO H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 21a__________________________________________________________________________ ##STR156##W R R.sub.1 R.sub.3 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H H OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H H CH.sub.3 NH.sub.2 CHO H H H CH.sub.3 NHCH.sub.3 CHO H H H CH.sub.3 N(CH.sub.3).sub.2 CHO H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO H H H CH.sub.3 CF.sub.3 CHO H H H CH.sub.3 SCH.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H H CH.sub.3 OCH.sub.2 CCH CHO H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H H CH.sub.3 ##STR157## CHO H H H CH.sub.3 ##STR158## CHO H H H CH.sub.3 ##STR159## CHO H H H CH.sub.3 H CHO H H H CH.sub.3 CN CHO H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H H CH.sub. 3 OCH.sub.2 F CHO H H H CH.sub.3 OCF.sub.3 CHO H H H CH.sub.3 SCH.sub.2 F CHO H H H CH.sub.3 SCF.sub.3 CHO H H H CH.sub.3 OCF.sub.2 H CHO H H H CH.sub.3 OCF.sub.2 CHClF CHO H H H CH.sub.3 OCF.sub.2 CHBrF CHO H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H H CH.sub.3 SCF.sub.2 H CHO H H H CH.sub.3 SCF.sub.2 CHClF CHO H H H CH.sub.3 SCF.sub.2 CHBrF CHO H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CCH.sub.3O H H H CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H H CH.sub.3 OCH.sub.3 CClO H H H CH.sub.3 OCH.sub.3 CBrO H H H F OCH.sub.3 CHO H H H Br OCH.sub.3 CHO H H H CH.sub.2 F OCH.sub.3 CHO H H CH.sub.3 OCF.sub.2 H OCH.sub.3 CH 213-216O H H H OCF.sub.3 OCH.sub.3 CHO H H H CF.sub.3 OCH.sub.3 CHO H .sub.--m-F H CH.sub.3 OCH.sub.3 CHO H .sub.-o-Cl H CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br H CH.sub.3 OCH.sub.3 CHO H .sub.-o-CH.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.-o-SCH.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.-o-OCF.sub.2 H H CH.sub.3 OCH.sub.3 CHO CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CH 221-223O H H H CH.sub.3 OCH.sub.3 CH 234-236O H H H OCH.sub.3 OCH.sub.3 CHO H H H Cl OCH.sub.3 CH 243-246O H H H CH.sub.3 OCH.sub.3 N 202-205O H H H OCH.sub.3 OCH.sub.3 N 207-210O H H CH.sub.3 CH.sub.3 CH.sub.3 CH 227-229O H H CH.sub.3 CH.sub.3 OCH.sub.3 CH 221-223O H H CH.sub.3 OCH.sub.3 OCH.sub.3 CH 228-230O H H CH.sub.3 Cl OCH.sub.3 CH 246-249O H H CH.sub.3 CH.sub.3 OCH.sub.3 N 201-203O H H CH.sub.3 OCH.sub.3 OCH.sub.3 N 187-200O H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CH 209-211O H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 N 199-202O H H H OCF.sub.2 H OCH.sub.3 CH 216-218O H H Cl OCH.sub.3 OCH.sub.3 CHO H H Br OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 22a__________________________________________________________________________ ##STR160##W n R R.sub.1 R.sub.3 R.sub.4 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H Cl OCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H OCH.sub. 3 OCH.sub.3 NO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 1 H H H H CH.sub.3 CH.sub.3 CHO 1 H H H H CH.sub.3 OCH.sub.3 CHO 1 H H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H H Cl CH.sub.3 CHO 1 H H H H CH.sub.3 OCH.sub.3 NO 1 H H H H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H Cl CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 Cl CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NS 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 NO 0 H .sub.-o-F H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-Cl H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-Br H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-OCH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H H CH.sub.3 CH.sub.3 NO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H H CH.sub.3 NH.sub.2 CHO 0 H H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H H CH.sub.3 CF.sub.3 CHO 0 H H H H CH.sub.3 SCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 ##STR161## CHO 0 H H H H OCH.sub.3 OCH.sub.3 CCH.sub.3O 0 H H H H OCH.sub.3 OCH.sub.3 CC.sub.2 H.sub.5O 0 H H H H OCH.sub.3 OCH.sub.3 CClO 0 H H H H OCH.sub.3 OCH.sub.3 CBrO 0 H H H H F OCH.sub.3 CHO 0 H H H H Br OCH.sub.3 CHO 0 H H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H H CF.sub.3 OCH.sub.3 CHO 0 H H H H CH.sub.3 ##STR162## CHO 0 H H H H CH.sub.3 ##STR163## CHO 0 H H H H CH.sub.3 H CHO 0 H H H H CH.sub.3 CN CHO 0 H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H H CH.sub.3 OCF.sub.3 CHO 0 H H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H H CH.sub.3 SCF.sub.3 CHO 0 H H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-CF.sub.2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H CH.sub.3 CH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 CHO 2 H H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H Cl OCH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 NO 2 H H H H OCH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H Cl OCH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H Cl Cl OCH.sub.3 OCH.sub.3 CHO 0 H H Br Br OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 22b__________________________________________________________________________ ##STR164##W n R R.sub.1 R.sub.3 R.sub.4 X Y Z m.p. (.degree.C.)__________________________________________________________________________O 0 H H H H CH.sub.3 CH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 CHO 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 H H H H Cl OCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.3 NO 0 H H H H OCH.sub. 3 OCH.sub.3 NO 0 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 H Cl OCH.sub.3 CHO 0 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 NO 0 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO 1 H H H H CH.sub.3 CH.sub.3 CHO 1 H H H H CH.sub.3 OCH.sub.3 CHO 1 H H H H OCH.sub.3 OCH.sub.3 CHO 1 H H H H Cl CH.sub.3 CHO 1 H H H H CH.sub. 3 OCH.sub.3 NO 1 H H H H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 H Cl CH.sub.3 CHO 1 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 Cl CH.sub.3 CHO 1 H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO 1 H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NS 0 H H H H OCH.sub.3 OCH.sub.3 CHO 0 CH.sub.3 H H H OCH.sub.3 OCH.sub.3 NO 0 H .sub.-o-F H H OCH.sub.3 OCH.sub. 3 CHO 0 H .sub.--m-Cl H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-Br H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-OCH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-CF.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 0 H H H H CH.sub.3 CH.sub.3 NO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO 0 H H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 1 H H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO 0 H H H H CH.sub.3 NH.sub.2 CHO 0 H H H H CH.sub.3 NHCH.sub.3 CHO 0 H H H H CH.sub.3 N(CH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 CH.sub.2 CH.sub.3 CHO 0 H H H H CH.sub.3 CF.sub.3 CHO 0 H H H H CH.sub.3 SCH.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO 0 H H H H CH.sub.3 OCH.sub.2 CCH CHO 0 H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO 0 H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO 0 H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 ##STR165## CHO 0 H H H H OCH.sub.3 OCH.sub.3 CCH.sub.3O 0 H H H H OCH.sub.3 OCH.sub.3 CC.sub.2 H.sub.5O 0 H H H H OCH.sub.3 OCH.sub.3 CClO 0 H H H H OCH.sub.3 OCH.sub.3 CBrO 0 H H H H F OCH.sub.3 CHO 0 H H H H Br OCH.sub.3 CHO 0 H H H H CH.sub.2 F OCH.sub.3 CHO 0 H H H H OCF.sub.2 H OCH.sub.3 CHO 0 H H H H OCF.sub.3 OCH.sub.3 CHO 0 H H H H CF.sub.3 OCH.sub.3 CHO 0 H H H H CH.sub.3 ##STR166## CHO 0 H H H H CH.sub.3 ##STR167## CHO 0 H H H H CH.sub.3 H CHO 0 H H H H CH.sub.3 CN CHO 0 H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO 0 H H H H CH.sub.3 OCH.sub.2 F CHO 0 H H H H CH.sub.3 OCF.sub.3 CHO 0 H H H H CH.sub.3 SCH.sub.2 F CHO 0 H H H H CH.sub.3 SCF.sub.3 CHO 0 H H H H CH.sub.3 OCF.sub.2 H CHO 0 H H H H CH.sub.3 OCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO 0 H H H H CH.sub.3 SCF.sub.2 H CHO 0 H H H H CH.sub.3 SCF.sub.2 CHClF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHBrF CHO 0 H H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO 0 H H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO 0 H .sub.--m-SCH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO 0 H .sub.-o-CF.sub.2 H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H CH.sub.3 CH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 CHO 2 H H H H OCH.sub.3 OCH.sub.3 CHO 2 H H H H Cl OCH.sub.3 CHO 2 H H H H CH.sub.3 OCH.sub.3 NO 2 H H H H OCH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO 2 H H CH.sub.3 H Cl OCH.sub.3 CHO 2 H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO 2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3 NO 0 H H Cl Cl OCH.sub.3 OCH.sub.3 CHO 0 H H Br Br OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 23a__________________________________________________________________________ ##STR168##W R R.sub.1 R.sub.3 X Y Z m.p. (.degree.C.)__________________________________________________________________________S H H H OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H H CH.sub.3 NH.sub.2 CHO H H H CH.sub.3 NHCH.sub.3 CHO H H H CH.sub.3 N(CH.sub.3).sub.2 CHO H H H CH.sub.3 CH.sub.2 CH.sub. 3 CHO H H H CH.sub.3 CF.sub.3 CHO H H H CH.sub.3 SCH.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H H CH.sub.3 OCH.sub.2 CCH CHO H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H H CH.sub.3 ##STR169## CHO H H H CH.sub.3 ##STR170## CHO H H H CH.sub.3 ##STR171## CHO H H H CH.sub.3 H CHO H H H CH.sub.3 CN CHO H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H H CH.sub.3 OCH.sub.2 F CHO H H H CH.sub.3 OCF.sub.3 CHO H H H CH.sub.3 SCH.sub.2 F CHO H H H CH.sub.3 SCF.sub.3 CHO H H H CH.sub.3 OCF.sub.2 H CHO H H H CH.sub.3 OCF.sub.2 CHClF CHO H H H CH.sub.3 OCF.sub.2 CHBrF CHO H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H H CH.sub.3 SCF.sub.2 H CHO H H H CH.sub.3 SCF.sub.2 CHClF CHO H H H CH.sub.3 SCF.sub.2 CHBrF CHO H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CCH.sub.3O H H H CH.sub.3 OCH.sub.3 CCH.sub.2 CH.sub.3O H H H CH.sub.3 OCH.sub.3 CClO H H H CH.sub.3 OCH.sub.3 CBrO H H H F OCH.sub.3 CHO H H H Br OCH.sub.3 CHO H H H CH.sub.2 F OCH.sub.3 CHO H H H OCF.sub.2 H OCH.sub.3 CHO H H H OCF.sub.3 OCH.sub.3 CHO H H H CF.sub.3 OCH.sub.3 CHO H .sub.--m-F H CH.sub.3 OCH.sub.3 CHO H .sub.-o-Cl H CH.sub.3 OCH.sub.3 CHO H .sub.--m-Br H CH.sub.3 OCH.sub.3 CHO H .sub.-o-CH.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.-o-SCH.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.--m-OCH.sub.3 H CH.sub.3 OCH.sub.3 CHO H .sub.-o-OCF.sub.2 H H CH.sub.3 OCH.sub.3 CHO CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 CHO H H H OCH.sub.3 OCH.sub.3 CHO H H H Cl OCH.sub.3 CHO H H H CH.sub.3 OCH.sub.3 NO H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H Cl OCH.sub.3 OCH.sub.3 CHO H H Br OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 24a__________________________________________________________________________ ##STR172##W R R.sub.1 R.sub.4 R.sub.5 X Y Z m.p. (.degree.C.)__________________________________________________________________________O H H CH.sub.3 H CH.sub.3 CH.sub.3 CH 233-237O H H CH.sub.3 H CH.sub.3 OCH.sub.3 CH 198-205O H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH 204-207O H H CH.sub.3 H CH.sub.3 CH.sub.3 N 212-217O H H CH.sub.3 H CH.sub.3 OCH.sub.3 N 208-212O H H CH.sub.3 H OCH.sub.3 OCH.sub.3 N 212-215O H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NS H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO CH.sub.3 H CH.sub.3 H CH.sub.3 OCH.sub.3 CH 140-143O H .sub.-o-F CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H .sub.--m-Cl CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H .sub.-o-Br CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H .sub.--m-CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H .sub.-o-OCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H .sub.--m-CF.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 CH.sub.3 NO H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H H CH.sub.3 H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 NH.sub.2 CHO H H CH.sub.3 H CH.sub.3 NHCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 N(CH.sub.3).sub.2 CHO H H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CHO H H CH.sub.3 H CH.sub.3 CF.sub.3 CHO H H CH.sub.3 H CH.sub.3 SCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.2 CCH CHO H H CH.sub.3 H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H CH.sub.3 H CH.sub.3 ##STR173## CHO H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CCH.sub.3O H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CC.sub.2 H.sub.5O H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CClO H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CBrO H H CH.sub.3 H F OCH.sub.3 CHO H H CH.sub.3 H Br OCH.sub.3 CHO H H CH.sub.3 H CH.sub.2 F OCH.sub.3 CHO H H CH.sub.3 H OCF.sub.2 H OCH.sub.3 CHO H H CH.sub.3 H OCF.sub.3 OCH.sub.3 CHO H H CH.sub.3 H CF.sub.3 OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 ##STR174## CHO H H CH.sub.3 H CH.sub. 3 ##STR175## CHO H H CH.sub.3 H CH.sub.3 H CHO H H CH.sub.3 H CH.sub.3 CN CHO H H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 H CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 H CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 H CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 H CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 H CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H H CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H .sub.--m-SCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H .sub.-o-CF.sub.2 H CH.sub.3 H OCH.sub.3 OCH.sub.3 CH__________________________________________________________________________
TABLE 25a__________________________________________________________________________ ##STR176##W R R.sub.1 R.sub.6 R.sub.7 X Y Z m.p. (.degree.C.)__________________________________________________________________________O H H H H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 CHO H H H H OCH.sub.3 OCH.sub.3 CHO H H H H Cl OCH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 NO H H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 H CH.sub. 3 CH.sub.3 CHO H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H .sub.--m-F H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H .sub.-o-Cl H H CH.sub.3 NH.sub.2 CHO H .sub.--m-Br H H CH.sub.3 NHCH.sub.3 CHO H .sub.-o-CH.sub.3 H H CH.sub.3 N(CH.sub.3).sub.2 CHO H .sub.--m-OCH.sub.3 H H CH.sub.3 C.sub.2 H.sub.5 CHO H .sub.-o-CF.sub.3 H H CH.sub.3 CF.sub.3 CHO H .sub.--m-SCH.sub.3 H H CH.sub.3 SCH.sub.3 CHO H .sub.-o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H .sub.-o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CCH CHO H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H H H CH.sub.3 ##STR177## CHO H H H H CH.sub.3 ##STR178## CHO H H H H CH.sub.3 ##STR179## CHO H H H H CH.sub.3 H CHO H H H H CH.sub.3 CN CHO H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H H H CH.sub.3 OCH.sub.2 F CHO H H H H CH.sub.3 OCF.sub.3 CHO H H H H CH.sub.3 SCH.sub.2 F CHO H H H H CH.sub.3 SCF.sub.3 CHO H H H H CH.sub.3 OCF.sub.2 H CHO H H H H CH.sub.3 OCF.sub.2 CHClF CHO H H H H CH.sub.3 OCF.sub.2 CHBrF CHO H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H H H CH.sub.3 SCF.sub.2 H CHO H H H H CH.sub.3 SCF.sub.2 CHClF CHO H H H H CH.sub.3 SCF.sub.2 CHBrF CHO H H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H H H CH.sub.2 F CH.sub.3 CHO H H H H F OCH.sub.3 CHO H H H H Br OCH.sub.3 CHO H H H H OCF.sub.2 H CH.sub.3 CHO H H H H OCF.sub.3 CH.sub.3 CHO H H H H CF.sub.3 CH.sub.3 CHS H H H H OCH.sub.3 OCH.sub.3 CHO CH.sub.3 H H H OCH.sub.3 OCH.sub.3 NO H H H H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 CHO H H H H OCH.sub.3 OCH.sub.3 CHO H H H H Cl OCH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 NO H H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H H H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 CHO H H H H OCH.sub.3 OCH.sub.3 CHO H H H H Cl OCH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 NO H H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 25b__________________________________________________________________________ ##STR180##W R R.sub.1 R.sub.6 R.sub.7 X Y Z m.p. (.degree.C.)__________________________________________________________________________O H H H H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 CHO H H H H OCH.sub.3 OCH.sub.3 CHO H H H H Cl OCH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 NO H H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H .sub.--m-F H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H -o-Cl H H CH.sub.3 NH.sub.2 CHO H .sub.--m-Br H H CH.sub.3 NHCH.sub.3 CHO H -o-CH.sub.3 H H CH.sub.3 N(CH.sub.3).sub.2 CHO H .sub.--m-OCH.sub.3 H H CH.sub.3 C.sub.2 H.sub.5 CHO H -o-CF.sub.3 H H CH.sub.3 CF.sub.3 CHO H .sub.--m-SCH.sub.3 H H CH.sub.3 SCH.sub.3 CHO H -o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H -o-OCF.sub.2 H H H CH.sub.3 OCH.sub.2 CCH CHO H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H H H CH.sub.3 ##STR181## CHO H H H H CH.sub.3 ##STR182## CHO H H H H CH.sub.3 ##STR183## CHO H H H H CH.sub.3 H CHO H H H H CH.sub.3 CN CHO H H H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H H H CH.sub.3 OCH.sub.2 F CHO H H H H CH.sub.3 OCF.sub.3 CHO H H H H CH.sub.3 SCH.sub.2 F CHO H H H H CH.sub.3 SCF.sub.3 CHO H H H H CH.sub.3 OCF.sub.2 H CHO H H H H CH.sub.3 OCF.sub.2 CHClF CHO H H H H CH.sub.3 OCF.sub.2 CHBrF CHO H H H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H H H CH.sub.3 SCF.sub.2 H CHO H H H H CH.sub.3 SCF.sub.2 CHClF CHO H H H H CH.sub.3 SCF.sub.2 CHBrF CHO H H H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H H H CH.sub.2 F CH.sub.3 CHO H H H H F OCH.sub.3 CHO H H H H Br OCH.sub.3 CHO H H H H OCF.sub.2 H CH.sub.3 CHO H H H H OCF.sub.3 CH.sub.3 CHO H H H H CF.sub.3 CH.sub.3 CHS H H H H OCH.sub.3 OCH.sub.3 CHO CH.sub.3 H H H OCH.sub.3 OCH.sub.3 NO H H H H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 CHO H H H H OCH.sub.3 OCH.sub.3 CHO H H H H Cl OCH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 NO H H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H H H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 CHO H H H H OCH.sub.3 OCH.sub.3 CHO H H H H Cl OCH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 NO H H H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 26__________________________________________________________________________ ##STR184##W R R.sub.1 R.sub.2 R.sub.6 R.sub.7 X Y Z m.p. (.degree.C.)__________________________________________________________________________O H H H H H CH.sub.3 CH.sub.3 CHO H H H H H CH.sub.3 OCH.sub.3 CHO H H H H H OCH.sub.3 OCH.sub.3 CHO H H H H H Cl OCH.sub.3 CHO H H H H H CH.sub.3 OCH.sub.3 NO H H H H H OCH.sub.3 OCH.sub.3 NO H H H CH.sub.3 H CH.sub.3 CH.sub.3 CHO H H H H CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H H H CH.sub.3 Cl OCH.sub.3 CHO H H H CH.sub.3 H CH.sub.3 OCH.sub.3 NO H H H H CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO H H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H H CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H H H H CH.sub.3 OCH.sub.2 CH.sub.3 CHO H .sub.--m-F H H H CH.sub.3 CH.sub.2 OCH.sub.3 CHO H -o-Cl H H H CH.sub.3 NH.sub.2 CHO H .sub.--m-Br H H H CH.sub.3 NHCH.sub.3 CHO H -o-CH.sub.3 H H H CH.sub.3 N(CH.sub.3).sub.2 CHO H --m-OCH.sub.3 H H H CH.sub.3 C.sub.2 H.sub.5 CHO H -o-CF.sub.3 H H H CH.sub.3 CF.sub.3 CHO H .sub.--m-SCH.sub.3 H H H CH.sub.3 SCH.sub.3 CHO H -o-OCF.sub.2 H H H H CH.sub.3 OCH.sub.2 CHCH.sub.2 CHO H -o-OCF.sub.2 H H H H CH.sub.3 OCH.sub.2 CCH CHO H H H H H CH.sub.3 OCH.sub.2 CF.sub.3 CHO H H H H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHO H H H H H CH.sub.3 CH(OCH.sub.3).sub.2 CHO H H H H H CH.sub.3 ##STR185## CHO H H H H H CH.sub.3 ##STR186## CHO H H H H H CH.sub.3 ##STR187## CHO H H CH.sub.3 H H CH.sub.3 H CHO H H CH.sub.3 H H CH.sub.3 CN CHO H H CH.sub.3 H H CH.sub.3 CH(OCH.sub.2 CH.sub.3).sub.2 CHO H H CH.sub.3 H H CH.sub.3 OCH.sub.2 F CHO H H CH.sub.3 H H CH.sub.3 OCF.sub.3 CHO H H CH.sub.3 H H CH.sub.3 SCH.sub.2 F CHO H H CH.sub.3 H H CH.sub.3 SCF.sub.3 CHO H H CH.sub.3 H H CH.sub.3 OCF.sub.2 H CHO H H CH.sub.3 H H CH.sub.3 OCF.sub.2 CHClF CHO H H CH.sub.3 H H CH.sub.3 OCF.sub.2 CHBrF CHO H H CH.sub.3 H H CH.sub.3 OCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 H H CH.sub.3 SCF.sub.2 H CHO H H CH.sub.3 H H CH.sub.3 SCF.sub.2 CHClF CHO H H CH.sub.3 H H CH.sub.3 SCF.sub.2 CHBrF CHO H H CH.sub.3 H H CH.sub.3 SCF.sub.2 CHFCF.sub.3 CHO H H CH.sub.3 H H CH.sub.2 F CH.sub.3 CHO H H H H H F OCH.sub.3 CHO H H H H H Br OCH.sub.3 CHO H H H H H OCF.sub.2 H CH.sub.3 CHO H H H H H OCF.sub.3 CH.sub.3 CHO H H H H H CF.sub.3 CH.sub.3 CHS H H H H H OCH.sub.3 OCH.sub.3 CHO CH.sub.3 H H H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 H H CH.sub.3 CH.sub.3 CHO H H CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H H Cl OCH.sub.3 CHO H H CH.sub.3 H H CH.sub.3 OCH.sub.3 NO H H CH.sub.3 H H OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 CHO H H CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 H CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 H CH.sub.3 OCH.sub.3 NO H H CH.sub.3 N CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 Cl OCH.sub.3 CHO H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 NO H H CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 CHO H H CH.sub.2 CH.sub.3 H H CH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 H H OCH.sub.3 OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 H H Cl OCH.sub.3 CHO H H CH.sub.2 CH.sub.3 H H CH.sub.3 OCH.sub.3 NO H H CH.sub.2 CH.sub.3 H H OCH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 27a__________________________________________________________________________ ##STR188##J W.sub.1 n R R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X.sub.1 Y.sub.1 m.p. (.degree.C.)__________________________________________________________________________J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3 O 201-203J-1 -- 0 H H CH.sub.3 -- -- H OCH.sub.3 OJ-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3 CH.sub.2J-1 -- 0 H H CH.sub.3 -- -- H OCH.sub.3 CH.sub.2J-2 -- 0 H H -- -- -- H CH.sub.3 OJ-2 -- 0 H H -- -- -- H OCH.sub.3 OJ-2 -- 0 H H -- -- -- H CH.sub.3 CH.sub.2J-2 -- 0 H H -- -- -- N OCH.sub.3 CH.sub.2J-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OJ-3 -- 0 H H CH.sub.3 -- -- H OCH.sub.3 OJ-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3 CH.sub.2J-3 -- 0 H H CH.sub.3 -- -- H OCH.sub.3 CH.sub.2J-4 -- 0 H H -- -- -- H CH.sub.3 OJ-4 -- 0 H H -- -- -- H OCH.sub.3 OJ-4 -- 0 H H -- -- -- H CH.sub.3 CH.sub.2J-4 -- 0 H H -- -- -- H OCH.sub.3 CH.sub.2J-5 -- 0 H H -- -- -- H CH.sub.3 OJ-5 -- 0 H H -- -- -- H OCH.sub.3 OJ-5 -- 0 H H -- -- -- H CH.sub.3 CH.sub.2J-5 -- 0 H H -- -- -- H OCH.sub.3 CH.sub.2J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3 OJ-6 -- 0 H H -- CH.sub.3 CH.sub.3 H OCH.sub.3 OJ-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.2J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H OCH.sub.3 CH.sub.2J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OJ-7 -- 0 H H CH.sub.3 -- -- H OCH.sub.3 OJ-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3 CH.sub.2J-7 -- 0 H H CH.sub.3 -- -- H OCH.sub.3 CH.sub.2J-8 -- 0 H H -- -- -- H CH.sub.3 OJ-8 -- 0 H H -- -- -- H OCH.sub.3 OJ-8 -- 0 H H -- -- -- H CH.sub.3 CH.sub.2J-8 -- 0 H H -- -- -- H OCH.sub.2 CH.sub.2J-9 -- 0 H H -- -- -- H CH.sub.3 OJ-9 -- 0 H H -- -- -- H OCH.sub.3 OJ-9 -- 0 H H -- -- -- H CH.sub.3 CH.sub.2J-9 -- 0 H H -- -- -- H OCH.sub.3 CH.sub.2J-10 O 0 H H -- -- -- H CH.sub.3 OJ-10 O 0 H H -- -- -- H OCH.sub.3 OJ-10 O 0 H H -- -- -- H CH.sub.3 CH.sub.2J-10 O 0 H H -- -- -- N OCH.sub.3 CH.sub.2J-22 O 0 H H -- H H -- OCH.sub.3 CH.sub.2J-23 -- -- H H -- H H -- OCH.sub.3 CH.sub.2J-24 -- -- H H -- -- CH.sub.3 H CH.sub.3 O 136-141J-10 S 0 H H -- -- -- H CH.sub.3 OJ-10 S 0 H H -- -- -- H OCH.sub.3 OJ-10 S 0 H H -- -- -- H CH.sub.3 CH.sub.2J-10 S 0 H H -- -- -- H OCH.sub.3 CH.sub.2__________________________________________________________________________
TABLE 27b______________________________________ ##STR189## m.p.J W.sub.1 n R R.sub.1 R.sub.2 R.sub.5 R.sub.6 R.sub.7 X.sub.1 Y.sub.1 (.degree.C.)______________________________________J-11 O 0 H H -- -- H H CH.sub.3 OJ-11 O 0 H H -- -- H H OCH.sub.3 OJ-11 O 0 H H -- -- H H CH.sub.3 CH.sub.2J-11 S 0 H H -- -- H H OCH.sub.3 CH.sub.2J-12 -- 0 H H -- H H H CH.sub.3 OJ-12 -- 0 H H -- H H H OCH.sub.3 OJ-12 -- 0 H H -- H H H CH.sub.3 CH.sub.2J-12 -- 0 H H -- H H H OCH.sub.3 CH.sub.2J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OJ-13 -- -- H H CH.sub.3 -- -- -- OCH.sub.3 OJ-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.2J-13 -- -- H H CH.sub.3 -- -- -- OCH.sub.3 CH.sub.2J-14 -- -- H H -- -- -- -- CH.sub.3 OJ-14 -- -- H H -- -- -- -- OCH.sub.3 OJ-14 -- -- H H -- -- -- -- CH.sub.3 CH.sub.2J-14 -- -- H H -- -- -- -- OCH.sub.3 CH.sub.2J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OJ-15 -- -- H H CH.sub.3 -- -- -- OCH.sub.3 OJ-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.2J-15 -- -- H H CH.sub.3 -- -- -- OCH.sub.3 CH.sub.2J-16 -- -- H H -- -- -- -- CH.sub.3 OJ-16 -- -- H H -- -- -- -- OCH.sub.3 OJ-16 -- -- H H -- -- -- -- CH.sub.3 CH.sub.2J-16 -- -- H H -- -- -- -- OCH.sub.3 CH.sub.2J-17 -- -- H H -- -- -- -- CH.sub.3 OJ-17 -- -- H H -- -- -- -- OCH.sub.3 OJ-17 -- -- H H -- -- -- -- CH.sub.3 CH.sub.2J-17 -- -- H H -- -- -- -- OCH.sub.3 CH.sub.2J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OJ-18 -- -- H H CH.sub.3 -- -- -- OCH.sub.3 OJ-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.2J-18 -- -- H H CH.sub.3 -- -- -- OCH.sub.3 CH.sub.2J-19 -- -- H H -- -- -- -- CH.sub.3 OJ-19 -- -- H H -- -- -- -- OCH.sub.3 OJ-19 -- -- H H -- -- -- -- CH.sub.3 CH.sub.2J-19 -- -- H H -- -- -- -- OCH.sub.3 CH.sub.2J-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OJ-20 -- -- H H CH.sub.3 -- -- -- OCH.sub.3 OJ-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.2J-20 -- -- H H CH.sub. 3 -- -- -- OCH.sub.3 CH.sub.2J-21 -- -- H H -- -- -- -- CH.sub.3 OJ-21 -- -- H H -- -- -- -- OCH.sub.3 OJ-21 -- -- H H -- -- -- -- CH.sub.3 CH.sub.2J-21 -- -- H H -- -- -- -- OCH.sub.3 CH.sub.2J-25 O -- H H -- -- H H CH.sub.3 OJ-25 O -- H H -- -- H H OCH.sub.3 OJ-25 O -- H H -- -- H H CH.sub.3 CH.sub.2J-25 O -- H H -- -- H H OCH.sub.3 CH.sub.2J-25 S -- H H -- -- H H OCH.sub.3 OJ-25 S -- H H -- -- H H OCH.sub.3 CH.sub.2J-26 -- -- H H CH.sub.3 -- H H CH.sub.3 OJ-26 -- -- H H CH.sub. 3 -- H H OCH.sub.3 OJ-26 -- -- H H CH.sub.3 -- H H CH.sub.3 CH.sub.2J-26 -- -- H H CH.sub.3 -- H H OCH.sub.3 CH.sub.2______________________________________
TABLE 28a______________________________________ ##STR190## m.p.J W.sub.1 n R R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X.sub.1 (.degree.C.)______________________________________J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-1 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-2 -- 0 H H -- -- -- H CH.sub.3J-2 -- 0 H H -- -- -- H OCH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-4 -- 0 H H -- -- -- H CH.sub. 3J-4 -- 0 H H -- -- -- H OCH.sub.3J-5 -- 0 H H -- -- -- H CH.sub.3J-5 -- 0 H H -- -- -- H OCH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H OCH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-8 -- 0 H H -- -- -- H CH.sub.3J-8 -- 0 H H -- -- -- H OCH.sub.3J-9 -- 0 H H -- -- -- H CH.sub.3J-9 -- 0 H H -- -- -- H OCH.sub.3J-10 O 0 H H -- -- -- H CH.sub.3J-10 O 0 H H -- -- -- H OCH.sub.3J-22 O 0 H H -- H H -- OCH.sub.3J-23 -- -- H H -- H H -- OCH.sub.3J-24 -- -- H H -- -- CH.sub.3 H OCH.sub.3J-10 S 0 H H -- -- -- H CH.sub.3J-10 S 0 H H -- -- -- H OCH.sub.3______________________________________
TABLE 28b______________________________________ ##STR191##J W.sub.1 n R R.sub.1 R.sub.2 R.sub.5 R.sub.6 R.sub.7 X.sub.1 m.p. (.degree.C.)______________________________________J-11 O 0 H H -- -- H H CH.sub.3J-11 O 0 H H -- -- H H OCH.sub.3J-12 -- 0 H H -- H H H CH.sub.3J-12 -- 0 H H -- H H H OCH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-14 -- -- H H -- -- -- -- CH.sub.3J-14 -- -- H H -- -- -- -- OCH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-16 -- -- H H -- -- -- -- CH.sub.3J-16 -- -- H H -- -- -- -- OCH.sub.3J-17 -- -- H H -- -- -- -- CH.sub.3J-17 -- -- H H -- -- -- -- OCH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-19 -- -- H H -- -- -- -- CH.sub.3J-19 -- -- H H -- -- -- -- OCH.sub.3J-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-21 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-21 -- -- H H -- -- -- -- CH.sub.3J-21 -- -- H H -- -- -- -- OCH.sub.3J-25 O -- H H -- -- H H CH.sub.3J-25 O -- H H -- -- H H OCH.sub.3J-25 S -- H H -- -- H H CH.sub.3J-25 S -- H H -- -- H H OCH.sub.3J-26 -- -- H H CH.sub.3 -- H H CH.sub.3J-26 -- -- H H CH.sub.3 -- H H OCH.sub.3______________________________________
TABLE 29a______________________________________ ##STR192## m.p.J W.sub.1 n R R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X.sub.1 (.degree.C.)______________________________________J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3 220- 222J-1 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-2 -- 0 H H -- -- -- H CH.sub.3J-2 -- 0 H H -- -- -- H OCH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-4 -- 0 H H -- -- -- H CH.sub.3J-4 -- 0 H H -- -- -- H OCH.sub.3J-5 -- 0 H H -- -- -- H CH.sub.3J-5 -- 0 H H -- -- -- H OCH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H OCH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-8 -- 0 H H -- -- -- H CH.sub.3J-8 -- 0 H H -- -- -- H OCH.sub.3J-9 -- 0 H H -- -- -- H CH.sub.3J-9 -- 0 H H -- -- -- H OCH.sub.3J-10 O 0 H H -- -- -- H CH.sub.3J-10 O 0 H H -- -- -- H OCH.sub.3J-22 O 0 H H -- H H -- OCH.sub.3J-23 -- -- H H -- H H -- OCH.sub.3J-24 -- -- H H -- -- CH.sub.3 H OCH.sub.3______________________________________
TABLE 29b______________________________________ ##STR193## m.p.J W.sub.1 n R R.sub.1 R.sub.2 R.sub.5 R.sub.6 R.sub.7 X.sub.1 (.degree.C.)______________________________________J-11 O 0 H H -- -- H H CH.sub.3J-11 O 0 H H -- -- H H OCH.sub.3J-12 -- 0 H H -- H H H CH.sub.3J-12 -- 0 H H -- H H H OCH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-14 -- -- H H -- -- -- -- CH.sub.3J-14 -- -- H H -- -- -- -- OCH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-16 -- -- H H -- -- -- -- CH.sub.3J-16 -- -- H H -- -- -- -- OCH.sub.3J-17 -- -- H H -- -- -- -- CH.sub.3J-17 -- -- H H -- -- -- -- OCH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-19 -- -- H H -- -- -- -- CH.sub.3J-19 -- -- H H -- -- -- -- OCH.sub.3J-20 -- -- H H CH.sub. 3 -- -- -- CH.sub.3J-20 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-21 -- -- H H -- -- -- -- CH.sub.3J-21 -- -- H H -- -- -- -- OCH.sub.3J-25 O -- H H -- -- H H CH.sub.3J-25 O -- H H -- -- H H OCH.sub.3J-26 -- -- H H CH.sub.3 -- H H CH.sub.3J-26 -- -- H H CH.sub.3 -- H H OCH.sub.3______________________________________
TABLE 30a__________________________________________________________________________ ##STR194##J W.sub.1 n R R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X.sub.2 Y.sub.2 m.p. (.degree.C.)__________________________________________________________________________J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3 CH.sub.3J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OCH.sub.3 208-210J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3 SCH.sub.3J-2 -- 0 H H -- -- -- H CH.sub.3 CH.sub.3J-2 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.3J-2 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-2 -- 0 H H -- -- -- H CH.sub.3 SCH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3 CH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OCH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-3 -- O H H CH.sub.3 -- -- H CH.sub.3 SCH.sub.3J-4 -- 0 H H -- -- -- H CH.sub.3 CH.sub.3J-4 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.3J-4 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-4 -- 0 H H -- -- -- H CH.sub.3 SCH.sub.3J-5 -- 0 H H -- -- -- H CH.sub.3 CH.sub.3J-5 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.3J-5 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-5 -- 0 H H -- -- -- H CH.sub.3 SCH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3 OCH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3 OCH.sub.2 CH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3 SCH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3 CH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OCH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3 SCH.sub.3J-8 -- 0 H H -- -- -- H CH.sub.3 CH.sub.3J-8 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.3J-8 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-8 -- 0 H H -- -- -- H CH.sub.3 SCH.sub.3J-9 -- 0 H H -- -- -- H CH.sub.3 CH.sub.3J-9 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.3J-9 -- 0 H H -- -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-9 -- 0 H H -- -- -- H CH.sub.3 SCH.sub.2J-10 O 0 H H -- -- -- H CH.sub.3 CH.sub.3J-10 O 0 H H -- -- -- H CH.sub.3 OCH.sub.3J-10 O 0 H H -- -- -- H CH.sub.3 OCH.sub.2 CH.sub.3J-10 O 0 H H -- -- -- H CH.sub.3 SCH.sub.3J-22 O 0 H H -- H H -- CH.sub.3 OCH.sub.3J-23 -- -- H H -- H H -- CH.sub.3 OCH.sub.3J-24 -- -- H H -- -- CH.sub.3 H CH.sub.3 OCH.sub.3__________________________________________________________________________
TABLE 30b__________________________________________________________________________ ##STR195##J W.sub.1 n R R.sub.1 R.sub.2 R.sub.5 R.sub.6 R.sub.7 X.sub.2 Y.sub.2 m.p. (.degree.C.)__________________________________________________________________________J-11 O 0 H H -- -- H H CH.sub.3 CH.sub.3J-11 O 0 H H -- -- H H CH.sub.3 OCH.sub.3J-11 O 0 H H -- -- H H CH.sub.3 OCH.sub.2 CH.sub.3J-11 O 0 H H -- -- H H CH.sub.3 SCH.sub.3J-12 -- 0 H H -- H H H CH.sub.3 CH.sub.3J-12 -- 0 H H -- H H H CH.sub.3 OCH.sub.3J-12 -- 0 H H -- H H H CH.sub.3 OCH.sub.2 CH.sub.3J-12 -- 0 H H -- H H H CH.sub.3 SCH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3 SCH.sub.3J-14 -- -- H H -- -- -- -- CH.sub.3 CH.sub.3J-14 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.3J-14 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-14 -- -- H H -- -- -- -- CH.sub.3 SCH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3 SCH.sub.3J-16 -- -- H H -- -- -- -- CH.sub.3 CH.sub.3J-16 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.3J-16 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-16 -- -- H H -- -- -- -- CH.sub.3 SCH.sub.3J-17 -- -- H H -- -- -- -- CH.sub.3 CH.sub.3J-17 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.3J-17 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-17 -- -- H H -- -- -- -- CH.sub.3 SCH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3 SCH.sub.3J-19 -- -- H H -- -- -- -- CH.sub.3 CH.sub.3J-19 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.3J-19 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-19 -- -- H H -- -- -- -- CH.sub.3 SCH.sub.2J-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3 CH.sub.3J-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3J-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3 SCH.sub.3J-21 -- -- H H -- -- -- -- CH.sub.3 CH.sub.3J-21 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.3J-21 -- -- H H -- -- -- -- CH.sub.3 OCH.sub.2 CH.sub.3J-21 -- -- H H -- -- -- -- CH.sub.3 SCH.sub.2J-25 O -- H H -- -- H H CH.sub.3 CH.sub.3J-25 O -- H H -- -- H H CH.sub.3 OCH.sub.3J-25 O -- H H -- -- H H CH.sub.3 OCH.sub.2 CH.sub.2J-25 O -- H H -- -- H H CH.sub.3 SCH.sub.3J-26 -- -- H H CH.sub.3 -- H H CH.sub.3 CH.sub.3J-26 -- -- H H CH.sub.3 -- H H CH.sub.3 OCH.sub.3J-26 -- -- H H CH.sub.3 -- H H CH.sub.3 OCH.sub.2 CH.sub.3J-26 -- -- H H CH.sub.3 -- H H CH.sub.3 SCH.sub.3__________________________________________________________________________
TABLE 31a______________________________________ ##STR196## m.p.J W.sub.1 n R R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X.sub.3 (.degree.C.)______________________________________J-1 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-1 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-2 -- 0 H H -- -- -- H CH.sub.3J-2 -- 0 H H -- -- -- H OCH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-3 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-4 -- 0 H H -- -- -- H CH.sub.3J-4 -- 0 H H -- -- -- H OCH.sub.3J-5 -- 0 H H -- -- -- H CH.sub.3J-5 -- 0 H H -- -- -- H OCH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H CH.sub.3J-6 -- 0 H H -- CH.sub.3 CH.sub.3 H OCH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H CH.sub.3J-7 -- 0 H H CH.sub.3 -- -- H OCH.sub.3J-8 -- 0 H H -- -- -- H CH.sub.3J-8 -- 0 H H -- -- -- H OCH.sub.3J-9 -- 0 H H -- -- -- H CH.sub.3J-9 -- 0 H H -- -- -- H OCH.sub.3J-10 O 0 H H -- -- -- H CH.sub.3J-10 O 0 H H -- -- -- H OCH.sub.3J-22 O 0 H H -- H H -- CH.sub.3J-23 -- -- H H -- H H -- CH.sub.3J-24 -- -- H H -- -- CH.sub.3 H CH.sub.3______________________________________
TABLE 31b______________________________________ ##STR197## m.p.J W.sub.1 n R R.sub.1 R.sub.2 R.sub.5 R.sub.6 R.sub.7 X.sub.3 (.degree.C.)______________________________________J-11 O 0 H H -- -- H H CH.sub.3J-11 O 0 H H -- -- H H OCH.sub.3J-12 -- 0 H H -- H H H CH.sub.3J-12 -- 0 H H -- H H H OCH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-13 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-14 -- -- H H -- -- -- -- CH.sub.3J-14 -- -- H H -- -- -- -- OCH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-15 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-16 -- -- H H -- -- -- -- CH.sub.3J-16 -- -- H H -- -- -- -- OCH.sub.3J-17 -- -- H H -- -- -- -- CH.sub.3J-17 -- -- H H -- -- -- -- OCH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-18 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-19 -- -- H H -- -- -- -- CH.sub.3J-19 -- -- H H -- -- -- -- OCH.sub.3J-20 -- -- H H CH.sub.3 -- -- -- CH.sub.3J-20 -- -- H H CH.sub.3 -- -- -- OCH.sub.3J-21 -- -- H H -- -- -- -- CH.sub.3J-21 -- -- H H -- -- -- -- OCH.sub.3J-25 O -- H H -- -- H H CH.sub.3J-25 O -- H H -- -- H H OCH.sub.3J-26 -- -- H H CH.sub.3 -- H H CH.sub.3J-26 -- -- H H CH.sub.3 -- H H OCH.sub.3______________________________________
FORMULATIONS
Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically,they will contain these ingredients in the following approximate proportions:
TABLE 32______________________________________ Active Weight Percent* Ingredient Diluent(s) Surfactant(s)______________________________________Wettable Powders 20-90 0-74 1-10Oil Suspensions, 3-50 40-95 0-15Emulsions, Solutions,(including EmulsifiableConcentrates)Aqueous Suspension 10-50 40-84 1-20Dusts 1-25 70-99 0-5Granules and Pellets 0.1-95 5-99.9 0-15High Strength 90-99 0-10 0-2Compositions______________________________________*Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.
Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound.Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell,New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0.degree. C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiologicalgrowth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying theactive material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 throughCol. 7, line 19 and Examples 10 through 41;
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;
G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., NewYork, 1961, pp. 81-96; and
J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
EXAMPLE 10
______________________________________Wettable Powder______________________________________N--[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfon-amide, 1,1-dioxide 80%sodium alkylnaphthalenesulfonate 2%sodium ligninsulfonate 2%synthetic amorphous silica 3%kaolinite 13%______________________________________
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
EXAMPLE 11
______________________________________Wettable Powder______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfonamide,1,1-dioxide 50%sodium alkylnaphthalenesulfonate 2%low viscosity methyl cellulose 2%diatomaceous earth 46%______________________________________
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.
EXAMPLE 12
______________________________________Granule______________________________________Wettable Powder of Example 11 5%attapulgite granules 95%(U.S.S. 20-40 mesh; 0.84-0.42 mm)______________________________________
A slurry of wettable powder containing .apprxeq.25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.
EXAMPLE 13
______________________________________Extruded Pellet______________________________________N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-propyl-1,2-benzisothiazole-7-sulfon-amide, 1,1-dioxide 25%anhydrous sodium sulfate 10%crude calcium ligninsulfonate 5%sodium alkylnaphthalenesulfonate 1%calcium/magnesium bentonite 59%______________________________________
The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42mm) openings) may be packaged for use and the fines recycled.
EXAMPLE 14
______________________________________Oil Suspension______________________________________N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-3,4-dihydro-2-methyl-2H-1,2-benzothiazine-8-sulfon-amide, 1,1-dioxide 25%polyoxyethylene sorbitol hexaoleate 5%highly aliphatic hydrocarbon oil 70%______________________________________
The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
EXAMPLE 15
______________________________________Wettable Powder______________________________________N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-(1-methylethyl)-1,2-benzisothiazole-7-sulfonamide, 1,1-dioxide 20%sodium alkylnaphthalenesulfonate 4%sodium ligninsulfonate 4%low viscosity methyl cellulose 3%attapulgite 69%______________________________________
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
EXAMPLE 16
______________________________________Low Strength Granule______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1,3-dihydro-3-oxoisobenzofuran-4-sulfonamide 1%N,N--dimethylformamide 9%attapulgite granules 90%(U.S.S. 20-40 sieve)______________________________________
The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying ofthe solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
EXAMPLE 17
______________________________________Aqueous Suspension______________________________________N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-bonyl]-2,3-dihydro-2-(1-methylethyl)-1,2-benziso-thiazole-7-sulfonamide, 1,1-dioxide 40%polyacrylic acid thickener 0.3%dodecylphenol polyethylene glycol ether 0.5%disodium phosphate 1%monosodium phosphate 0.5%polyvinyl alcohol 1.0%water 56.7%______________________________________
The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
EXAMPLE 18
______________________________________Solution______________________________________N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-bonyl]-2,3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfonamide, 1,1-dioxide, sodium salt 5%water 95%______________________________________
The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
EXAMPLE 19
______________________________________Low Strength Granule______________________________________N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1,3-dihydro-2-methyl-1-oxo-1H-isoindole-7-sulfon-amide, 0.1%attapulgite granules 99.9%(U.S.S. 20-40 mesh)______________________________________
The active ingredient is dissolved in a solvent and the solution is sprayedupon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
EXAMPLE 20
______________________________________Granule______________________________________N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-bonyl]-2,3-dihydro-2-ethyl-1,2-benzisothiazole-7-sulfonamide, 1,1-dioxide 80%wetting agent 1%crude ligninsulfonate salt (containing 10%5-20% of the natural sugars)attapulgite clay 9%______________________________________
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until thewater content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally14-100 mesh (1410-149 microns), and packaged for use.
EXAMPLE 21
______________________________________High Strength Concentrate______________________________________N--[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfon-amide, 1,1-dioxide 99%silica aerogel 0.5%synthetic amorphous silica 0.5%______________________________________
The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S. Ser. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
EXAMPLE 22
______________________________________Wettable Powder______________________________________N--[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfon-amide, 1,1-dioxide 90%dioctyl sodium sulfosuccinate 0.1%synthetic fine silica 9.9%______________________________________
The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.
EXAMPLE 23
______________________________________Wettable Powder______________________________________N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfonamide,1,1-dioxide 40%sodium ligninsulfonate 20%montmorillonite clay 40%______________________________________
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.
EXAMPLE 24
______________________________________Oil Suspension______________________________________N--[(4-methoxymethyl-6-methylpyrimidin-2-yl)aminocar-bonyl]-2,3-dihydro-2-methyl-1,2-benzisothiazole-7-sulfonamide, 1,1-dioxide 35%blend of polyalcohol carboxylic 6%esters and oil soluble petroleumsulfonatesxylene 59%______________________________________
The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.
UTILITY
Test results indicate that the compounds of the present invention are active herbicides. They should have utility for broad-spectrum pre- and/orpost-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures, or on fallow land. Alternatively, some of the subject compounds should be useful for the selective pre- or post-emergence weed control in crops, especially wheat, cotton and soybeans.
The rates of application for the compounds of the invention are determined by a number of factors, including their use as selective or general herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subjectcompounds should be applied at levels of around 0.001 to 5 kg/ha, the lower rates being suggested for use on lighter soils and/or those having alow organic matter content, for selective weed control or for situations where only short-term persistence is required.
The compounds of the invention may be used in combination with any other commercial herbicide; examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types. They also may be used in combination with mefluidide.
The herbicidal properties of the subject compounds were discovered in a number of green house tests. The test procedures and results follow.
TEST A
Seeds of crabgrass (Digitaria sp.), barnyard-grass (Echinochloa crusgalli),wild oats (Avena fatua), sicklepos (Cassia obtusifolia), morningglory (Ipomoea sp.), cocklebur (Xanthium pensylvanicum), sorghum, corn, soybean,sugar beet, rice, wheat, purple nutsedge (Cyperus rotundus) tubers, and in certain cases, cotton were planted and treated pre-emergence with the testchemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species, along with cotton and bush bean, were treated with a soil/foilage application. At the time of treatment, the plants ranged inheight from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0=no injury, to 10=complete kill. The accompanying descriptive symbols have thefollowing meanings:
C=chlorosis/necrosis;
E=emergence inhibition;
G=growth retardation;
H=formative effects;
L=lodging;
U=unusual pigmentation;
X=axillary stimulation; and
6Y=abscised flowers or buds.
The data show that most of the compounds tested are highly active herbicides with growth modifying properties and that some of the compoundstested provide selective weed control in crops such as wheat, cotton and soybeans. ##STR198##
TABLE A______________________________________ Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean 6C,9G,6Y 9C 4C,8G,6Y 4C,7G,6YCotton 5C,9G 6C,9G 4C,5H 2C,3HMorningglory 6C,9G 10C 2C,5G 1CCocklebur 6C,9G 9C 2C,7G 4GSicklepod 4C,9G 9C 2C,5G 3C,8GNutsedge 9C 9C 6G 8GCrabgrass 9C 9C 2G 2C,7GBarnyardgrass 9C 9C 5C,9H 9CWild Oats 9C 9C 3C,9G 9CWheat 9C 9C 9C 4C,9GCorn 9C 9C 6C,9G 9CSoybean 5C,9G 6C,9G 3C,9G 3C,8HRice 6C,9G 6C,9G 3C,9G 5C,9GSorghum 5C,9G 9C 2C,9G 2C,9GSugar beet 9C 9C 3C,9G 4C,9GPRE-EMER-GENCEMorningglory 9G 9C 3H 2GCocklebur 9H 9H 3G 2GSicklepod 8G 9G 8G 7GNutsedge 10E 10E 0 0Crabgrass 3G 5C,9G 0 0Barnyardgrass 2C,7H 6C,9H 2C 1CWild Oats 5C,8H 6C,9H 2C,8G 2C,8GWheat 5C,9G 10H 2C,9G 8GCorn 5C,9G 10E 4C,9G 3C,9GSoybean 4C,3H 9H 1C,2G 0Rice 10E 10E 10E 10ESorghum 5C,9H 6C,9H 4C,9G 2C,9GSugar beet 5C,9G 6C,9G 8G 4C,9G______________________________________ Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean 9C 9C 5C,9G,6Y 5C,9G,6YCotton 6C,9G 9C 5C,9G 2C,2HMorningglory 9C 10C 5C,9G 2C,4GCocklebur 9C 10C 9C 1C,3GSicklepod 9C 9C 5C,8G 3CNutsedge 10C 10C 3C,9G 5C,9GCrabgrass 9C 9C 6C,9G 2C,5GBarnyardgrass 9C 9C 9C 5C,9HWild Oats 9C 4C,9G 9C 5C,9GWheat 9C 9C 9C 9CCorn 9C 9C 5U,9C 3U,9GSoybean 6C,9G 3C,9G 5C,9G 4C,9GRice 9C 6C,9G 5C,9G 5C,9GSorghum 10C 9C 4C,9G 2C,9GSugar beet 9C 9C 9C 2C,8GPRE-EMER-GENCEMorningglory 9C 9C 9C 1CCocklebur 9H 9H 9H 2C,8GSicklepod 9C 9G 9G 3GNutsedge 10E 10E 10E 3GCrabgrass 6C,9G 5C,9G 2C,5G 1C,3GBarnyardgrass 6C,9H 6C,9H 2C,9G 2CWild Oats 6C,9H 5C,9G 4C,9G 2C,7GWheat 10H 3C,9G 9H 2C,8GCorn 10H 4C,9H 5C,9H 2C,7HSoybean 9H 6H 4C,5H 1CRice 10E 10E 10E 5C,9HSorghum 10H 6C,9H 5C,9H 2C,5GSugar beet 9C 10E 5C,9G 7G______________________________________ Cmpd. 9 Cmpd. 10 Cmpd. 11 Cmpd. 12Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 4C,9H 5C,9G 9C 4C,8GMorningglory 4C,8H 10C 9C 5C,9HCocklebur 3C,7H 9C 10C 2C,5GSicklepod 3C,7H 9C 9C 3C,5HNutsedge 2C,8G 4C,9G 2C,9G 5GCrabgrass 4C,9G 9C 9C 2C,5GBarnyardgrass 5C,9G 9C 9C 5C,9HWild Oats 9C 9C 9C 6C,9GWheat 10C 10C 9C 5C,9GCorn 5C,9G 10C 10C 5U,9GSoybean 2C,9G,5X 5C,9G 9C 3C,8G,5XRice 6C,9G 9C 6C,9G 5C,9GSorghum 4C,9H 9C 9C 5C,9GSugar beet 4C,8H 9C 9C 9CPRE-EMER-GENCEMorningglory 3C,8H 9C 10E 7HCocklebur 2C,3H 9H 9H 0Sicklepod 2C 9G 9G 7GNutsedge 5C,8G 10E 10E 2GCrabgrass 5C,9G 9C 6C,9G 0Barnyardgrass 5C,9H 5C,9H 10H 4C,5GWild Oats 10C 9C 6C,9H 2C,9GWheat 10C 10C 10E 5C,9GCorn 2U,8G 5C,9H 10H 5C,9HSoybean 3C 9H 9H 1C,2HRice 10E 10E 10E 10Sorghum 10C 5C,9H 10E 5C,9HSugar beet 9C 10C 10E 9CCotton 3C,4H 9G 2C,9G 5G______________________________________ Cmpd. 13 Cmpd. 14 Cmpd. 15 Cmpd. 16Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 4C,9G 3C,9G 3C,9H 10CMorningglory 4C,8H 4C,8G 5C,9G 9CCocklebur 8H 4C,9G 4C,9H 10CSicklepod 3G 9G 5C,9G 9CNutsedge 3C,7G 5G 9G 4C,9GCrabgrass 5C,9G 3C,9G 6C,9G 5C,9GBarnyardgrass 9C 5C,9H 6C,9G 9CWild Oats 2C,9G 9C 6C,9G 9CWheat 5C,9G 9C 9C 9CCorn 10C 4U,9G 5U,9C 9CSoybean 2C,6G 5C,9G 5C,9G 9CRice 5C,9G 3C,9G 5C,9G 5C,9GSorghum 9C 2C,9G 5C,9G 4U,9CSugar beet 9C 5C,9G 9C 9CPRE-EMER-GENCEMorningglory 9C 9G 2C,6H 9HCocklebur 9H 8H 2C,3H 9HSicklepod 8G 8G 8G 9CNutsedge 10E 10E 10E 10ECrabgrass 5C,9G 4C,8G 5C,8G 5C,9GBarnyardgrass 10H 2C,8H 9H 9HWild Oats 5C,9G 2C,8G 5C,8H 5C,9HWheat 4C,9G 2C,8G 4C,9H 9HCorn 5C,9H 8G 3C,9G 5C,9HSoybean 2C,3G 1C,1H 2C,4G 9HRice 10E 10E 10E 10ESorghum 7C,9H 2C,9G 4C,9H 5C,9HSugar beet 9C 3C,9G 4C,9G 10ECotton 8G 2G 3G 9H______________________________________ Cmpd. 17 Cmpd. 18 Cmpd. 19 Cmpd. 20Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 10C 10C 10C 3C,7HMorningglory 10C 10C 10C 2C,5HCocklebur 9C 10C 10C 2GSicklepod 9C 9C 10C 3C,6HNutsedge 10C 5C,9G 9C 1C,2GCrabgrass 9C 5C,9G 9C 3GBarnyardgrass 9C 9C 9C 3C,9HWild Oats 9C 9C 5C,9G 5C,9GWheat 9C 9C 6C,9G 5C,9GCorn 5U,9C 10C 9C 5C,9GSoybean 6C,9G 6C,9G 6C,9G 2C,2HRice 9C 9C 6C,9G 5C,9GSorghum 4U,9G 9C 9C 3C,9HSugar beet 9C 9C 9C 3C,7GPRE-EMER-GENCEMorningglory 9H 10E 9G 8GCocklebur 9H 9H 9H 8HSicklepod 9G 9C 9G 8GNutsedge 10E 10E 3C,8G 0Crabgrass 5C,9G 6C,9G 5C,9G 0Barnyardgrass 6C,9H 6C,9H 6C,9H 3C,3HWild Oats 9C 6C,9H 6C,9H 3C,9HWheat 10E 10E 10H 2C,9HCorn 10E 10E 6C,9H 3C,9GSoybean 9H 9H 9H 3GRice 10E 10E 10E 10ESorghum 10E 10E 10E 5C,9HSugar beet 10E 10E 10E 8GCotton 5C,9G 9C 3C,9G 3G______________________________________ Cmpd. 21 Cmpd. 22 Cmpd. 23 Cmpd. 24Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 9C 0 4C,9H 4C,9GMorningglory 9C 2C,5G 4C,8H 5C,9GCocklebur 9C 3G 2C,7H 4C,9HSicklepod 9C 0 4C,8G 2C,6GNutsedge 9C 0 2C,8G 9CCrabgrass 6C,9G 2C,5G 4C,9G 9CBarnyardgrass 9C 5C,9H 9C 9CWild Oats 5C,9G 9C 9C 9CWheat 10C 2C,8G 2G 2C,5GCorn 10C 2U,8H 7U,9C 10CSoybean 5C,9G 2C,5G 5C,9G 4C,9GRice 6C,9G 4C,9G 6C,9G 5C,9GSorghum 9C 4C,9H 5C,9G 8C,9HSugar beet 9C 0 0 3C,7GPRE-EMER-GENCEMorningglory 9H 2C,4G 4C,8H 5C,9GCocklebur 9H 0 5C,9H 9HSickelpod 2C,9G 0 2C,5G 3C,9HNutsedge 10E 0 8G 10ECrabgrass 2C,5G 2C,6G 6G 5C,9GBarnyardgrass 5C,9H 2C 3C,8H 5C,9HWild Oats 2C,9G 5C,9H 5C,9H 6C,9HWheat 4C,9H 5G 0 2C,9GCorn 2C,9H 3C,8H 2C,9G 5C,9HSoybean 9H 2C 4C,7H 4C,8GRice 10E 5C,9H 10E 10ESorghum 10H 3C,6H 3C,9H 2C,9HSugar beet 3C,9G 5G 3C,8H 9CCotton 3C,9G 1C 6G 9G______________________________________ Cmpd. 25 Cmpd. 26 Cmpd. 27 Cmpd. 28Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 2C,7H 0 0 9CMorningglory 2C,4G 3G 0 9CCocklebur 4G 3G 0 9CSicklepod 2C,2G 3G 0 5C,9GNutsedge 0 0 0 10CCrabgrass 2C,8G 2G 0 9CBarnyardgrass 9C 5C,9H 3C,8H 9CWild Oats 9C 9C 3C,8G 0Wheat 0 0 0 0Corn 6C,9H 3U,9G 2C,8H 10CSoybean 4C,8H 0 lC 2C,7GRice 6C,9G 5C,9G 7G 9CSorghum 7C,9H 3C,9H 2C,6G 9CSugar beet lC 0 0 9CPRE-EMER-GENCEMorningglory 4C,8G 0 0 9GCocklebur 2C,5G 2C,3G 0 9HSicklepod 2C 0 0 9GNutsedge 8G 0 0 10ECrabgrass 3C,8G 3G 2G 5C,9GBarnyardgrass 3C,9H 2H 0 6C,9HWild Oats 3C,8G 4G 5G 2C,5GWheat 3C,8G 0 0 0Corn 3C,9H 2C,7G 3G 3C,9HSoybean 3C,6H 0 0 3C,6GRice 10E 3C,7H 2C,7G 10ESorghum 5C,9H 9H 0 10HSugar beet 8G 0 0 10ECotton 6G 0 0 9G______________________________________ Cmpd. 29 Cmpd. 30 Cmpd. 31 Cmpd. 32Rate g/ha 50 50 50 50 2000______________________________________POST-EMER-GENCEBush bean -- -- -- -- --Cotton 5C,9G 6C,9G 3C,8H 0 3C,9GMorningglory 9C 5C,9G 3C,7H 0 3C,9HCocklebur 10C 10C 7G 0 3C,9HSicklepod 9C 2C,8G 8G 0 3C,9GNutsedge 10C 5C,9G 2C,5G 0 2C,9GCrabgrass 10C 5C,9G 4G 0 3C,9HBarnyardgrass 10C 9C 2C,8G 0 9CWild Oats 9C 9C 2C,3G 0 4C,8GWheat 9C 9C 2G 0 9CCorn 10C 9C 2C,6H 0 9CSoybean 5C,9G 5C,9G 2H 0 3C,9HRice 6C,9G 6C,9G 5G 0 6C,9GSorghum 9C 9C 2C,8H 0 2C,9GSugar beet 9C 9C 0 0 3C,8GPRE-EMER-GENCEMorningglory 9G 9H 8H 0 10CCocklebur 2C,9H 8H 9H 0 9HSicklepod 9C 9G 5C,9G 0 9CNutsedge 10E 10E 7G 0 3GCrabgrass 9C 4C,7G 6G 0 0Barnyardgrass 6C,9H 5C,9H 4C,8H 0 4C,6HWild Oats 6C,9H 5C,9H 9G 0 3C,9GWheat 10E 5C,9H 9G 0 3C,9GCorn 10E 9H 3C,9H 0 3U,9GSoybean 9H 2C,7H lC,3G 0 4GRice 10E 10E 10E 0 3C,8GSorghum 10H 10H 9H 0 3C,9HSugar beet 6C,9G 5C,9G 7G 0 8GCotton 9G 9G 9G 0 8______________________________________ Cmpd. 33 Cmpd. 34 Cmpd. 35 Cmpd. 36Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton lC 9C 9C 4GMorningglory 2C 4C,9H 5C,9G 2C,8GCocklebur lC 5C,9G 2C,8G 6GSicklepod 0 2C,4G 2C,7G 3C,8HNutsedge 0 4C,9G 10C 9CCrabgrass 0 0 lC 3C,9HBarnyardgrass 2C,6H 3C,8H 3C,8H 9CWild Oats 2C,7G 3C,8G 3C,9G 3C,9GWheat 2C,4G 5C,9G 9C 5C,9GCorn 9C 3H,5L 3H,5L 10CSoybean 0 4C,8H 4C,9G 3C,8HRice 4C,9G 5C,9G 4C,9G 3C,9GSorghum 2C,9G 2U,9H 9G 5U,9GSugar beet 2C,3H 9C 5C,9G 2C,9GPRE-EMER-GENCEMorningglory 1C 3C,8G 2C 2C,8GCocklebur 4H 2C,8H 2C,7H 3C,9HSicklepod 0 8G 2G 4C,8GNutsedge 0 0 0 10ECrabgrass 0 0 0 3C,7GBarnyardgrass 0 0 0 5C,9HWild Oats 0 0 0 3C,9GWheat 0 0 0 10HCorn 2C,8H 0 2G 9HSoybean 0 0 0 3C,8HRice 2C,8H 5G 7H 10ESorghum 8H 2C,8G 2C,9H 6C,9HSugar beet 0 2C,8G 7H 9GCotton 0 2G 2G 8G______________________________________ Cmpd. 37 Cmpd. 38 Cmpd. 39 Cmpd. 40Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 4C,8G 0 5G 0Morningglory 2C,8H 1C 2C,3G 3HCocklebur 2C,5G 2G 4G 4GSicklepod 4C,4H 1C 4G lCNutsedge 0 0 8G 5C,9GCrabgrass 3G 2C,8G 5C,9G 9CBarnyardgrass 9C 2C,9H 10C 9CWild Oats 9C 5C,9G 5C,9G 6C,9GWheat 9C 9C 8G 9GCorn 6U,9C 2C,7H 5C,9G 2C,8HSoybean 4C,8G 2G lC,3H 5GRice 5C,9G 5C,9G 9C 9CSorghum 4C,9G 4C,9H 9C 3C,9GSugar beet 9C 0 4C,9H 2C,5GPRE-EMER-GENCEMorninglory 8H 0 3G 2C,2HCocklebur 9H 0 3G 6HSicklepod 6G 0 3G 3GNutsedge 3G 0 8G 7GCrabgrass 0 0 3C,8G 4GBarnyardgrass 3C,8H 1H 5C,9H 3C,8HWild Oats 5C,9G 2C 3C,9G 2C,9GWheat 3C,9G 0 7G 8GCorn 5C,9H 2G 9G 2C,8GSoybean 2C 0 1C,3G 2GRice 10E 5G 10E 10ESorghum 6C,9H 0 10H 5C,9HSugar beet 4C,9G 0 7G 5GCotton 7G 0 2G 1C______________________________________ Cmpd. 41 Cmpd. 42 Cmpd. 43 Cmpd. 44Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 0 0 2C,5G 6C,9GMorningglory 5G 0 2G 6C,9GCocklebur 3G 0 3G 9CSicklepod 2G 0 2G 9CNutsedge 3G 0 5G 3C,9GCrabgrass 3G 2G 6G 9CBarnyardgrass 4C,9H 3C,8H 2C,8H 5C,9GWild Oats 4C,9H 3C,9H 4C,8H 9CWheat 9C 3C,9H 9C 10CCorn 2C,8H 0 2C,9H 9CSoybean 0 0 6H 5C,9GRice 3C,9G 9G 4C,9G 6C,9GSorghum 3C,9H 0 3C,8H 9CSugar beet 0 0 2C 9CPRE-EMER-GENCEMorningglory 2C 0 3H 9GCocklebur 0 0 2H 9HSicklepod 0 0 0 8GNutsedge 0 0 0 3C,9GCrabgrass 0 0 0 5C,9GBarnyardgrass 2H 0 3G 3C,9HWild Oats 2C,4G 2G 2G 5C,9GWheat 8G 2G 2G 6C,9HCorn 4G 0 0 5C,9HSoybean 0 0 3G 4C,8HRice 5G 0 0 10ESorghum 2G 0 0 5C,9HSugar beet 0 0 0 5C,9GCotton 0 0 0 8G______________________________________ Cmpd. 45 Cmpd. 46 Cmpd. 47 Cmpd. 48Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 10C 5C,9G 0 3C,8HMorningglory 5C,9G 4C,9G 1C 2C,7HCocklebur 9C 9C 1C 3C,8HSicklepod 9C 5C,9G 0 lC,3HNutsedge 3C,9G 2C,8G 0 3C,8GCrabgrass 9C 2C,9G 0 2HBarnyardgrass 9C 9C 3C,7H 4C,9HWild Oats 9C 9C 2C,5G 5C,9GWheat 10C 10C 6G 9CCorn 9C 10C 2C,8H 2C,8HSoybean 9C 5C,9G 0 3C,6HRice 6C,9G 5C,9G 3C,9G 6C,9GSorghum 9C 10C 2C,8H 6HSugar beet 9C 9C lC 2C,5GPRE-EMER-GENCEMorningglory 9H 9G 1C 0Cocklebur 9H 8H 0 0Sicklepod 9G 9G 0 0Nutsedge 10E 8G 0 0Crabgrass 5C,9G 2C,7G 0 1CBarnyardgrass 9H 3C,9H 0 0Wild Oats 5C,9H 3C,8G 0 3C,9HWheat 10E 4C,9H 0 9HCorn 5C,9G 5C,9H 2C,3G 3C,6HSoybean 9H 4C,5H 0 2C,3HRice 10E 10E 2C,5G 8HSorghum 5C,9H 4C,9H 2C,8G 2C,9HSugar beet 5C,9G 5C,9G 1C 3C,4HCotton 9G 8G 0 0______________________________________ Cmpd. 49 Cmpd. 50 Cmpd. 51 Cmpd. 52Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 7G 3G 3C,9H 3C,9GMorningglory 2C,5G lH 3C,8G 9CCocklebur 4H 2C,4G 3C,9H 9CSicklepod 2G 2C 3C,9G 9CNutsedge 2C,9G 2C,8G 9C 9CCrabgrass 0 3C,9G 6C,9G 9CBarnyardgrass 7H 9C 9C 9CWild Oats 3C,9H 9C 9C 9CWheat 5C,9H 9C 9C 9CCorn 2C,5H 3U,9G 6C,9G 9CSoybean 3C,8H 2C,7G 3C,9G 9CRice 4C,9G 5C,9G 6C,9G 9CSorghum 2C,7H 3C,9H 4U,9G 9CSugar beet 2C,3G 2C,6G 9C 9CPRE-EMER-GENCEMorningglory 0 3H 9G 9GCocklebur 0 lH 9H 9HSicklepod 0 0 8G 8GNutsedge 0 0 3C,8G 10ECrabgrass 0 7G 5C,9G 6C,9HBarnyardgrass 0 2G 2C,9H 5C,9HWild Oats 0 2C,8G 6C,9H 6C,9HWheat 0 2C,5H 5C,9H 10ECorn 0 3C,7G 4C,9H 4C,9HSoybean 0 0 3C,6G 3C,7HRice 0 5C,9H 10E 10ESorghum 0 3C,7G 5C,9H 6C,9HSugar beet 0 3G 5C,9G 6C,9GCotton 0 0 8G 3C,9G______________________________________ Cmpd. 53 Cmpd. 54 Cmpd. 55 Cmpd. 56Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 3C,9H 2C,7G 3C,9G 2C,8GMorningglory 3C,8G 3C,7G 5C,9G 4C,8GCocklebur 4C,9H 3G 5C,9G 5C,9GSicklepod 3C,7G lC,2G 3C,8G 3C,9HNutsedge 9C lC,3G 2C,8G 6C,9GCrabgrass 9C 2G 2G 3C,8GBarnyardgrass 10C 9C 2C,8H 4C,9HWild Oats 9C 0 0 5C,9GWheat 9C 9G 0 5C,9GCorn 9C 2C,9H 0 9CSoybean 4C,9G 3C,8H 5C,9G 4C,9GRice 9C 4C,9H 5G 9CSorghum 10C 3C,6G 2C,5G 4C,9HSugar beet 9C 5C,9G 3C,9G 9CPRE-EMER-GENCEMorningglory 8G 0 0 9GCocklebur 9H 0 0 9HSicklepod 7G 0 0 6GNutsedge 10E 0 0 0Crabgrass 6C,9G 0 0 2C,3GBarnyardgrass 6C,9H 0 0 3C,4HWild Oats 4C,9G 0 0 4C,9GWheat 3C,8G 0 0 2C,9GCorn 3C,9H 0 0 3C,9HSoybean 5G 0 0 4C,6GRice 10E 0 0 9HSorghum 10H 0 0 2C,9HSugar beet 6C,9G 0 0 5C,9GCotton 8G 0 0 7G______________________________________ Cmpd. 57 Cmpd. 58 Cmpd. 59 Cmpd. 60Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 2C,8H 5G 10C 0Morningglory 5C,9G 3C,7G 9C 0Cocklebur 5C,9G 2C,8H 9C 0Sicklepod 2C,5G 6G 10C 0Nutsedge 2C,9G 8G 9C 0Crabgrass 2C,3H 7G 7G 0Barnyardgrass 4C,9H 3C,9H 10C 0Wild Oats 9C 2C,6G 4C,9G 0Wheat 9C 2C,6G 9C 0Corn 9C 3C,9H 10C 0Soybean 4C,9H 2H,5G 9C 0Rice 9C 3C,9G 9C 0Sorghum 4C,9G 3U,9G 10C 0Sugar beet 5C,9G 5G 9C 0PRE-EMER-GENCEMorningglory 9H 8G 9G 0Cocklebur 2C,8H 2C,8H 9H 0Sicklepod lC 8G 5C,9G 0Nutsedge 2C,6G 8G 10E 0Crabgrass 2C,2G 3C,6G lC,3G 0Barnyardgrass 2C,3H 4C,9H 5C,9H 0Wild Oats 5C,9H 3C,9H 5C,8G 0Wheat 9C 2C,8G 5C,9H 0Corn 9G 3C,9H 3C,9G 0Soybean 2C,3G lC,6G 3C,8H 0Rice 5C,9H 10E 10E 0Sorghum 5C,9H 2C,8H 5C,9H 0Sugar beet 5C,9G 8G 9C 0Cotton 8G 8G 9G 0______________________________________ Cmpd. 61 Cmpd. 62 Cmpd. 63 Cmpd. 64Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 0 9G,2C 8G 2C,5GMorningglory 0 3C,8H lC,3G 2CCocklebur 0 9C 3C,9H 3C,7HSicklepod 0 3C,8H 3G 2CNutsedge 0 2C,8G 5G 0Crabgrass 0 4C,9G 2C,8G 1HBarnyardgrass 2H 5C,9H 5C,9H 2C,9HWild Oats 0 9C 4G 0Wheat 0 9C 2C,5G 10CCorn 0 2C,9G 2C,9G 3U,9GSoybean 0 3C,9G 2G 4C,9GRice 2G 5C,9G 5C,9G 5C,9GSorghum 2H 5C,9H 3C,9H 2C,9HSugar beet 0 5C,9G 2C,4G 3C,3HPRE-EMER-GENCEMorningglory 0 9G 5G 2C,6GCocklebur 0 2C,9H 8H 8HSicklepod 0 3C,6H 4G 5GNutsedge 0 5G 4G 0Crabgrass 0 3C,7G 5G 0Barnyardgrass 0 3C,9H 9H 2C,6HWild Oats 0 4C,9G 1C,3G 2C,5GWheat 0 5C,9G 2C,8G 9GCorn 0 2C,9G 2C,9G 9GSoybean 0 2C,7H 1H 2C,3GRice 0 5C,9H 10E 5C,9HSorghum 0 5C,9G 2C,9H 3C,9HSugar beet 0 5C,9G 2C,8G 3C,8GCotton 0 8G 5G 5G______________________________________ Cmpd. 65 Cmpd. 66 Cmpd. 67 Cmpd. 68Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 2G 3C,9G 5C,9G 2C,7GMorningglory 2C,2H 9C 10C 2C,8GCocklebur 3C,5G 5C,9G 5C,9G 5C,9GSicklepod 2C 5C,9G 5C,9G 2C,8GNutsedge 4G 4C,9G 3C,9G 9CCrabgrass 3G 2C,9G 7H 2C,7GBarnyardgrass 3C,9H 2C,9H 5C,9H 10CWild Oats 2C,8G 3C,9G 5C,9G lCWheat 9C 2C,9G 5C,9G lCCorn 5C,9G 10C 10C 10CSoybean 2C,7G 5C,9G 4C,9G 2C,8GRice 5C,9G 6C,9G 6C,9G 5C,9GSorghum 2C,9H 6C,9G 6C,9G 10CSugar beet 0 5C,9G 9C 5C,9GPRE-EMER-GENCEMorningglory 2C,4H 10C 5C,9G 9GCocklebur 7H 2C,9H 4C,9H 9HSicklepod 3C,5G 5C,9G 2C,9G 8GNutsedge 0 9G 10E 2C,7GCrabgrass 2C 3C,8G 4C,6G 1CBarnyardgrass 2C,4H 9H 5C,9H 3C,9HWild Oats 3C,7G 6C,9G 4C,9H 1CWheat 9G 10E 10E 4GCorn 1C,9G 5C,9H 5C,9H 9HSoybean 2C,5G 4C,9G 2C,6H 4GRice 5C,9H 10E 10E 10ESorghum 2C,9G 7C,9H 10H 3C,9HSugar beet 3G 3C,9G 9G 2C,9GCotton 2G 9G 9G 8G______________________________________ Cmpd. 69 Cmpd. 70 Cmpd. 71 Cmpd. 72Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 4C,9G 9C 10C 9CMorningglory 9C 9C 9C 9CCocklebur 6C,9G 9C 9C 10CSicklepod 5C,9G 10C 9C 10CNutsedge 2C,8G 10C 10C 10CCrabgrass 9C 9C 9C 9CBarnyardgrass 9C 9C 9C 9CWild Oats 0 9C 9C 9CWheat 5C,9H 9C 9C 9CCorn 10C 10C 10C 10CSoybean 5C,9G 6C,9G 9C 9CRice 5C,9G 9C 6C,9G 6C,9GSorghum 10C 9C 9C 10CSugar beet 9C 9C 9C 9CPRE-EMER-GENCEMorningglory 5C,9G 9C 9C 10CCocklebur 9H 9H 9H 9HSicklepod 9C 9C 9C 9CNutsedge 7G 10E 10E 10ECrabgrass 4C,9G 6C,9G 9C 9CBarnyardgrass 4C,9H 6C,9H 6C,9H 2C,9HWild Oats 2C,5G 6C,9H 9C 7C,9HWheat 2C,9H 10H 10H 10HCorn 3C,9H 10H 10H 10HSoybean 3C,9H 9H 4C,9H 3C,9HRice 10E 10E 10E 10ESorghum 7C,9H 10H 9C 10HSugar beet 5C,9G 10C 10C 10ECotton 9G 9C 9C 9G,4C______________________________________ Cmpd. 73 Cmpd. 74 Cmpd. 75 Cmpd. 76Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 9C 10C 9C 10CMorningglory 10C 6C,9G 10C 9CCocklebur 10C 10C 10C 10CSicklepod 9C 9C 9C 9CNutsedge 9C 9C 9C 9CCrabgrass 9C 10C 10C 10CBarnyardgrass 9C 9C 9C 9CWild Oats 9C 9C 6C,9G 9CWheat 10C 10C 6C,9G 9CCorn 10C 10C 10C 10CSoybean 9C 9C 6C,9G 6C,9GRice 6C,9G 9C 9C 9CSorghum 9C 9C 10C 10CSugar beet 9C 9C 10C 9CPRE-EMER-GENCEMorningglory 9C 9H 9C 9CCocklebur 9H 9H 4C,9G 9HSicklepod 9C 9C 9C 9CNutsedge 5C,9G 10E 9G 9GCrabgrass 9C 9C 9C 4C,9GBarnyardgrass 5C,9H 5C,9H 9C 5C,9HWild Oats 10C 6C,9H 6C,9G 9CWheat 10H 10H 10E 10CCorn 5C,9H 9C 10E 5C,9HSoybean 3C,9H 9H 9H 8HRice 10E 10E 10E 10ESorghum 10H 10H 9C 10HSugar beet 10C 10C 10E 6C,9GCotton 10C 9G 9G 9C______________________________________ Cmpd. 77 Cmpd. 78 Cmpd. 79 Cmpd. 80Rate g/ha 50 50 50 50______________________________________POST-EMER-GENCEBush bean -- -- -- --Cotton 9C lC 2C,8H 4C,9HMorningglory 4C,8H 5G 3C,9G 4C,9GCocklebur 9C 5G 3C,8H 4C,9HSicklepod 9C 3C,6G 4C,9G 5C,9GNutsedge 9C 2C 3C,7G 3C,8GCrabgrass 5C,9G 2C,8H 2C,8G 9GBarnyardgrass 9C 3C,9H 9C 9CWild Oats 5C,9G 3C,8G 2C,8G 5C,9GWheat 6C,9G 5C,9G 2C,9G 2C,9GCorn 10C 4U,9G 10C 10CSoybean 5C,9G 3C,8G 4C,9G 4C,9GRice 9C 4C,9G 4C,9G 6C,9GSorghum 10C 3C,9G 4C,9G 9CSugar beet 9C 3C,8G 9C 9CPRE-EMER-GENCEMorningglory 9C 2C,7G 4C,9G 9GCocklebur 5C,9H 9H 3C,9H 9HSicklepod 9C 3C,8G 5C,9G 8GNutsedge 10E 2C,5G 2C,8G 2C,9GCrabgrass 2C,5G 2C,3H 5C,9G 2C,8GBarnyardgrass 4C,9H 3C,9H 5C,9H 9HWild Oats 9G 3C,9G 4C,9G 2C,9GWheat 10H 2C,9G 10H 4C,9HCorn 5C,9G 2C,8G 3C,9H 2C,9HSoybean 4C,9H 2G 3C,9H 3C,7HRice 10E 9H 10E 10ESorghum 9C 3C,9H 10H 4C,9HSugar beet 9C 2C,8G 9C 9CCotton 9C 8G 9G 9G______________________________________
TEST B
Two plastic bulb pans were filled with fertilized and limed Woodstown sandyloam soil. One pan was planted with corn, sorghum, Kentucky bluegrass and several grass weeds. The other pan was planted with cotton, soybeans, purple nutsedge (Cyperus rotundus), and several broadleaf weeds. The following grass and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot was also filled with prepared soil and planted with rice and wheat. Another 12.5 cm pot was planted with sugar beets. The above four containers were treated pre-emergence with several test compounds within the scope of the invention.
Twenty-eight days after treatment, the plants were evaluated and visually rated for response to the chemical treatments utilizing the rating system described previously for Test A. The data are summarized in Table B.
TABLE B______________________________________PRE-EMERGENCE ONWOODSTOWN SANDY LOAM______________________________________ Compound 1Rate g/ha 1 4 16 62 250______________________________________Crabgrass 0 0 4G 7G 8GBarnyardgrass 0 0 2G 8G 9GSorghum -- -- -- -- --Wild Oats 0 0 2G 7G 9GJohnsongrass 0 0 8G 8G 9GDallisgrass -- -- -- -- --Giant foxtail 0 0 7G 9G 9GKy. bluegrass -- -- -- -- --Cheatgrass -- -- -- -- --Sugar beets 0 3G 7G 7G 9GCorn 3G 3G 9G 9G 10GMustard -- -- -- -- --Cocklebur 0 5G 7G 8G 8GPigweed -- -- -- -- --Nutsedge 6G 9G 10G 10G 10GCotton 0 0 0 3G 9GMorningglory 0 0 6G 8G 9GSicklepod 0 0 2G 8G 9GTeaweed 0 0 0 2G 9GVelvetleaf 0 1G 6G 6G 9GJimsonweed 0 0 6G 9G 9GSoybean 0 0 2G 1G 9GRice 8G 9G 10G 10G 10GWheat 0 2G 8G 9G 9G______________________________________ Compound 2Rate g/ha 1 4 16 62 250______________________________________Crabgrass 0 3G 8G 8G 9GBarnyardgrass 0 0 7G 8G 9GSorghum -- -- -- -- --Wild Oats 0 0 6G 8G 8GJohnsongrass 0 0 8G 7G 9GDallisgrass -- -- -- -- --Giant foxtail 4G 9G 9G 8G 9GKy. bluegrass -- -- -- -- --Cheatgrass -- -- -- -- --Sugar beets 6G 7G 8G 9G 9GCorn 5G 8G 8G 10G 10GMustard -- -- -- -- --Cocklebur 0 7G 8G 9G 9GPigweed -- -- -- -- --Nutsedge 8G 9G 10G 10G 10GCotton 0 0 8G 9G 9GMorningglory 0 3G 7G 9G 9GSicklepod 0 4G 7G 9G 9GTeaweed 0 0 8G 9G 9GVelvetleaf 0 0 8G 9G 9GJimsonweed 0 7G 8G 9G 9GSoybean 0 3G 7G 9G 9GRice 9G 9G 10G 10G 10GWheat 8G 9G 9G 10G 10G______________________________________ Compound 5Rate g/ha 4 31______________________________________Crabgrass 10C 10CBarnyardgrass 10C 10CSorghum 10C 10CWild Oats 9G 9GJohnsongrass 9G 10CDallisgrass 9G 10CGiant foxtail 9G 10CKy. bluegrass 10C 10CCheatgrass 9G 10CSugar beets 10C 10CCorn 10C 10CMustard 8G 9GCocklebur 6G 9GPigweed -- --Nutsedge 10C 10CCotton 7G 9GMorningglory 9G 9GSicklepod 7G 9GTeaweed 6G 9GVelvetleaf 6G 9CJimsonweed 8G 9GSoybean 7G,5H 9GRice 10C 10CWheat 10C 10C______________________________________
TEST C
The test chemicals, dissolved in a non-phytotoxic solvent, were applied in an overall spray to the foliage and surrounding soil of selected plant species. One day after treatment, plants were observed for rapid burn injury. Approximately fourteen days after treatment, all species were visually compared to untreated controls and rated for response to treatment. The rating system was so described previously for Test A. The data are presented in Table C.
All plant species were seeded in Woodstown sandy loam soil and grown in a green house. The following species were grown in soil contained in plasticpots (25 cm diameter by 13 cm deep): soybeans, cotton, corn, rice, wheat, velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), sicklepod(Cassia obtusifolia), morningglory (Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria sp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua). Sugar beets were grown separately in soil in a paper cup (12 cm diameter by 13 cm deep). All plants were sprayed approximately 14 days after planting. Additional plant species are sometimes added to this standard test in order to evaluate unusual selectivity.
TABLE C______________________________________Over-the-Top Soil/Foliage Treatment______________________________________ Compound 1Rate g/ha 1 4 16 62______________________________________Soybeans 2G 0 10C 10CVelvetleaf 0 8C 9G 9CSesbania 2G 2G 7G 7GSicklepod 2G 4G 4G 9GCotton 3G 3G 4G 7GMorningglory 3G 8G 9G 10GAlfalfa -- -- -- --Jimsonweed 0 0 -- --Cocklebur 2G 2G 9G 10GSunflower -- -- -- --Mustard -- -- -- --Sugar beets 8G 10G 10G 10CCorn 6U 10C 10C 10CCrabgrass 0 4G 7G 8GRice 3C 7G 8C 8CNutsedge 5H 6G 6C 6GBarnyardgrass 5G 8C 10G 10CWheat 2G 4G 6C 7CGiant foxtail 3G 6G 6G 7GWild Oats 2G 6G 8G 9CSorghum -- -- -- --Johnsongrass 6U 9U 10C 10CField Bindweed -- -- -- --______________________________________ Compound 2Rate g/ha 1 4 16 62______________________________________Soybeans 8G 10G 10G 10GVelvetleaf 0 9G 9C 9CSesbania 5G 7G 8G 10CSicklepod 5G 7G 9G 10GCotton 0 8G 9G 10GMorningglory 7G 9G 9G 10GAlfalfa -- -- -- --Jimsonweed 0 -- -- --Cocklebur 0 5G 10G 10CSunflower -- -- -- --Mustard -- -- -- --Sugar beets 7G 10G 10C 10CCorn 7C 10C 10C 10UCrabgrass 2G 7G 9C 8CRice 5G 8C 9C 8GNutsedge 0 1G 2G 5CBarnyardgrass 6G -- 9C 9CWheat 3G 4G 5G 6CGiant foxtail 4G 7G 8G 7CWild Oats 6G 6G 8C 7GSorghum -- -- -- --Johnsongrass 8U 10U 10U 10UField Bindweed -- -- -- --______________________________________ Compound 5Rate g/ha 1 4 4 16 16 62______________________________________Soybeans 8G 10G 10C 10G 10C 10CVelvetleaf 8G 10G 9C 10G 10C 10CSesbania -- -- -- -- -- --Sicklepod 6G 10G 9G 10G 10C 10CCotton 7G 10G 10C 10G 10C 10CMorningglory 5G 9G 8G 10G 9G 10CAlfalfa -- -- -- -- -- --Jimsonweed 7G 10G 9G 10G 10C 10CCocklebur 5G 7G 9C 10G 10C 10CSunflower -- -- -- -- -- --Mustard -- -- -- -- -- --Sugar beets 10G 10G 10C 10G 10C 10CCorn 9G 10G 9C 10G 9C 10CCrabgrass 8G 10G 9G 10G 10C 10CRice 6G 10G 9C 10G 9C 10CNutsedge 0 8G 7G 10G 7G 8GBarnyardgrass 8G 10G 10C 10G 10C 10CWheat 8G 9G 7G 10G 7G 8GGiant foxtail 8G 9G 10C 10G 10C 10CWild Oats 7G 9G 7G 10G 8C 8GSorghum -- -- -- -- -- --Johnsongrass 10G 10G 10C 10G 10C 10CField Bindweed -- -- -- -- -- --______________________________________ Compound 6Rate g/ha 1 4 16 62______________________________________Soybeans 2G 8G 9G 10GVelvetleaf 4G 8G 9C 9GSesbania 6G 7G 8G 10GSicklepod 2G 6G 9G 10GCotton 0 3G 7G 10GMorningglory 2G 6G 9G 10GAlfalfa -- -- -- --Jimsonweed 0 3G 8G --Cocklebur 0 0 5G 10CSunflower -- -- -- --Mustard -- -- -- --Sugar beets 5G 10C 10G 10CCorn 6C 9G 10U 10UCrabgrass 0 3G 7G 8GRice 3G 6G 8C 8CNutsedge 0 0 4G 4GBarnyardgrass 6C 9G 9G 9GWheat 0 0 0 4GGiant foxtail 0 0 5G 6GWild Oats 0 0 0 5GSorghum -- -- -- --Johnsongrass 10U 10U 10U 10UField Bindweed -- -- -- --______________________________________ Compound 7Rate g/ha 1 4 16 62______________________________________Soybeans 0 5G 10G 10GVelvetleaf 1C 5C 8G 8GSesbania 2G 4G 7G 8GSicklepod 2G 8G 8G --Cotton 3G 7G 7G 9GMorningglory 0 4G 8G 9GAlfalfa -- -- -- --Jimsonweed 0 7G -- --Cocklebur 0 3G 6G --Sunflower -- -- -- --Mustard -- -- -- --Sugar beets 3G 7C 10G 10GCorn 4G 7U 10U 10UCrabgrass 0 2G 7G 8GRice 3G 8G 8C 8CNutsedge 0 0 4G 3GBarnyardgrass 4G 6G 9G 9GWheat 1G 6G 7C 7CGiant foxtail 3G 5G 7C 8GWild Oats 0 4G 7G 8GSorghum -- -- -- --Johnsongrass 8U 9U 10C 10CField Bindweed -- -- -- --______________________________________
TEST D
Post-emergence phase
Two round pans (25 cm diameter by 12.5 cm deep) were filled with Woodstown sandy loam soil. One pan was planted with sugar beets, nutsedge (Cyperus rotundus) tubers, crabgrass (Digitaria sanguinalis), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), and giant foxtail (Setaria faberii). The other pan was planted with wheat, cotton, rice, corn, soybean, wild oats (Avena fatua), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense) and barnyardgrass (Echinochloa crusgalli). The plants were grown for approximately fourteen days, then sprayed post-emergence with the chemicals dissolved in a non-phytotoxic solvent.
Pre-emergence phase
Two round pans (25 cm diameter by 12.5 cm deep) were filled with Woodstown sandy loam soil. One pan was planted with sugar beets, nutsedge, crabgrass, sicklepod, teaweed, jimsonweed, velvetleaf and giant foxtail. The other pan was planted with wheat, cotton, rice, corn, soybeans, wild oats, cocklebur, morningglory, johnsongrass and barnyardgrass. The two pans were sprayed pre-emergence with the chemicals dissolved in a non-phytotoxic solvent.
Treated plants and controls were maintained in the green house for 28 days,then all treated plants were compared to controls and visually rated for response utilizing the rating system as described above for Test A. The data are given in Table D.
It will be seen that the compounds tested have utility for weed control in cotton.
TABLE D______________________________________PRE-EMERGENCE Compound 14Rate g/ha 4 16 62 250______________________________________Corn 0 3G 6G 8GWheat 0 2G 8G 9GRice 3G 8G 10G 10GSoybean 0 2G 6G 8GCotton 0 3G 4G 6GSugar beet 0 3G 7G 9GCrabgrass 0 5G 8G 9GJohnsongrass 0 3G 9G 9GBarnyardgrass 0 3G 8G 9GNutsedge 0 2G 7G 9GGiant Foxtail -- -- -- --Wild Oats 0 3G 8G 8GCocklebur 0 4G 5G 7GMorningglory 0 0 0 3GTeaweed 0 2G 6G 8GSicklepod 0 4G 4G 5GJimsonweed 0 0 4G 8GVelvetleaf 0 0 0 3G______________________________________PRE-EMERGENCE Compound 15Rate g/ha 4 16 62 250______________________________________Corn 0 0 0 0Wheat 0 0 8G 10GRice 0 6G 10G 10GSoybean 0 0 2G 4GCotton 0 0 0 0Sugar beet 0 0 3G 9GCrabgrass 4G 7G 8G 9GJohnsongrass 0 3G 7G 8GBarnyardgrass 0 0 8G 8GNutsedge 0 0 8G 0Giant Foxtail 0 3G 7G 9GWild Oats 0 4G 8G 8GCocklebur 0 0 0 0Morningglory 0 0 2G 5GTeaweed 0 5G 6G 6GSicklepod 0 0 4G 9GJimsonweed 0 0 4G 6GVelvetleaf 0 0 0 0______________________________________POST-EMERGENCE Compound 14Rate g/ha 1 4 16 62______________________________________Corn 3G 9G 10C 10CWheat 0 3G 8G 8GRice 0 5G 9G 10GSoybean 3G 9G 9G 9GCotton 0 2G 3G 4GSugar beet 0 6G 10G 10GCrabgrass 0 5G 10C 10GJohnsongrass 0 5G 9C 10CBarnyardgrass 0 5G 9C 9CNutsedge 0 0 4G 6GGiant Foxtail 0 0 3G 9GWild Oats 0 4G 9G 9GCocklebur 0 2G 5G 8GMorningglory 2G 4G 5G 7GTeaweed 0 5G 9G 10GSicklepod 0 3G 7G 8GJimsonweed 0 3G 7G 10GVelvetleaf 0 3G 3G 8G______________________________________POST-EMERGENCE Compound 15Rate g/ha 1 4 16 62______________________________________Corn 0 6G 10C 10CWheat 0 0 9C 10CRice 3G 8G 10C 10CSoybean 0 7G 9G 10CCotton 0 0 0 0Sugar beet 0 4G 10G 10CCrabgrass 3G 7G 10C 10CJohnsongrass 0 3G 10C 10CBarnyardgrass 0 7G 9C 10CNutsedge 0 0 5G 6GGiant Foxtail 0 3G 8G 10CWild Oats 0 5G 9C 10CCocklebur 0 0 0 5GMorningglory 0 0 7G 8GTeaweed 0 0 3G 10CSicklepod 0 5G 10G 10CJimsonweed 0 0 0 5GVelvetleaf 0 0 7G 8G______________________________________
TEST E
This test was conducted to evaluate compounds for potential utility in fallow weed control. Plastic pots lines with polyethylene bags were filledwith Woodstown sandy loam and planted to kochia (Kochia scoparia) and Russian thistle (Salsola kali). About 10 days later, seeds of wheat (Triticum aestivum), wild oats (Avena fatua), cheatgrass (Bromus secalinus) and green foxtail (Setaria lutescens) were planted in the same pots. After an additional 10 days, wheat, barley, corn and sorghum were planted. Immediately after the last planting, the test chemical, dissolvedin a non-phytotoxic solvent, was applied to the soil surface and the foliage of the emerged plants.
Twenty one days after treatment, all species were rated utilizing the rating system as described for Test A. The response data are summarized inTable E. It will be seen that all species are killed or seriously injured at very low rates of application of compound No. 5, regardless of whether the treatments were applied pre- or post-emergence.
TABLE E______________________________________ Compound 5Rate g/ha 4 1______________________________________Post-EmergenceRussian thistle 10C 10CKochia 10C 2GCheatgrass 6G 1GGreen foxtail 9G,9C 2GWild Oats 9G 4GVolunteer Wheat 8G,2C 2GPre-EmergenceWheat 8G,8C 4GBarley 10C 6GCorn 4G 1GSorghum 10C 5G______________________________________

Number	Name	Date
4127405	Levitt	Nov 1978
4169719	Levitt	Oct 1979
4369320	Levitt et al.	Jan 1983
4465506	Welch	Aug 1984
4492596	Pasteris	Jan 1985
4514211	Rorer	Apr 1985
4634465	Ehrenfreund et al.	Jan 1987

Number	Date	Country
30141	Jun 1981	EPX
1468747	Jan 1967	FRX
121788	Sep 1966	NLX

	Number	Date
Parent	878216	Jun 1986
Parent	709340	Mar 1985
Parent	533341	Sep 1983

	Number	Date	Country
Parent	499443	May 1983
Parent	437632	Oct 1982

Phenyl-substituted sulfonamides

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