Herbicidal N-hydroxy-N'-sulfonylguanidines

BACKGROUND OF THE INVENTION
This invention relates to certain novel N-hydroxy-N'-sulfonylguanidine compounds, to compositions containing such compounds, and to a method of use of such compositions to control the growth of undesired vegetation.
U.S. Pat. No. 4,127,405 issued Nov. 28, 1978 discloses substituted triazinyl arylsulfonylurea compounds of the following formula: ##STR1## while U.S. Pat. No. 4,169,719 issued Oct. 2, 1979 discloses substituted pyrimidinyl arylsulfonylurea compounds of the following formula: ##STR2## The triazine and pyrimidine compounds within the scope of the '405 and '719 patents include those wherein W can be oxygen or sulfur.
U.S. Pat. No. 4,310,346 issued Jan. 12, 1982 discloses sulfonylisothiourea compounds of the formula ##STR3## wherein B is C.sub.1 -C.sub.6 alkyl, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3, CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 Q, ##STR4## where Q is CO.sub.2 -C.sub.1-3 alkyl, ##STR5## phenyl, phenyl substituted with chlorine, CN, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, OR.sub.11, where R.sub.11 is C.sub.1 -C.sub.4 alkyl, --CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 or --CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3.
South African Pat. No. 79/2657, published Jun. 30, 1980 discloses sulfonylisothiourea compounds of the formula ##STR6## wherein R.sub.2 is C.sub.1 -C.sub.20 alkyl; CH.sub.2 CH.sub.2 OCH.sub.3 ; CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 ; CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ; CH.sub.2 OA' where A' is C.sub.1 -C.sub.12 alkyl, --CH.sub.2 CH.sub.2 OCH.sub.3, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3, phenyl or phenyl substituted with 1-2 NO.sub.2, 1-2 Cl, or 1-2 CH.sub.3 ; CH.sub.2 A, ##STR7## where A is CO.sub.2 (H, C.sub.1 -C.sub.4 alkyl), ##STR8## phenyl, CN, C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.4 alkynyl, phenyl substituted with 1-2 CH.sub.3, 1-2 NO.sub.2, 1-2 OCH.sub.3, 1-2 chlorine or phenoxy.
U.S. Pat. No. 4,301,286 issued Nov. 17, 1981 discloses O-alkylsulfonylisoureas of the formula ##STR9## wherein W is Cl, Br or OR.sup.12 ; and
R.sup.12 is C.sub.1 -C.sub.12 alkyl, C.sub.3 -C.sub.4 alkenyl, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3, (CH.sub.2).sub.3 OCH.sub.3, benzyl, CHR.sup.13 CO.sub.2 R.sup.14, where R.sup.13 is H or CH.sub.3 and R.sup.14 is C.sub.1 -C.sub.4 alkyl.
South African patent application No. 84/4808 discloses herbicidal sulfonamides of formula ##STR10## wherein R.sub.1 is a phenyl or phenoxy group; each of
R.sub.2 and R.sub.3 is a lower alkyl or lower alkoxy group; and
R.sub.4 is a hydrogen atom, a lower alkyl group or a lower alkoxy group.
The compounds taught in the above references are useful as general or selective herbicides having both preemergent and postemergent herbicidal activity or plant growth regulant activity.
SUMMARY OF THE INVENTION
The novel sulfonylguanidine compounds of the present invention incorporating a guanidyloxyl moiety are highly active herbicides in both preemergent and postemergent applications. Certain compounds additionally exhibit selective herbicidal safety to wheat and barley. Specifically, the invention relates to novel compounds of formula I, agriculturally suitable compositions containing them and their method-of-use as pre-emergent and/or post-emergent herbicides or plant growth regulants. ##STR11## wherein R is H or CH.sub.3 ;
R' is OH, OC(O)R.sub.1, OC(O)NR.sub.2 R.sub.3, OCOR.sub.4, OR.sub.3 or R.sub.3 ;
R.sub.1 is C.sub.1 -C.sub.3 alkyl or CF.sub.3 ;
R.sub.2 is H, CH.sub.3 or C.sub.2 H.sub.5 ;
R.sub.3 is C.sub.1 -C.sub.3 alkyl;
R.sub.4 is C.sub.1 -C.sub.3 alkyl;
L is ##STR12## R.sub.5 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, OCH.sub.2 CH.sub.2 OCH.sub.3, F, Cl, Br, NO.sub.2, CF.sub.3, CO.sub.2 R.sub.19, SO.sub.2 NR.sub.20 R.sub.21, SO.sub.2 N(OCH.sub.3)CH.sub.3, OSO.sub.2 R.sub.22, S(O).sub.n R.sub.23, WCF.sub.3, WCHF.sub.2, C.sub.3 -C.sub.4 alkenyloxy, C.sub.3 -C.sub.4 alkynyloxy, C.sub.1 -C.sub.2 alkyl substituted with OCH.sub.3 or OCH.sub.2 CH.sub.3, C.sub.6 H.sub.5, ##STR13## R.sub.6 is H, F, Cl, Br, CF.sub.3, CH.sub.3, OCH.sub.3, SCH.sub.3 or OCF.sub.2 H;
R.sub.7 is H, CH.sub.3, OCH.sub.3, F, Cl, Br, SO.sub.2 N(CH.sub.3).sub.2, OSO.sub.2 CH.sub.3 or S(O).sub.n CH.sub.3 ;
R.sub.8 is CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, F, Cl, Br, SO.sub.2 NR.sub.20 R.sub.21, SO.sub.2 N(OCH.sub.3)CH.sub.3 or S(O).sub.n R.sub.23 ;
R.sub.9 is C.sub.1 -C.sub.3 alkyl, F, Cl, Br, NO.sub.2, CO.sub.2 R.sub.19, SO.sub.2 NR.sub.20 R.sub.21, SO.sub.2 N(OCH.sub.3)CH.sub.3 or S(O).sub.n R.sub.23 ;
R.sub.10 is Cl, NO.sub.2, CO.sub.2 CH.sub.3, CO.sub.2 CH.sub.2 CH.sub.3, SO.sub.2 N(CH.sub.3).sub.2, OSO.sub.2 CH.sub.3, SO.sub.2 CH.sub.3, SO.sub.2 CH.sub.2 CH.sub.3, OCH.sub.3 or OCH.sub.2 CH.sub.3 ;
R.sub.11 is H, CH.sub.3 or CH.sub.2 CH.sub.3 ;
R.sub.12 is H, CH.sub.3 or CH.sub.2 CH.sub.3 ;
R.sub.13 is H or CH.sub.3 ;
R.sub.14 is H or CH.sub.3 ;
R.sub.15 is H or CH.sub.3 ;
R.sub.16 is CH.sub.3 or CH.sub.2 CH.sub.3 ;
R.sub.17 is H or C.sub.1 -C.sub.4 alkyl;
R.sub.18 is H or CH.sub.3 ;
R.sub.19 is C.sub.1 -C.sub.4 alkyl, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 Cl or CH.sub.2 CH.dbd.CH.sub.2 ;
R.sub.20 is C.sub.1 -C.sub.3 alkyl;
R.sub.21 is C.sub.1 -C.sub.3 alkyl;
R.sub.22 is C.sub.1 -C.sub.3 alkyl or N(CH.sub.3).sub.2 ;
R.sub.23 is C.sub.1 -C.sub.3 alkyl or CH.sub.2 CH.dbd.CH.sub.2 ;
m is 0 or 1;
n is 0 or 2;
Q.sub.1 is O, S, SO.sub.2 or NR.sub.17 ;
Q.sub.2 is O, S or NR.sub.17 ; and
W is O, S or SO.sub.2 ;
A is ##STR14## 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, OCH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, CH.sub.2 OCH.sub.2 CH.sub.3, N(CH.sub.3).sub.2, CH.sub.2 CH.sub.3, 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.sub.2 SCH.sub.3, OCF.sub.2 H, SCF.sub.2 H, CR.sub.24 (QCH.sub.3).sub.2, ##STR15## or CR.sub.24 (QCH.sub.2 CH.sub.3).sub.2 ; Q is O or S;
R.sub.24 is H or CH.sub.3 ;
Z is CH or N;
Y.sub.1 is CH.sub.2 or O;
X.sub.1 is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3 or OCF.sub.2 H;
Y.sub.2 is H or CH.sub.3 ;
X.sub.2 is CH.sub.3, CH.sub.2 CH.sub.3 or CH.sub.2 CF.sub.3 ;
Y.sub.3 is OCH.sub.3, OCH.sub.2 CH.sub.3, SCH.sub.3, CH.sub.3 or CH.sub.2 CH.sub.3 ;
X.sub.3 is CH.sub.3 or OCH.sub.3 ;
provided that
(1) the total number of carbon atoms of R.sub.20 and R.sub.21 is less than or equal to four;
(2) when m is 1, then R.sub.13 is H;
(3) when L is L-17, then R.sub.17 and R.sub.18 are not simultaneously H;
(4) when X is Cl, F or Br, then Z is CH and Y is OCH.sub.3, OCH.sub.2 CH.sub.3, N(CH.sub.3).sub.2 or OCF.sub.2 H;
(5) when R' is C.sub.1 -C.sub.3 alkoxy or C.sub.1 -C.sub.3 alkyl, and L is L-1 then either R.sub.5 is other than C.sub.6 H.sub.5 or R.sub.6 is other than H; and
(6) when X or Y is OCF.sub.2 H, then Z is CH.
This invention also relates to novel compounds of Formula II, suitable agricultural compositions containing them and their method of use as general or selective preemergent or postemergent herbicides or plant growth regulants. ##STR16## wherein R" is C.sub.1 -C.sub.3 alkyl;
R, L and A are defined for Formula I;
provided that
(1) when L is L-1 and A is A-1, R.sub.5 is C.sub.2 -C.sub.4 alkyl, C.sub.2 -C.sub.4 alkoxy, OCH.sub.2 CH.sub.2 OCH.sub.3, OSO.sub.2 R.sub.22, S(O).sub.n CH.sub.2 CH.dbd.CH.sub.2, WCF.sub.2, WCHF.sub.2, C.sub.3 -C.sub.4 alkenyloxy, C.sub.3 -C.sub.4 alkynyloxy, C.sub.1 -C.sub.2 alkyl substituted with OCH.sub.3 or OCH.sub.2 CH.sub.3, C.sub.6 H.sub.5, ##STR17## (2) when L is L-1 and A is A-2 or A-3, then R.sub.5 is C.sub.2 -C.sub.4 alkyl, C.sub.2 -C.sub.4 alkoxy, OCH.sub.2 CH.sub.2 OCH.sub.3, OSO.sub.2 R.sub.22, WCF.sub.3, WCHF.sub.2, C.sub.3 -C.sub.4 alkenyloxy, C.sub.3 -C.sub.4 alkynyloxy, C.sub.1 -C.sub.2 alkyl substituted with OCH.sub.3 or OCH.sub.2 CH.sub.3, C.sub.6 H.sub.5, ##STR18## (3) when L is L-3 and A is A-1, A-2 or A-3, then R.sub.8 is SO.sub.2 NR.sub.20 R.sub.21, SO.sub.2 N(OCH.sub.3)CH.sub.3 or SO.sub.2 R.sub.23 ;
(4) when L is L-4, L-5 or L-6 and A is A-1, A-2 and A-3, then R.sub.9 is C.sub.1 -C.sub.3 alkyl, F, Cl, Br, NO.sub.2, SO.sub.2 NR.sub.20 R.sub.21, SO.sub.2 N(OCH.sub.3)CH.sub.3 or S(O).sub.n R.sub.23 ; and
(5) when L is L-2, then A is A-5 or A-6.
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 R is H, R' is OH and A is A-1.
(2) Compounds of Formula I where R is H, R' is C.sub.1 -C.sub.2 alkoxy and A is A-1.
(3) Compounds of Preferred 1 where Y is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, OCH.sub.2 CF.sub.3 or CH(OCH.sub.3).sub.2 and X is CH.sub.3, OCH.sub.3, Cl or CF.sub.3.
(4) Compounds of Preferred 2 where Y is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, OCH.sub.2 CF.sub.3 or CH(OCH.sub.3).sub.2 and X is CH.sub.3, OCH.sub.3, Cl or CF.sub.3.
(5) Compounds of Preferred 3 where L is L-1, L-2, L-3, L-5, L-8, L-10, L-11, L-16 or L-17.
(6) Compounds of Preferred 5 where L is L-1, R.sub.5 is OCH.sub.3, OCH.sub.2 CH.sub.3, Cl, NO.sub.2, CF.sub.3, CO.sub.2 CH.sub.3, CO.sub.2 CH.sub.2 CH.sub.3, SO.sub.2 N(CH.sub.3).sub.2, SO.sub.2 N(OCH.sub.3)CH.sub.3, OSO.sub.2 R.sub.22, S(O).sub.n R.sub.23, OCF.sub.2 H, SCF.sub.2 H, C.sub.6 H.sub.5, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 C.tbd.CH. ##STR19## R.sub.22 is C.sub.1 -C.sub.3 alkyl; R.sub.23 is CH.sub.3 and n is 2.
(7) Compounds of Preferred 4 where L is L-1, L-2, L-3, L-5, L-8, L-10, L-11, L-16 or L-17.
(8) Compounds of Preferred 7 where L is L-1, R.sub.5 is OCH.sub.3, OCH.sub.2 CH.sub.3, Cl, NO.sub.2, CF.sub.3, CO.sub.2 CH.sub.3, CO.sub.2 CH.sub.2 CH.sub.3, SO.sub.2 N(CH.sub.3).sub.2, SO.sub.2 N(OCH.sub.3)CH.sub.3, OSO.sub.2 R.sub.22, S(O).sub.n R.sub.23, OCF.sub.2 H, SCF.sub.2 H, C.sub.6 H.sub.5, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 C.tbd.CH, ##STR20## R.sub.22 is C.sub.1 -C.sub.3 alkyl; R.sub.23 is CH.sub.3 and n is 2.
(9) Compounds of Preferred 5 where L is L-2 and R.sub.7 is Cl, CH.sub.3, OCH.sub.3, SCH.sub.3 or Br.
(10) Compounds of Preferred 5 where L is L-3 and R.sub.8 is Cl, SO.sub.2 CH.sub.3 or SO.sub.2 N(CH.sub.3).sub.2.
(11) Compounds of Preferred 5 where L is L-5 and R.sub.9 is CO.sub.2 CH.sub.3 or CO.sub.2 CH.sub.2 CH.sub.3.
(12) Compounds of Preferred 5 where L is L-8.
(13) Compounds of Preferred 5 where L is L-10.
(14) Compounds of Preferred 5 where L is L-11.
(15) Compounds of Preferred 5 where L is L-16.
(16) Compounds of Preferred 5 where L is L-17.
(17) Compounds of Preferred 7 where L is L-2 and R.sub.7 is Cl, CH.sub.3, OCH.sub.3, SCH.sub.3 or Br.
(18) Compounds of Preferred 7 where L is L-3 and R.sub.8 is Cl, SO.sub.2 CH.sub.3 or SO.sub.2 N(CH.sub.3).sub.2.
(19) Compounds of Preferred 7 where L is L-5 and R.sub.9 is CO.sub.2 CH.sub.3 or CO.sub.2 CH.sub.2 CH.sub.3.
(20) Compounds of Preferred 7 where L is L-8.
(21) Compounds of Preferred 7 where L is L-10.
(22) Compounds of Preferred 7 where L is L-11.
(23) Compounds of Preferred 7 where L is L-16.
(24) Compounds of Preferred 7 where L is L-17.
(25) Compounds of Formula II where R is H and A is A-1.
(26) Compounds of Preferred 25 where Y is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, OCH.sub.2 CF.sub.3 or CH(OCH.sub.3).sub.2 and X is CH.sub.3, OCH.sub.3, Cl or CF.sub.3 ;
(27) Compounds of Preferred 26 where L is L-1 and R.sub.5 is OSO.sub.2 R.sub.22, SO.sub.2 CH.sub.2 CH.dbd.CH.sub.2, OCF.sub.2 H, SCF.sub.2 H, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 C.tbd.H, ##STR21## or C.sub.6 H.sub.5.
Specifically Preferred for reasons of their highest herbicidal activity or greatest plant growth regulant activity or most favorable ease of synthesis are:
2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]aminosulfonyl]benzoic acid methyl ester;
2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]aminosulfonyl]benzoic acid methyl ester;
N',N'-dimethyl-N-[[1-(4,6-dimethyl-1,3,5-triazin-2-yl)amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfonamide;
N',N'-dimethyl-N-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfonamide;
3-chloro-N-[[1-(4,6-dimethoxypyrimidin-2-yl)amino]-1-[methoxyimino]methyl][1,1'-biphenyl]-2-sulfonamide;
N-[[1-(4,6-dimethoxy-1,3,5-triazin-2-yl)amino]-1-[methoxyimino]methyl]-3-methoxy[1,1'-biphenyl]-2-sulfonamide; and
N-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]-2-chlorobenzenesulfonamide, m.p. 165-167.
DETAILED DESCRIPTION OF THE INVENTION
Synthesis
The compounds of Formula Ia may be prepared by the reaction of hydroxylamine with an appropriately substituted S-alkyl benzenesulfonyl isothiourea of Formula II, as shown in Equation 1.
Equation 1 ##STR22## wherein L, R, R" and A are as previously defined.
The reaction of Equation 1 is conducted by contacting 1-3 equivalents of hydroxylamine hydrochloride and an equivalent amount of sodium acetate with a compound of Formula II in a suitable solvent, such as tetrahydrofuran, at 0.degree.-30.degree. for 1-24 hours. The product may be isolated by removal of solvent and trituration of the residue with water.
The compounds of Formula II may be prepared by the methods described in U.S. Pat. No. 4,301,286 and are herein incorporated by reference. Alternatively, they may be prepared by the procedure outlined in Equation 2.
Equation 2 ##STR23## wherein L, R, R" and A are as previously defined.
The reaction of Equation 2 may be carried out by contacting a sulfonyl chloride of Formula III with an appropriately substituted S-alkyl isothiourea of Formula IV in an inert solvent, such as methylene chloride or tetrahydrofuran, in the presence of an acid scavenger, such as aqueous sodium bicarbonate or a tertiary amine, such as triethylamine, for 1-3 days at 20.degree.-40.degree.. The product is isolated by removal of solvent and trituration of the residue with water, or by extraction from water with an organic solvent, concentration, and chromatography.
Reference to the following patents and patent applications is suggested for details regarding the preparation of the sulfonyl chlorides III: U.S. Pat. No. 4,169,719, U.S. Pat. No. 4,127,405; U.S. Pat. No. 4,383,113; U.S. Pat. No. 4,394,506; U.S. Pat. No. 4,120,691; U.S. Pat. No. 4,238,621; European patent application No. 80304286.0, published Jun. 10, 1981; European patent application No. 79302769.9, published Jul. 23, 1980; Canadian Pat. No. 1128042; European patent application No. 82301500.3, published Nov. 17, 1982; European patent application No. 81305160.4, published May 12, 1982; and copending U.S. patent application Ser. No. 410,993, filed Aug. 27, 1982; U.S. patent application Ser. No. 406,191, filed Aug. 11, 1982, U.S. patent application Ser. No. 499,443, filed May 31, 1983 and U.S. patent application Ser. No. 436,631, filed Oct. 10, 1982.
The preparation of the compounds of Formula IV is shown in Equations 3, 4 and 5.
Equation 3 ##STR24## wherein R, R" and A are as previously defined.
The reaction of Equation 3a may be carried out by saturation of a solution of a compound of Formula V in pyridine with hydrogen sulfide, allowing to react for 1 to 5 days at 25.degree. to 40.degree., removal of pyridine in vacuo, and crystallization of the product with water or an organic solvent such as ether or methylene chloride. The resulting compound of Formula VI may be reacted according to Equation 3b with one equivalent of a dialkyl sulfate or alkyl iodide at 20.degree. to 80.degree. for 1 to 3 days to provide the corresponding alkyl sulfate or iodide salt of IV. The free base may be obtained by extraction from aqueous sodium bicarbonate with an organic solvent, such as ethyl acetate. An alternative synthesis of compounds of Formula VI is shown in Equation 4.
Equation 4 ##STR25## wherein R and A are as previously defined; and J is C.sub.6 H.sub.5 or C.sub.6 H.sub.5 O.
The reaction of Equation 4a is carried out by contacting a compound of Formula VII with 1-1.5 equivalents of benzoyl- or phenoxycarbonylisothiocyanate at 30.degree.-80.degree. for 1-24 hours in a suitable solvent, such as acetonitrile or tetrahydrofuran. The product may be isolated by cooling or concentration and filtration. The reaction of Equation 4b may be performed by heating the compound of Formula VIII in an aqueous medium, with or without a cosolvent, in the presence of 1 to 2 equivalents of an alkali metal hydroxide or an alkali earth oxide at 30.degree. to 80.degree. for 1-24 hours. The product is isolated by cooling, neutralization to pH 8, and filtration in the case where an alkali metal hydroxide is used, and in the case where an alkali earth oxide is used, the reaction mixture is filtered and the filtrate is concentrated, cooled, and filtered.
Heterocyclic amines of Formula VII and methods for preparing them are known in the art. The synthesis of heterocyclic amines such as those of Formula VII has been reviewed in "The Chemistry of Heterocyclic Compounds", a series published by Interscience Publ., N.Y. and London. 2-Aminopyrimidines are described by D. J. Brown in "The Pyrimidines", Vol. XVI of this series. 2-Amino-1,3,5-triazines can be prepared according to methods described by E. M. Smolin and L. Rapaport in "s-Triazines and Derivatives", Vol. XIII of the same series. The synthesis of triazines is also described by F. C. Schaefer, U.S. Pat. No. 3,154,547 and by K. R. Huffman and F. C. Schaefer; J. Org. Chem., 28, 1816 (1963). See also U.S. patent application Ser. No. 434,038, filed Oct. 20, 1982, European patent application No. 80300505.7, published Sept. 17, 1980 (Pub. No. 15,683), European patent application No. 81303837.9, published Mar. 3, 1982 (Pub. No. 46,677); European patent application No. 82306492.8, published Jul. 27, 1983 (Pub. No. 84,224); and European patent application No. 82303611.6, published Mar. 9, 1983 (Pub. No. 73,562), for description of methods for preparing heterocyclic amine derivatives.
A third method by which certain compounds of Formula IV may be obtained is shown in Equation 5.
Equation 5 ##STR26## wherein R, R", X and Y are as previously defined.
The reaction of Equation 5 may be carried out by contacting a chlorotriazine of Formula IX with an S-alkyl isothiourea of Formula X in the same manner as was described in the reaction of Equation 2.
Compounds of Formulae Ib and Ic may be obtained from those of Formula Ia by the reactions of Equation 6.
Equation 6 ##STR27## wherein R.sup.a is C(O)R.sub.1, C(O)NR.sub.2 R.sub.3, or CO.sub.2 R.sub.4, and L, R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, and A are as previously defined.
The reaction of Equation 6a is carried out by contacting Ia with 1-10 equivalents of the appropriate carboxylic acid chloride or anhydride, or alkyl chloroformate, or dialkyl carbamoyl chloride in the presence of an acid scavenger, such as pyridine or a tertiary amine, at 0.degree. to 40.degree. for 2 to 24 hours, adding ice-water, and filtering or extracting the product into an organic solvent.
The reaction of Equation 6b may be conducted by treating a solution of Ia in an inert solvent such as methylene chloride or acetonitrile with 1-1.5 equivalents of an alkyl isocyanate at 20.degree.-80.degree. for 1 to 24 hours. The product is isolated by concentrating the reaction mixture and trituration with a solvent such as ether or chlorobutane.
Additional methods for preparation of compounds of this invention are described in South African patent application 84/4808.
Agriculturally suitable salts of compounds of Formulae I and II are also useful herbicides. Salts of compounds of Formulae I and II can be prepared in a number of ways known to the art. For example, metal salts can be made by treating compounds of Formulae I and II with a 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 Formulae I and II can also be prepared by exchange of one cation for another. Cationic exchange can be effected by direct treatment of an aqueous solution of a salt of a compound of Formulae I and II (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 a compound of Formulae I and II (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to 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 Formulae I and II with a suitable acid, e.g., p-toluenesulfonic acid, trichloroacetic acid or the like. The disclosures of all references cited above are herein incorporated by reference.
In the following examples, all parts are by weight and temperatures in .degree.C. unless otherwise indicated.

EXAMPLE 1
2-Chloro-N-[[(4,6-dimethylpyrimidin-2-yl)amino]hydroxyiminomethyl]benzenesulfonamide
To a solution of 0.5 g of methyl N'-(2-chlorophenylsulfonyl)-N-(4,6-dimethylpyrimdin-2-yl)carbamimidothioate in 10 ml of tetrahydrofuran was added 0.3 g of hydroxylamine hydrochloride and 0.3 g of sodium acetate. The mixture was stirred at room temperature for 2 hours, whereupon the product was precipitated with ice-water, filtered, washed with water, and dried by suction to afford 0.3 g of the title compound, m.p. 165.degree.-167.degree.. NMR(CDCl.sub.3 /DMSO-d.sub.6) .delta.2.6 (s, 6), 6.8 (s, 1), 7.4 (m, 3), 8.2 (m, 1), 10.2 (br, 1), 12.0 (br, 1). m/e: 355 (M.sup.+).
EXAMPLE 2
N-(4,6-Dimethylpyrimidin-2-yl)thiourea
A suspension of 10 g of 2-cyanoamino-4,6-dimethylpyrimidine in 50 ml of pyridine was saturated with hydrogen sulfide and stored for 1 hour at 25.degree.. The H.sub.2 S treatment was repeated twice more, and the mixture was allowed to stir at 25.degree. for 16 hours. Methylene chloride was added, and the product was filtered and washed with methylene chloride to afford 8 g of 4,6-dimethylpyrimidin-2-yl thiourea, m.p. >260.degree.. IR (Nujol) 3280, 3180, 3120, 1610 cm.sup.-1.
EXAMPLE 3
N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminothioxomethyl]benzamide
To a hot solution of 14 g of ammonium thiocyanate in 300 ml of acetonitrile was added 24 ml of benzoyl chloride. The mixture was heated on the steam bath for 30 minutes and filtered. The filtrate was heated with 21 g of 4-methoxy-6-methylpyrimidine-2-amine for 30 minutes and cooled. The product was collected by filtration and washed with a little acetonitrile to provide 28 g of N-[[(4-methoxy-6-methylpyrimidin-2-yl)aminothiocarbonyl]amino]benzamide, m.p. 193.degree.-195.degree.. IR (Nujol) 3290, 1720 cm.sup.-1.
EXAMPLE 4
N-(4-Methoxy-6-methylpyrimidin-2-yl)thiourea
A mixture of 25 g of the compound from Example 3 and 55 ml of 10% aqueous sodium hydroxide was heated on the steam bath for 30 minutes, cooled, neutralized with aqueous HCl to pH 8, filtered, washed with water, dried by suction, and washed with ether to afford 16 g of the title compound, m.p. 220.degree. d.
Anal. Calc'd.: C: 42.4, H: 5.06, N: 28.2, S: 16.2 Found: C: 42.6, H: 4.8, N: 28.8, S: 15.3 m/e 198 (M.sup.+).
EXAMPLE 5
Methyl 2-[[1-(4-methoxy-6-methylpyrimidin-2-ylimino)-1-(methylthio)methyl]aminosulfonyl]benzoate
To 9 g of the compound from Example 4 and 100 ml of tetrahydrofuran was added 7.6 g of dimethyl sulfate and the mixture was stirred for 2 days at room temperature. The product was filtered and washed with a little tetrahydrofuran to give 22 g of crude product. Five grams of this material was suspended in 150 ml of methylene chloride and 1 ml of water, and 5 g of sodium bicarbonate and 6 g of methyl 2-chlorosulfonyl benzoate were added. The mixture was stirred for 24 hours, washed with dilute aqueous HCl, dried with sodium sulfate, filtered, and chromatographed on silica gel to afford 2.8 g of the title compound as a crystalline solid, m.p. 143.degree.-144.degree..
Anal. Calc'd.: C: 45.22, H: 4.55, N: 14.06, S: 16.1 Found: C: 46.8, H: 4.35, N: 13.2, S: 16 m/e 395 (M.sup.+ --CH.sub.3),
NMR(CDCl.sub.3) .delta.2.35 (s, 3), 2.45 (s, 3), 3.90 (s, 3), 4.0 (s, 3) 6.35 (s, 1), 7.7 (m, 3), 8.2 (m, 1), 10.8 (brs. 1).
EXAMPLE 6
Methyl N-(4,6-dimethoxy-1,3,5-triazin-2-yl)carbaminidothioate
A mixture of 20 g of 2-chloro-4,6-dimethoxy-s-triazine, 20 g of S-methyl isothiouronium sulfate, 16 g of sodium carbonate, and 50 ml of water was stirred for 72 hours, concentrated at reduced pressure, and extracted with 300 ml of methylene chloride. The organic layer was dried with Na.sub.2 SO.sub.4, filtered, concentrated to dryness, and recrystallized from chlorobutane to afford 10 g of title compound, m.p. 94.degree.-100.degree.. NMR(CDCl.sub.3) .delta.2.6 (s, 3), 4.0 (s, 6), 8.2 (brs, 1).
Using the procedures and examples shown above, the compounds in Tables 1-13 can be prepared.
TABLE 1a__________________________________________________________________________ ##STR28##R.sub.5 R.sub.6 R" R X Y m.p. (.degree.C.)__________________________________________________________________________SCH.sub.2 CHCH.sub.2 3-Cl CH.sub.3 H OCH.sub.3 OCH.sub.3SCH.sub.2 CHCH.sub.2 H C.sub.2 H.sub.5 H OCH.sub.3 OC.sub.2 H.sub.5OSO.sub.2 .sub.--n-C.sub.3 H.sub.7 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3OSO.sub.2 .sub.--n-C.sub.3 H.sub.7 H CH.sub.3 H CH.sub.3 SCH.sub.3OSO.sub.2 CH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3OSO.sub.2 CH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3CH.sub.2 CH.sub.3 5-Br CH.sub.3 H CH.sub.3 OCH.sub.3CH.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 .sub.--n-C.sub.4 H.sub.9 H .sub.--n-C.sub.3 H.sub.7 H OCH.sub.3 OCH.sub.3 .sub.-i-C.sub.3 H.sub.7 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)OCH.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H CH.sub.3 H OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H CH.sub.3 H OCH.sub.3 C.sub.2 H.sub.5O .sub.--n-C.sub.4 H.sub.9 H CH.sub.3 H CH.sub.3 CH(OCH.sub.3).sub.2O .sub.--n-C.sub.4 H.sub.9 H CH.sub.3 H CH.sub.3 OC.sub.2 H.sub.5SO.sub.2 CF.sub.2 H 5-CH.sub.3 CH.sub. 3 H OCH.sub.3 OCH.sub.3SO.sub.2 CF.sub.2 H H C.sub.2 H.sub.5 H OCH.sub.3 OC.sub.2 H.sub.5SCF.sub.2 H 6-SCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3SCF.sub.2 H H CH.sub.3 H CH.sub.3 SCH.sub.3OCF.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3OCF.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3CH.sub.2 OCH.sub.3 H .sub.--n-C.sub.3 H.sub.7 H OCH.sub.3 OCH.sub.3CH.sub.2 OCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H CH.sub.3 H Cl OCH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H CH.sub.3 H Cl CH.sub.3OCF.sub.2 H H CH.sub.3 H OCH.sub.3 CH.sub.3OCF.sub.2 H H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)__________________________________________________________________________
TABLE 1b__________________________________________________________________________ ##STR29##R.sub.5 R.sub.6 R" R X Y m.p. (.degree.C.)__________________________________________________________________________SO.sub.2 CH.sub.2 CHCH.sub.2 H CH.sub.3 H OCH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 H CH.sub.3 H OCH.sub.3 C.sub.2 H.sub.5OSO.sub.2 .sub.--n-C.sub.3 H.sub.7 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3OSO.sub.2 .sub.--n-C.sub.3 H.sub.7 H CH.sub.3 H CH.sub.3 SCH.sub.3OSO.sub.2 CH.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3OSO.sub.2 CH.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3CH.sub.2 CH.sub.3 3-Br CH.sub.3 H CH.sub.3 OCH.sub.3CH.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 .sub.--n-C.sub.4 H.sub.9 H .sub.--n-C.sub.3 H.sub.7 H OCH.sub.3 OCH.sub.3 .sub.-i-C.sub.3 H.sub.7 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 H CH.sub.3 H CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)OCH.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H CH.sub.3 H OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H CH.sub.3 H OCH.sub.3 C.sub.2 H.sub.5O .sub.--n-C.sub.4 H.sub.9 H CH.sub.3 H CH.sub.3 CH(OCH.sub.3).sub.2O .sub.--n-C.sub.4 H.sub.9 H CH.sub.3 H CH.sub.3 OC.sub.2 H.sub. 5SO.sub.2 CF.sub.2 H 6-SCH.sub.3 CH.sub.3 H OCH.sub.3 OCH.sub.3SO.sub.2 CF.sub.2 H H C.sub.2 H.sub.5 H OCH.sub.3 OC.sub.2 H.sub.5SCF.sub.2 H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3SCF.sub.2 H H CH.sub.3 H CH.sub.3 SCH.sub.3OCF.sub.3 H CH.sub.3 H OCH.sub.3 CH.sub.3OCF.sub.3 H CH.sub.3 H OCH.sub.3 OCH.sub.3CH.sub.2 OCH.sub.3 H .sub.--n-C.sub.3 H.sub.7 H OCH.sub.3 OCH.sub.3CH.sub.2 OCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 CH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H CH.sub.3 H Cl OCH.sub.3CH.sub.2 OCH.sub.2 CH.sub.3 H CH.sub.3 H Cl CH.sub.3OCF.sub.2 H H CH.sub.3 H OCH.sub.3 CH.sub.3OCF.sub.2 H H CH.sub.3 H OCH.sub.3 OCH.sub.3OCF.sub.2 H H CH.sub.3 H CH.sub.3 CH.sub.3CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 H CH.sub.3 H OCH.sub.3 CH.sub.3__________________________________________________________________________
TABLE 1c__________________________________________________________________________ ##STR30## m.p.R" R R.sub.5 R.sub.6 X Y Z (.degree.C.)__________________________________________________________________________CH.sub.3 H OCH.sub.2 CH.sub.2 OCH.sub.3 H CH.sub.3 H CHCH.sub.3 H OCH.sub.2 CHCH.sub.2 H CH.sub.3 CH.sub.3 NCH.sub.3 H OCH.sub.2 CHCH 6-OCH.sub.3 CH.sub.3 CH.sub.3 CHCH.sub.3 H C.sub.6 H.sub.5 H CH.sub.3 CH.sub.3 NCH.sub.3 H ##STR31## H CH.sub.3 OCH.sub.3 CHCH.sub.3 H ##STR32## H OCH.sub.3 OCH.sub.3 NCH.sub.3 H ##STR33## H OCH.sub.3 OCH.sub.2 CCH NCH.sub.3 H ##STR34## H OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 NCH.sub.3 H C.sub.2 H.sub.5 H OCH.sub.3 OCF.sub.2 H CHCH.sub.3 H OCF.sub.3 H OCH.sub.3 SCF.sub.2 H CHCH.sub.3 H SO.sub.2 CH.sub.3 3-OCF.sub.2 H OCH.sub.3 C(CH.sub.3)(OCH.sub.3).sub.2 CHCH.sub.3 H OCH.sub.2 CH.sub.3 H OCH.sub.3 CF.sub.3 NCH.sub.3 H SO.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 N(CH.sub.3).sub.2 CHCH.sub.3 CH.sub.3 SO.sub.2 CH.sub. 2 CH.sub.3 H OCH.sub.3 C(CH.sub.3)(SCH.sub.3).sub.2 NCH.sub.3 H SO.sub.2 CH.sub.2 CH.sub.3 H OCF.sub.2 H CH(SCH.sub.2 CH.sub.2 S) CHCH.sub.3 H SO.sub.2 CH.sub.2 CH.sub.3 H CF.sub.3 CH.sub.2 CH.sub.3 CHCH.sub.3 H SO.sub.2 CH.sub.2 CH.sub.3 H F OCH.sub.3 CHCH.sub.3 H SO.sub.2 CH.sub.2 CH.sub.3 H OC.sub.2 H.sub.5 C(CH.sub.3)(OCH.sub.2 CH.sub.2 O) CH__________________________________________________________________________
TABLE 1d__________________________________________________________________________ ##STR35## m.p.R" R L X Y Z (.degree.C.)__________________________________________________________________________CH.sub.3 H L.sub.2 :R.sub.7 = Cl CH.sub.3 H CHCH.sub.3 H L.sub.2 :R.sub.7 = OCH.sub.3 CH.sub.3 CH.sub.3 CHCH.sub.3 H L.sub.2 :R.sub.7 = SO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 CHCH.sub.3 H L.sub.3 :R.sub.8 = SO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 CHCH.sub.3 H L.sub.3 :R.sub.8 = SO.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHCH.sub.3 CH.sub.3 L.sub.3 :R.sub.8 = SO.sub.2 CH.sub.2 CH.sub.3 Cl OCH.sub.3 CH .sub.-i-C.sub.3 H.sub.7 H L.sub.4 :R.sub.9 = Br OCH.sub.3 OCH.sub.3 CHCH.sub.3 H L.sub.5 :R.sub.9 = C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.2 CHCH.sub.2 CHCH.sub.3 H L.sub.6 :R.sub.9 = Cl OCH.sub.3 OCH.sub.2 CCH NCH.sub.3 H L.sub.7 :R.sub.10 = CO.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.2 CF.sub.3 NCH.sub.3 H L.sub.8 :Q.sub.1 = O, m = 0, R.sub.11 = R.sub.12 = R.sub.13 = CH.sub.3 OCH.sub.3 CH.sub.2 SCH.sub.3 CHCH.sub.3 H L.sub.9 :Q.sub.2 = S, R.sub.14 = R.sub.15 = H OCH.sub.3 OCF.sub.2 H CHCH.sub.3 H L.sub.10 :m = 0, R.sub.13 = H, R.sub.16 = CH.sub.3 OCH.sub.3 SCF.sub.2 H CHCH.sub.3 H L.sub.11 :m = 0, R.sub.13 = H OCH.sub.3 C(CH.sub.3)(OCH.sub.3).sub.2 CHCH.sub.3 H L.sub.12 :m = 1, R.sub.13 = CH.sub.3 OCH.sub.3 CF.sub.3 CHCH.sub.3 H L.sub.13 :m = 0, R.sub.13 = H OCH.sub.3 N(CH.sub.3).sub.2 CHCH.sub.3 CH.sub.3 L.sub.14 :R.sub.16 = CH.sub.2 CH.sub.3 OCH.sub.3 C(CH.sub.3)(SCH.sub.3).sub.2 CHCH.sub.3 H L.sub.15 :R.sub.17 = CH.sub.3 OCF.sub.2 H CH(SCH.sub.2 CH.sub.2 S) CHCH.sub.3 H L.sub.16 :R.sub.17 = H CF.sub.3 CH.sub.2 CH.sub.3 CHCH.sub.3 H L.sub.17 :R.sub.17 = R.sub.18 = CH.sub.3 F OCH.sub.3 CHCH.sub.3 H L.sub.17 :R.sub.17 = R.sub.18 = CH.sub.3 OC.sub.2 H.sub.5 C(CH.sub.3)(OCH.sub.2 CH.sub.2 O) CH__________________________________________________________________________
TABLE 1e__________________________________________________________________________ ##STR36## m.p.L R" R A (.degree.C.)__________________________________________________________________________L.sub.1 :R.sub.5 = CO.sub.2 CH.sub.3, R.sub.6 = H CH.sub.3 H A.sub.4 :X.sub.1 = CH.sub.3, Y.sub.2 = HL.sub.1 :R.sub.5 = SO.sub.2 CH.sub.3, R.sub.6 = H CH.sub.3 H A.sub.5 :X.sub.2 = CH.sub.2 CH.sub.3, Y.sub.3 = SCH.sub.3L.sub.1 :R.sub.5 = NO.sub.2, R.sub.6 = H CH.sub.3 H A.sub.6 :X.sub.3 = OCH.sub.3L.sub.1 :R.sub.5 = Br, R.sub.6 = H CH.sub.3 H A.sub.3 :X.sub.1 = OCH.sub.3L.sub.1 :R.sub.5 = Cl, R.sub.6 = H CH.sub.3 H A.sub.5 :X.sub. 2 = CH.sub.3, Y.sub.3 = OC.sub.2 H.sub.5L.sub.1 :R.sub.5 = C.sub.2 H.sub.5, R.sub.6 = H CH.sub.3 H A.sub.2 :X.sub.1 = OCH.sub.3, Y.sub.1 = OL.sub.1 :R.sub.5 = SCF.sub.3, R.sub.6 = H C.sub.2 H.sub.5 H A.sub.3 :X.sub.1 = OCF.sub.2 HL.sub.17 :R.sub.17 = H, R.sub.18 = CH.sub.3 CH.sub.3 H A.sub.2 :X.sub.1 = OCH.sub.3, Y.sub.1 = CH.sub.2L.sub.16 :R.sub.17 = CH.sub.3 CH.sub.3 H A.sub.3 :X.sub.1 = OCF.sub.2 HL.sub.2 :R.sub.7 = SCH.sub.3 CH.sub.3 H A.sub.4 :X.sub.1 = CH.sub.3, Y.sub.2 = CH.sub.3L.sub.3 :R.sub.8 = F CH.sub.3 H A.sub.5 :X.sub.2 = CH.sub.2 CH.sub.3, Y.sub.3 = OCH.sub.3L.sub.4 :R.sub.9 = .sub.-i-C.sub.3 H.sub.7 CH.sub.3 H A.sub.5 :X.sub.2 = CH.sub.3, Y.sub.3 = CH.sub.2 CH.sub.3L.sub.5 :R.sub.9 = SO.sub.2 CH.sub.3 CH.sub.3 H A.sub.6 :X.sub.3 = OCH.sub.3L.sub.6 :R.sub.9 = SO.sub.2 CH.sub.3 CH.sub.3 H A.sub.2 :X.sub.1 = OCH.sub.3, Y.sub.1 = OL.sub.7 :R.sub.10 = OCH.sub.2 CH.sub.3 CH.sub.3 H A.sub.3 :X.sub.1 = CH.sub.3L.sub.8 :Q.sub.1 = S, R.sub.11 = R.sub.12 = CH.sub.3, m = 1, R.sub.13 = CH.sub.3 H A.sub.6 :X.sub.3 = CH.sub.3L.sub.9 :Q.sub.2 = O, R.sub.14 = R.sub.15 = CH.sub.3 CH.sub.3 H A.sub.4 :X.sub.1 = OCH.sub.3, Y.sub.2 = CH.sub.3L.sub.10 :R.sub. 16 = C.sub.2 H.sub.5, R.sub.13 = CH.sub.3, m CH.sub.3 H A.sub.5 :X.sub.2 = CH.sub.3, Y.sub.3 = SCH.sub.3L.sub.11 :m = 1, R.sub.13 = H CH.sub.3 H A.sub.2 :X.sub.1 = CH.sub.3, Y.sub.1 = CH.sub.2L.sub.12 :m = 0, R.sub.13 = CH.sub.3 CH.sub.3 H A.sub.2 :X.sub.1 = OCH.sub.3, Y.sub.1 = CH.sub.2L.sub.13 :m = 1, R.sub.13 = H CH.sub.3 H A.sub.5 :X.sub.2 = CH.sub.2 CF.sub.3, Y.sub.3 = CH.sub.2 CH.sub.3L.sub.14 :R.sub.16 = CH.sub.3 CH.sub.3 H A.sub.4 :X.sub.1 = OCH.sub.3, Y.sub.2 = HL.sub.15 :R.sub.17 = CH.sub.3 CH.sub.3 H A.sub.4 :X.sub.1 = OCH.sub.3, Y.sub.2 =__________________________________________________________________________ H
TABLE 2A__________________________________________________________________________ ##STR37##R.sub.5 R.sub.6 R R' X Y m.p. (.degree.C.)__________________________________________________________________________Cl H H OH CH.sub.3 CH.sub.3 165-167.degree.Cl H H OH CH.sub.3 OCH.sub.3 121-128.degree.Cl H H OH OCH.sub.3 OC.sub.2 H.sub.5Cl H H OH OCH.sub.3 OCH.sub.3 142-144.degree.F H H OH CH.sub.3 CH.sub.3F H H OH CH.sub.3 OCH.sub.3Br H H OH OCH.sub.3 CH.sub.3Br H H OH OCH.sub.3 OCH.sub.3NO.sub.2 H H OH CH.sub.3 CH(OCH.sub.2 CH.sub. 2 O)NO.sub.2 H CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CF.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5CF.sub.3 H H OH OCH.sub.3 CH.sub.3OCH.sub.3 H H OH CH.sub.3 OCH.sub.3OCH.sub.3 H H OH CH.sub.3 CH(OCH.sub.3).sub.2OCH.sub.3 H H OH Cl CH.sub.3OCH.sub.3 H H OH Cl OCH.sub.3OC.sub.2 H.sub.5 H H OH CH.sub.3 CH.sub.2 OCH.sub.3OC.sub.2 H.sub.5 H H OH CH.sub.3 CH.sub.3OC.sub.2 H.sub.5 H CH.sub.3 OH OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 CH.sub.3O -n-C.sub.3 H.sub.7 H H OH CH.sub.3 OCH.sub.3O -n-C.sub.3 H.sub.7 H H OH CH.sub.3 CH.sub.3O .sub.-i-C.sub.4 H.sub.9 H H OH OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.4 H.sub.9 H H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H H OH CH.sub.3 CH.sub.3 M.sup.+ = 379*CO.sub.2 CH.sub.3 H H OH CH.sub.3 OCH.sub.3 M.sup.+ = 395*CO.sub.2 CH.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 N(CH.sub.3).sub.2 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 OCH.sub.3 166-168.degree.SO.sub.2 N(CH.sub.3).sub.2 H H OH OCH.sub.3 OCH.sub.2 CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2 H CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2 H H OH OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2 H H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 H H OH CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 H H OH CH.sub.3 CH(OCH.sub.3).sub.2CO.sub.2 CH.sub.3 H H OH Cl CH.sub.3CO.sub.2 CH.sub.3 H H OH Cl OCH.sub.3CO.sub.2 CH.sub.3 H H OH CH.sub.3 CH.sub.2 OCH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 H H OH CH.sub.3 CH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 H CH.sub.3 OH OCH.sub.3 OCH.sub.3SO.sub.2 N(OCH.sub.3)CH.sub.3 H H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H H OH CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 Cl H H OH OCH.sub.3 OCH.sub.3CO.sub.2 -n-C.sub.4 H.sub.9 H H OH OCH.sub.3 CH.sub.3SO.sub.2 CH.sub.3 H H OH CH.sub.3 CH.sub.3SO.sub.2 CH.sub.3 H H OH CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 CH.sub.3 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 H H OH CH.sub.3 CH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 H H OH CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H H OH OCH.sub.3 CH.sub.3SCH.sub.2 CH.sub.3 H H OH OCH.sub.3 OCH.sub.3SCF.sub.3 H H OH CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 CHF.sub.2 H CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CH.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5 .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 CH.sub.3 -n-C.sub.4 H.sub.9 H H OH CH.sub.3 OCH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 CH(OCH.sub.3).sub.2OSO.sub.2 N(CH.sub.3).sub.2 H H OH Cl CH.sub.3OSO.sub.2 CH(CH.sub.3).sub.2 H H OH Cl OCH.sub.3OSO.sub.2 C.sub.2 H.sub.5 H H OH CH.sub.3 CH.sub.2 OCH.sub.3OSO.sub.2 CH.sub.3 H CH.sub.3 OH OCH.sub.3 OCH.sub.3OSO.sub.2 CH.sub.3 H H OH OCH.sub.3 CH.sub.3CH.sub.2 OCH.sub.3 H H OH CH.sub.3 OCH.sub.3CH.sub.2 CH.sub.2 OCH.sub.3 H H OH CH.sub.3 CH.sub.3OCF.sub.3 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 CH.sub.3Cl H H CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 131-136.degree. dCl 5-CF.sub.3 H OH CH.sub.3 OCH.sub.3Cl H H CH.sub.3 OCO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5Cl 6-SCH.sub.3 H OH OCH.sub.3 OCH.sub.3F 5-SCH.sub.3 H CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3F 6-OCH.sub.3 H OH CH.sub.3 OCH.sub.3Br H H (CH.sub.3).sub.2 NCO.sub.2 OCH.sub.3 CH.sub.3Br 3-OCH.sub.3 H OH OCH.sub.3 OCH.sub.3NO.sub.2 H H CH.sub.3 NHCO.sub.2 CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)NO.sub.2 6-CH.sub.3 CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CF.sub.3 5-CH.sub.3 H CF.sub.3 CO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5CF.sub.3 6-Cl H C.sub.2 H.sub.5 CO.sub.2 OCH.sub.3 CH.sub.3OCH.sub.3 H H C.sub.2 H.sub.5 OCO.sub.2 CH.sub.3 OCH.sub.3OCH.sub.3 5-Cl H OH CH.sub.3 CH(OCH.sub.3).sub.2OCH.sub.3 3-Cl H OH Cl CH.sub.3OCH.sub.3 H H CH.sub.3 CO.sub.2 Cl OCH.sub.3OC.sub.2 H.sub.5 5-F H OH CH.sub.3 CH.sub.2 OCH.sub.3OC.sub.2 H.sub.5 5-F H Et.sub.2 NCO.sub.2 CH.sub.3 CH.sub.3OC.sub.2 H.sub.5 3-Br CH.sub.3 OH OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H EtOCO.sub.2 OCH.sub.3 CH.sub.3O -n-C.sub.3 H.sub.7 H H O -n-C.sub.3 H.sub.7 CH.sub.3 OCH.sub.3O -n-C.sub.3 H.sub.7 6-CH.sub.3 H OH CH.sub.3 CH.sub.3O .sub.-i-C.sub.4 H.sub.9 3-CF.sub.3 H CH.sub.3 OCO.sub.2 OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.4 H.sub.9 6-CF.sub.3 H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 6-CF.sub.3 H OH CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.3 H H OH CH.sub.3 OCO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 N(CH.sub.3).sub. 3 6-SCH.sub.3 H OH OCH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.3 5-SCH.sub.3 H CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3SO.sub.2 N(CH.sub.3).sub.3 6-OCH.sub.3 H OH CH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.3 H H (CH.sub.3).sub.2 NCO.sub.2 OCH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.3 3-OCH.sub.3 H OH OCH.sub.3 OCH2 CH.sub.3SO.sub.2 N(CH.sub.3).sub.3 H H CH.sub.3 NHCO.sub.2 CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 N(CH.sub.2 CH.sub.3).sub.3 3-CH.sub.3 CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5SO.sub.2 N(CH.sub.2 CH.sub.3).sub.3 5-CH.sub.3 H CF.sub.3 CO.sub.2 OCH.sub.3 OC.sub.3 H.sub.5SO.sub.2 N(CH.sub.2 CH.sub.3).sub.3 6-Cl H C.sub.2 H.sub.5 CO.sub.2 OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 CO.sub.2 CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 CO.sub.2 CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.3 H H CH.sub.3 OCO.sub.2 Cl OCH.sub.3CO.sub.2 CH.sub.3 5-F H OH CH.sub.3 CH.sub.2 OCH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 5-F H (C.sub.2 H.sub.5).sub.2 NCO.sub.2 CH.sub.3 CH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 3-Br CH.sub.3 OH OCH.sub.3 OCH.sub.3SO.sub.2 N(OCH.sub.3)CH.sub.3 H H -n-C.sub.3 H.sub.7 CO.sub.2 OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 6-CH.sub.3 H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 Cl 3-CF.sub.3 h OH OCH.sub.3 OCH.sub.3CO.sub.2 -n-C.sub.4 H.sub.9 6-CF.sub.3 H OH OCH.sub.3 CH.sub.3SO.sub.2 CH.sub.3 5-CF.sub.3 H OH CH.sub.3 CH.sub.3SO.sub.2 CH.sub.3 3-CF.sub.3 H OH CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.3 H H CH.sub.3 OCO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 CH.sub.3 6-SCH.sub.3 H OH OCH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CHCH.sub. 2 5-SCH.sub.3 H CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 6-OCH.sub.3 H OH CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H H (CH.sub.3).sub.2 NCO.sub.3 OCH.sub.3 CH.sub.3SCH.sub.2 CH.sub.3 3-OCH.sub.3 H OH OCH.sub.3 OCH.sub.3SCF.sub.3 H H CH.sub.3 NHCO.sub.2 CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 CHF.sub.2 3-CH.sub.3 CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CH.sub.3 5-CH.sub.3 H CF.sub.3 CO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5 .sub.-i-C.sub.3 H.sub.7 6-Cl H OH OCH.sub.3 CH.sub.3 -n-C.sub.4 H.sub.9 H H C.sub.2 H.sub.5 CO.sub.2 CH.sub.3 OCH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 6-Cl H OH Cl CH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 H H CH.sub.3 OCO.sub.2 Cl OCH.sub.3OSO.sub.2 CH(CH.sub.3).sub.2 5-F H CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.2 OCH.sub.3OSO.sub.2 CH.sub.3 3-Br CH.sub.3 OH OCH.sub.3 OCH.sub.3OSO.sub.2 CH.sub.3 H H -n-C.sub.3 H.sub.7 OCO.sub.2 OCH.sub.3 CH.sub.3CH.sub.2 OCH.sub.3 H H C.sub.3 H.sub.7 CO.sub.2 CH.sub.3 OCH.sub.3CH.sub.2 CH.sub.2 OCH.sub.3 6-CH.sub.3 H OH CH.sub.3 CH.sub.3OCF.sub.3 3-CF.sub.3 H OH OCH.sub.3 OCH.sub.3SO.sub.2 .sub.-i-C.sub.3 H.sub.7 5-CF.sub.3 H OH OCH.sub.3 CH.sub.3CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 H H OH OCH.sub.3 OCH.sub.3C.sub.6 H.sub.5 6-Cl H OCH.sub.3 OCH.sub.3 OCH.sub.3C.sub.6 H.sub.5 6-Cl H OCH.sub.3 OCH.sub.3 CH.sub.3C.sub.6 H.sub.5 6-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CH.sub.3C.sub.6 H.sub.5 6-OCH.sub.3 H OCH.sub.3 OCH.sub.3 OCH.sub.3__________________________________________________________________________ *Data refer to molecular ion in electronimpact mass spectrum.
TABLE 2B__________________________________________________________________________ ##STR38##R.sub.5 R.sub.6 R R' X Y m.p. (.degree.C.)__________________________________________________________________________Cl H H OH CH.sub.3 CH.sub.3Cl H H OH CH.sub.3 OCH.sub.3Cl H H OH OCH.sub.3 OC.sub.2 H.sub.5Cl H H OH OCH.sub.3 OCH.sub.3 137-140.degree.F H H OH CH.sub.3 CH.sub.3F H H OH CH.sub.3 OCH.sub.3Br H H OH OCH.sub.3 CH.sub.3Br H OH OCH.sub.3 OCH.sub.3NO.sub.2 H H OH CH.sub.3 CH(OCH.sub. 2 CH.sub.2 O)NO.sub.2 H CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CF.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5CF.sub.3 H H OH OCH.sub.3 CH.sub.3OCH.sub.3 H H OH CH.sub.3 OCH.sub.3OCH.sub.3 H H OH CH.sub.3 CH(OCH.sub.3)OCH.sub.3 H H OH CH.sub.3 CH.sub.3OCH.sub.3 H H OH OCH.sub.3 OCH.sub.3OC.sub.2 H.sub.5 H H OH CH.sub.3 CH.sub.2 OCH.sub.3OC.sub.2 H.sub.5 H H OH CH.sub.3 CH.sub.3OC.sub.2 H.sub.5 H CH.sub.3 OH OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 CH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H OH CH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H OH CH.sub.3 CH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H H OH CH.sub.3 OCH.sub.3CO.sub.3 CH.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 N(CH.sub.3).sub.2 H H OH OCH.sub.3 OCH.sub.3 .delta. 3.0 and 4.0 (1:1)**SO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 CH.sub.3 4.O (1:1)*SO.sub.2 N(CH.sub.3).sub.2 H H OH H OCH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 N(CH.sub.3).sub.2 H CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5SO.sub.2 N(CH.sub.3).sub.2 H H OH OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 N(CH.sub.3).sub.2 H H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 H H OH CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 H H OH CH.sub.3 CH(OCH.sub.3).sub.2CO.sub.2 CH.sub.3 H H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H H OH CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.3 H H OH CH.sub.3 CH.sub.2 OCH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 H H OH CH.sub.3 CH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 N(OCH.sub.3)CH.sub.3 H H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H H OH CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 H H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 Cl H H OH OCH.sub.3 OCH.sub.3CO.sub.2 -n-C.sub.4 H.sub.9 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 CH.sub.3 H H OH CH.sub.3 CH.sub.3SO.sub.2 CH.sub.3 H H OH CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 CH.sub.3 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 H H OH CH.sub.3 CH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 H H OH CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H H OH OCH.sub.3 CH.sub.3SCH.sub.2 CH.sub.3 H H OH OCH.sub.3 OCH.sub.3SCF.sub.3 H H OH CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 CHF.sub.2 H CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CH.sub.3 H H OH OCH.sub.3 OC.sub.2 H.sub.5 .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 CH.sub.3 -n-C.sub.4 H.sub.9 H H OH CH.sub.3 OCH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 CH(OCH.sub.3).sub.2OSO.sub.2 N(CH.sub.3).sub.2 H H OH CH.sub.3 CH.sub.3OSO.sub.2 CH(CH.sub.3).sub.2 H H OH CH.sub.3 OCH.sub.3OSO.sub.2 C.sub.2 H.sub.5 H H OH CH.sub.3 CH.sub.2 OCH.sub.3OSO.sub.2 CH.sub.3 H CH.sub.3 OH OCH.sub.3 OCH.sub.3OSO.sub.2 CH.sub.3 H H OH OCH.sub.3 CH.sub.3CH.sub.2 OCH.sub.3 H H OH CH.sub.3 OCH.sub.3CH.sub.2 CH.sub.2 OCH.sub.3 H H OH CH.sub.3 CH.sub.3OCF.sub.3 H H OH OCH.sub.3 OCH.sub.3SO.sub.2 .sub.-i-C.sub.3 H.sub.7 H H OH OCH.sub.3 CH.sub.3Cl 3-CF.sub.3 H OH CH.sub.3 CH.sub.3Cl 5-CF.sub.3 H OH CH.sub.3 OCH.sub.3Cl H H CH.sub.3 OCO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5Cl 6-SCH.sub.3 H OH OCH.sub.3 OCH.sub.3F 5-SCH.sub.3 H CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3F 6-OCH.sub.3 H OH CH.sub.3 OCH.sub.3Br H H (CH.sub.3).sub.2 NCO.sub.2 OCH.sub.3 CH.sub.3Br 3-OCH.sub.3 H OH OCH.sub.3 OCH.sub.3NO.sub.2 H H CH.sub.3 NHCO.sub.2 CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)NO.sub.2 3-CH.sub.3 CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CF.sub.3 5-CH.sub.3 H CF.sub.3 CO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5CF.sub.3 6-Cl H C.sub.2 H.sub.5 CO.sub.2 OCH.sub.3 CH.sub.3OCH.sub.3 H H C.sub.2 H.sub.5 OCO.sub.2 CH.sub.3 OCH.sub.3OCH.sub.3 5-Cl H OH CH.sub.3 CH(OCH.sub.3).sub.2OCH.sub.3 6-Cl H OH CH.sub.3 CH.sub.3OCH.sub.3 H H -n-C.sub.3 H.sub.7 CO.sub.2 CH.sub.3 OCH.sub.3OC.sub.2 H.sub.5 5-F H OH CH.sub.3 CH.sub.2 OCH.sub.3OC.sub.2 H.sub.5 5-F H Et.sub.2 NCO.sub.2 CH.sub.3 CH.sub.3OC.sub.2 H.sub.5 3-Br CH.sub.3 OH OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 H H EtOCO.sub.2 OCH.sub.3 CH.sub.3O -n-C.sub.3 H.sub.7 H H -n-C.sub.3 H.sub.7 CO.sub.2 CH.sub.3 OCH.sub.3O -n-C.sub.3 H.sub.7 6-CH.sub.3 H OH CH.sub.3 CH.sub.3O .sub.-i-C.sub.4 H.sub.9 3-CF.sub.3 H CH.sub.3 OCO.sub.2 OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.4 H.sub.9 5-CF.sub.3 H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 3-CF.sub.3 H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 5-CF.sub.3 H OH CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.3 H H CH.sub.3 OCO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 N(CH.sub.3).sub.2 6-SCH.sub.3 H OH OCH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.2 5-SCH.sub.3 H CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 6-OCH.sub.3 H OH CH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H H (CH.sub.3).sub.2 NCO.sub.2 OCH.sub.3 OCH.sub.3SO.sub.2 N(CH.sub.3).sub.2 3-OCH.sub.3 H OH OCH.sub.3 OCH.sub.2 CH.sub.3SO.sub.2 N(CH.sub.3).sub.2 H H CH.sub.3 NHCO.sub.2 CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2 3-CH.sub.3 CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2 5-CH.sub.3 H -n-C.sub.3 H.sub.7 CO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2 6-Cl H OH OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 H H CF.sub.3 CO.sub.2 CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 5-Cl H C.sub.2 H.sub.5 OCO.sub.2 CH.sub.3 CH(OCH.sub.3).sub.2CO.sub.2 CH.sub.3 6-Cl H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 CO.sub.2 CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.3 5-F H OH CH.sub.3 CH.sub.2 OCH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 5-F H OH CH.sub.3 CH.sub.3CO.sub.2 .sub.-i-C.sub.3 H.sub.7 3-Br CH.sub.3 OH OCH.sub.3 OCH.sub.3SO.sub.2 N(OCH.sub.3)CH.sub.3 H H Et.sub.2 NCO.sub.2 OCH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H H -n-C.sub.3 H.sub.7 OCO.sub.2 CH.sub.3 OCH.sub.3CO.sub.2 CH.sub.2 CHCH.sub.2 6-CH.sub.3 H OH CH.sub.3 CH.sub.3CO.sub.2 CH.sub.2 CH.sub.2 Cl H H CH.sub.3 OCO.sub.2 OCH.sub.3 OCH.sub.3CO.sub.2 -n-C.sub.4 H.sub.9 H H C.sub.2 H.sub.5 CO.sub.2 OCH.sub.3 CH.sub.3SO.sub.2 CH.sub.3 3-CF.sub.3 H OH CH.sub.3 CH.sub.3SO.sub.2 CH.sub.3 5-CF.sub.3 H OH CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.3 H H CH.sub.3 OCO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5SO.sub.2 CH.sub.3 6-SCH.sub.3 H OH OCH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 5-SCH.sub.3 H OH CH.sub.3 CH.sub.3SO.sub.2 CH.sub.2 CHCH.sub.2 6-OCH.sub.3 H (CH.sub.3).sub.2 NCO.sub.2 CH.sub.3 OCH.sub.3SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H H OH OCH.sub.3 CH.sub.3SCH.sub.2 CH.sub.3 3-OCH.sub.3 H OH OCH.sub.3 OCH.sub.3SCF.sub.3 H H CH.sub.3 NHCO.sub.2 CH.sub.3 CH(OCH.sub.2 CH.sub.2 O)SO.sub.2 CHF.sub.2 3-CH.sub.3 CH.sub.3 OH CH.sub.3 C.sub.2 H.sub.5CH.sub.3 5-CH.sub.3 H C.sub.2 H.sub.5 OCO.sub.2 OCH.sub.3 OC.sub.2 H.sub.5 .sub.-i-C.sub.3 H.sub.7 6-Cl H OH OCH.sub.3 CH.sub.3 -n-C.sub.4 H.sub.9 H H -n-C.sub.3 H.sub.7 OCO.sub.2 CH.sub.3 OCH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 6-Cl H C.sub.2 H.sub.5 CO.sub.2 CH.sub.3 CH.sub.3OSO.sub.2 N(CH.sub.3).sub.2 H H -n-C.sub.3 H.sub.7 CO.sub.2 CH.sub.3 OCH.sub. 3OSO.sub.2 CH(CH.sub.3).sub.2 5-F H OH CH.sub.3 CH.sub.2 OCH.sub.3OSO.sub.2 CH.sub.3 3-Br CH.sub.3 C.sub.2 H.sub.5 NHCO.sub.2 OCH.sub.3 OCH.sub.3OSO.sub.2 CH.sub.3 H H (C.sub.2 H.sub.5).sub.2 NCO.sub.2 OCH.sub.3 CH.sub.3CH.sub.2 OCH.sub.3 H H CH.sub.3 CO.sub.2 CH.sub.3 OCH.sub.3CH.sub.2 CH.sub.2 OCH.sub.3 6-CH.sub.3 H OH CH.sub.3 CH.sub.3OCF.sub.3 H H C.sub.2 H.sub.5 OCO.sub.2 OCH.sub.3 OCH.sub.3SO.sub.2 .sub.-i-C.sub.3 H.sub.7 H H -n-C.sub.3 H.sub.7 NHCO.sub.2 OCH.sub.3 CH.sub.3CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 H H OH OCH.sub.3 CH.sub.3C.sub.6 H.sub.5 6-Cl H OCH.sub.3 OCH.sub.3 OCH.sub.3C.sub.6 H.sub.5 6-Cl H OCH.sub.3 OCH.sub.3 CH.sub.3C.sub.6 H.sub.5 6-OCH.sub.3 H OCH.sub.3 OCH.sub.3 OCH.sub.3C.sub.6 H.sub.5 6-OCH.sub.3 H OCH.sub.3 OCH.sub.3 CH.sub.3__________________________________________________________________________ **Data refer to characteristic signals in NMR spectrum (CDCl.sub.3) in pp downfield form tetramethylsilane.
TABLE 2c__________________________________________________________________________ ##STR39## m.p.R' R R.sub.5 R.sub.6 X Y Z (.degree.C.)__________________________________________________________________________OH H OCH.sub.2 CH.sub.2 OCH.sub.3 H CH.sub.3 H CHOH H OCH.sub.2 CHCH.sub.2 H CH.sub.3 CH.sub.3 NOH H OCH.sub.2 CHCH 6-OCH.sub.3 CH.sub.3 CH.sub.3 CHOH H C.sub.6 H.sub.5 H CH.sub.3 CH.sub.3 NOH H N N H CH.sub.3 OCH.sub.3 CH O CH.sub.3OH H N N H OCH.sub.3 OCH.sub.3 N OOH H Cl H OCH.sub.3 OCH.sub.2 CCH NCONHCH.sub.3 H Cl H OCH.sub.3 OCH.sub.2 CF.sub.3 CHOH H Cl H OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 NOH H Cl H OCH.sub.3 CH.sub.2 SCH.sub.3 CHOH H F H OCH.sub.3 OCF.sub.2 H CHOH H F H OCH.sub.3 SCF.sub.2 H CHOH H F 3-OCF.sub.2 H OCH.sub.3 C(CH.sub.3)(OCH.sub.3).sub.2 CHOH H F H OCH.sub.3 CF.sub.3 NOH H Br H OCH.sub.3 N(CH.sub.3).sub.2 CHOH CH.sub.3 Br H OCH.sub.3 C(CH.sub.3)(SCH.sub.3).sub.2 NOH CH.sub.3 Br H OCF.sub.2 H CH(SCH.sub.2 CH.sub.2 S) CHOH CH.sub.3 Br H CF.sub.3 CH.sub.2 CH.sub.3 CHOH CH.sub.3 Br H F OCH.sub.3 CHOH CH.sub.3 Br H OC.sub.2 H.sub.5 C(CH.sub.3)(OCH.sub.2 CH.sub.2 O) CHOH H ##STR40## H CH.sub.3 H CHOH H ##STR41## H CH.sub.3 CH.sub.3 CHOH H ##STR42## H CH.sub.3 OCH.sub.3 CHCOCF.sub.3 H O .sub.-n-C.sub.3 H.sub.7 H OCH.sub.3 OCH.sub.3 CHOH H O .sub.-n-C.sub.3 H.sub.7 H OCH.sub.3 OCH.sub.2 CHCH.sub.2 CHOH H O .sub.-n-C.sub.3 H.sub.7 H OCH.sub.3 OCH.sub.2 CCH NOH H OCH.sub.3 5-Br OCH.sub.3 OCH.sub.2 CF.sub.3 NOH H OCH.sub.3 H OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 NOH H OCH.sub.3 H OCH.sub.3 CH.sub.2 SCH.sub.3 CHOH H NO.sub.2 H OCH.sub.3 OCF.sub.2 H CHOH H NO.sub.2 H OCH.sub.3 SCF.sub.2 H CHOH H NO.sub.2 H OCH.sub.3 C(CH.sub.3)(OCH.sub.3).sub.2 CHOH H CF.sub.3 H OCH.sub.3 CF.sub.3 CHOH H CF.sub.3 H OCH.sub.3 N(CH.sub.3).sub.2 CHOH CH.sub.3 CF.sub.3 H OCH.sub.3 C(CH.sub.3)(SCH.sub.3).sub.2 CHOH CH.sub.3 CO.sub.2 CH.sub.3 H OCF.sub.2 H CH(SCH.sub.2 CH.sub.2 S) CHOH CH.sub.3 CO.sub.2 CH.sub.3 H CF.sub.3 CH.sub.2 CH.sub.3 CHOH CH.sub.3 CO.sub.2 CH.sub.3 H F OCH.sub.3 CHOH CH.sub.3 CO.sub.2 CH.sub.3 H OC.sub.2 H.sub.5 C(CH.sub.3)(OCH.sub.2 CH.sub.2 O) CHOH H ##STR43## H CH.sub.3 H NOH H ##STR44## H CH.sub.3 CH.sub.3 NOH H ##STR45## H CH.sub.3 OCH.sub.3 CHOH H CO.sub.2 CH.sub.2 CHCH.sub.2 H OCH.sub.3 OCH.sub.3 CHOH H CO.sub.2 CH.sub.2 CHCH.sub.2 H OCH.sub.3 OCH.sub.2 CHCH.sub.2 CHOH H CO.sub.2 CH.sub.2 CHCH.sub.2 H OCH.sub.3 OCH.sub.2 CCH NOH H SO.sub.2 N(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.2 CF.sub.3 NOH H SO.sub.2 N(CH.sub.3).sub.2 H OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 NOH H SO.sub.2 N(CH.sub.3).sub.2 H OCH.sub.3 CH.sub.2 SCH.sub.3 NOH H SO.sub.2 N(OCH.sub.3)CH.sub.3 H OCH.sub.3 OCF.sub.2 H CHOH H SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5 H OCH.sub.3 SCF.sub.2 H CHOH H SCF.sub.3 H OCH.sub.3 C(CH.sub.3)(OCH.sub.3).sub.2 CHOH H SO.sub.2 CHF.sub.2 H OCH.sub.3 CF.sub.3 CHOH H CO.sub.2 CH.sub.2 CH.sub.2 Cl H OCH.sub.3 N(CH.sub.3).sub.2 CHOH CH.sub.3 CO.sub.2 CH.sub.2 CH.sub.3 H OCH.sub.3 C(CH.sub.3)(SCH.sub.3).sub.2 CHOH H CO.sub.2 CH.sub.2 CH.sub.3 H OCF.sub.2 H CH(SCH.sub.2 CH.sub.2 S) CHOH H CO.sub. 2 CH.sub.2 CH.sub.3 H CF.sub.3 CH.sub.2 CH.sub.3 CHOH H SO.sub.2 CH.sub.3 H F OCH.sub.3 CHOCO .sub.-i-C.sub.3 H.sub.7 H SO.sub.2 CH.sub.3 H OC.sub.2 H.sub.5 C(CH.sub.3)(OCH.sub.2 CH.sub.2 O) CHOH H ##STR46## H CH.sub.3 H NOH H ##STR47## H CH.sub.3 CH.sub.3 NOH H ##STR48## 6-OCF.sub.2 H CH.sub.3 OCH.sub.3 CHOH H ##STR49## H OCH.sub.3 OCH.sub.3 CHOH H OCH.sub.3 H OCH.sub.3 OCH.sub.2 CCH CHOH H OCH.sub.3 H OCH.sub.3 OCH.sub.2 CF.sub.3 CHOH H OCH.sub.3 H OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 CHOH H OC.sub.2 H.sub.5 H OCH.sub.3 CH.sub.2 SCH.sub.3 CHOH H OC.sub.2 H.sub.5 3-F OCH.sub.3 OCF.sub.2 H CHOCO.sub.2 CH.sub.2 CH.sub.3 H OC.sub.2 H.sub.5 H OCH.sub.3 SCF.sub.2 H CHOH H CH.sub.3 H OCH.sub.3 C(CH.sub.3)(OCH.sub.3).sub.2 NOH H CH.sub.3 H OCH.sub.3 CF.sub.3 NOH H CH.sub.3 H OCH.sub.3 N(CH.sub.3).sub.2 NOH CH.sub.3 .sub.-i-C.sub.3 H.sub.7 H OCH.sub.3 C(CH.sub.3)(SCH.sub.3).sub.2 CHOH H .sub.-i-C.sub.3 H.sub.7 H OCF.sub.2 H CH(SCH.sub.2 CH.sub.2 S) CHOH H .sub.-i-C.sub.3 H.sub.7 H CF.sub.3 CH.sub.2 CH.sub.3 CHOH H .sub.-i-C.sub.3 H.sub.7 H F OCH.sub.3 CHOH H .sub.-n-C.sub.4 H.sub.9 H OC.sub.2 H.sub.5 C(CH.sub.3)(OCH.sub.2 CH.sub.2 O) N__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR50##R.sub.7 R R' X Y Z m.p. (.degree.C.)__________________________________________________________________________OH H OH CH.sub.3 CH.sub.3 CHCH.sub.3 H OCON(CH.sub.3).sub.2 OCH.sub.3 CH.sub.3 NOCH.sub.3 H OH Cl CH.sub.3 CHF H OH CH.sub.3 CH.sub.3 CHCl H OH OCH.sub.3 OCH.sub.3 CHBr H OH F OCH.sub.3 CHSO.sub.2 N(CH.sub.3).sub.2 H OH CH.sub.3 OCH.sub.3 CHOSO.sub.2 CH.sub.3 H OH OCF.sub.2 H OCH.sub.3 CHSO.sub.2 CH.sub.3 H OH CH.sub.2 F OC.sub.2 H.sub.5 CHOH CH.sub.3 OH OCH.sub.2 CH.sub.3 CH.sub.2 OCH.sub.3 NCH.sub.3 H OH CF.sub.3 N(CH.sub.3).sub.2 CHOCH.sub.3 H OH OCH.sub.3 CF.sub.3 CHF H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CH(OCH.sub.3).sub.2 CHCl H OH OCH.sub.3 OCF.sub.2 H NBr H OH OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 NSO.sub.2 N(CH.sub.3).sub.2 H OH OCH.sub.3 CH.sub.2 SCH.sub.3 NOSO.sub.2 CH.sub.3 H OH OCH.sub.3 OCH.sub.2 CCH CHSCH.sub.3 SCH.sub.3 H H OH OH OCH.sub.2 CH.sub.3 CH.sub.3 ##STR51## CH CHCH.sub.3 H OH CH.sub.3 OCH.sub.3 NOH H OH CH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 4__________________________________________________________________________ ##STR52## m.p.R.sub.8 R R' X Y Z (.degree.C.)__________________________________________________________________________CH.sub.3 H OCON(CH.sub.3).sub.2 OCH.sub.3 ##STR53## NCH.sub.2 CH.sub.3 H OH Cl OCH.sub.3 CHOCH.sub.3 H OH CH.sub.3 CH.sub.2 OC.sub.2 H.sub.5 CHOCH.sub.2 CH.sub.3 H OH OCH.sub.3 CH.sub.3 CHF H OH F CH.sub.3 CHCl H OH CH.sub.3 CH.sub.3 CHBr H OH OCF.sub.2 H CH.sub.3 CHSO.sub.2 N(CH.sub.2 CH.sub.3).sub. 2 H OH CH.sub.2 F OCH.sub.3 CHSO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 OH OCH.sub.2 CH.sub.3 OCH.sub.3 NSO.sub.2 N(OCH.sub.3)CH.sub.3 H OH CF.sub.3 OCH.sub.3 CHSCH.sub.2 CHCH.sub.2 H OH OCH.sub.3 OCH.sub.3 CHSO.sub.2 C.sub.2 H.sub.5 H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHS .sub.-n-C.sub.3 H.sub.7 H OH OCH.sub.3 C.sub.2 H.sub.5 NSO.sub.2 CH.sub.3 H OH OCH.sub.3 OC.sub.2 H.sub.5 NSCH.sub.3 H OH OCH.sub.3 SCF.sub.2 H NCH.sub.3 H OH OCH.sub.3 C(CH.sub.3)(SCH.sub.3).sub.2 CHF H OH OCH.sub.2 CH.sub.3 OCF.sub.2 H CHCl H OH CH.sub.3 CH(OC.sub.2 H.sub.5).sub.2 CHBr H OH CH.sub.3 CH.sub.3 NOCH.sub.3 H OH CH.sub.3 CH.sub.3 N__________________________________________________________________________
TABLE 5__________________________________________________________________________ ##STR54## m.p.L R.sub.9 R R' X Y Z (.degree.C.)__________________________________________________________________________L.sub.4 CH.sub.3 H OH CH.sub.3 OCH.sub.3 CHL.sub.4 F H OCON(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 NL.sub.4 NO.sub.2 H OH Cl OCH.sub.3 CHL.sub.4 CO.sub.2 C.sub.2 H.sub.5 H OH CH.sub.3 OCH.sub.3 CHL.sub.4 SO.sub.2 N(CH.sub.3).sub.2 H OH OCH.sub.3 CH.sub.2 SCH.sub.3 CHL.sub.4 S .sub.-i-C.sub.3 H.sub.7 H OH F CH.sub.3 CHL.sub.5 .sub.-n-C.sub.3 H.sub.7 H OH CH.sub.3 N(CH.sub.3).sub.2 CHL.sub.5 Cl H OH OCF.sub. 2 H CH.sub.2 OCH.sub.3 CHL.sub.5 Br H OH CH.sub.2 F CH.sub.2 OCH.sub.3 CHL.sub.5 CO.sub.2 CH.sub.3 CH.sub.3 OH OCH.sub.2 CH.sub.3 CH.sub.2 OCH.sub.3 NL.sub.5 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H OH CF.sub.3 CH.sub.3 CHL.sub.5 SO.sub.2 N(OCH.sub.3)CH.sub.3 H OH OCH.sub.3 CH.sub.3 CHL.sub.5 SO.sub.2 C.sub.2 H.sub.5 H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CHL.sub.5 SCH.sub.2 CHCH.sub.2 H OH OCH.sub.3 CH.sub.3 NL.sub.5 SO.sub.2 CH.sub.3 H OH OCH.sub.3 ##STR55## NL.sub.6 F H OH OCH.sub.3 CH(OCH.sub.3).sub.2 CHL.sub.6 CO.sub.2 .sub.-i-C.sub.3 H.sub.7 H OH OCH.sub.2 CH.sub.3 OCH.sub.3 CHL.sub.6 SO.sub.2 CH.sub.3 H OH CH.sub.3 OCH.sub.3 CHL.sub.6 SO.sub.2 N(CH.sub.3).sub.2 H OH CH.sub.3 OCH.sub.3 NL.sub.6 Br H OH CH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 6__________________________________________________________________________ ##STR56## m.p.R.sub.10 R R' X Y Z (.degree.C.)__________________________________________________________________________Cl H OH CH.sub.3 CH.sub.3 CHNO.sub.2 H OCON(CH.sub.3).sub.2 OCH.sub.3 CH.sub.3 NCO.sub.2 CH.sub.3 H OH Cl CH.sub.3 CHCO.sub.2 CH.sub.2 CH.sub.3 H OH CH.sub.3 CH.sub.3 CHSO.sub.2 N(CH.sub.3).sub.2 H OH OCH.sub.3 CH.sub.3 CHOSO.sub.2 CH.sub.3 H OH F OCH.sub.3 CHSO.sub.2 CH.sub.3 H OH CH.sub.3 OCH.sub.3 CHSO.sub.2 CH.sub.2 CH.sub.3 H OH OCF.sub.2 H OCH.sub.3 CHOCH.sub.3 H OH CH.sub.2 F OCH.sub.3 CHOCH.sub.2 CH.sub.3 CH.sub.3 OH OCH.sub.2 CH.sub.3 OCH.sub.3 NOCH.sub.2 CH.sub.3 H OH CF.sub.3 CH.sub.2 SCH.sub.3 CHOCH.sub.2 CH.sub.3 H OH OCH.sub.3 CF.sub.3 CHOCH.sub.3 H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CHSO.sub.2 CH.sub.2 CH.sub.3 H OH OCH.sub.3 OCH.sub.3 NSO.sub.2 CH.sub.3 H OH OCH.sub.3 SCF.sub.2 H NOSO.sub.2 CH.sub.3 H OH OCH.sub.3 CH.sub.3 NCO.sub.2 CH.sub.2 CH.sub.3 H OH OCH.sub.3 CH.sub.3 CHCO.sub.2 CH.sub.3 H OH OCH.sub.2 CH.sub.3 CH.sub.3 CHCO.sub.2 CH.sub.3 H OH CH.sub.3 CH.sub.3 CHCO.sub.2 CH.sub.3 H OH CH.sub.3 OCH.sub.3 NNO.sub.2 H OH CH.sub.3 OCH.sub.3 N__________________________________________________________________________
TABLE 7__________________________________________________________________________ ##STR57## m.p.Q.sub.1 R.sub.11 R.sub.12 R.sub.13 R R' X Y Z (.degree.C.)__________________________________________________________________________O H H H H OH CH.sub.3 OCH.sub.3 CHS H H H H OCON(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 NSO.sub.2 H H H H OH Cl OCH.sub.3 CHNH H H H H OH CH.sub.3 OCH.sub.3 CHNCH.sub.3 H H H H OH OCH.sub.3 CH.sub.3 CHO CH.sub.3 CH.sub.3 H H OH F CH.sub.3 CHS CH.sub.3 CH.sub.3 H H OH CH.sub.3 CH.sub.3 CHSO.sub.2 CH.sub.3 CH.sub.3 H H OH OCF.sub.2 H CH.sub.3 CHNH CH.sub.3 CH.sub.3 H H OH CH.sub.2 F OCH.sub.2 CH.sub.3 CHNCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 OH OCH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.3 NO CH.sub.2 CH.sub.3 CH.sub.3 H H OH CF.sub.3 OCH.sub.2 CH.sub.3 CHS CH.sub.2 CH.sub.3 CH.sub.3 H H OH OCH.sub.3 CF.sub.3 CHSO.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 H H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 OCF.sub.2 H CHNH CH.sub.2 CH.sub.3 CH.sub.3 H H OH OCH.sub.3 OCH.sub.3 NNCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H H OH OCH.sub.3 OCH.sub.3 NO H CH.sub.3 H H OH OCH.sub.3 OCH.sub.3 NS H CH.sub.3 H H OH OCH.sub.3 OCH.sub.3 CHSO.sub.2 H CH.sub.3 H H OH OCH.sub.2 CH.sub.3 OCH.sub.3 CHNH H CH.sub.3 H H OH CH.sub.3 C(CH.sub.3)(OCH.sub.3).sub.2 CHNCH.sub.3 H CH.sub.3 H H OH CH.sub.3 CH.sub.3 NO CH.sub.3 CH.sub.3 H H OH CH.sub.3 CH.sub.3 N__________________________________________________________________________
TABLE 8__________________________________________________________________________ ##STR58## m.p.Q.sub.2 R.sub.14 R.sub.15 R R' X Y Z (.degree.C.)__________________________________________________________________________O H H H OH CH.sub.3 CH.sub.3 CHO H CH.sub.3 H OCON(CH.sub.3).sub.2 OCH.sub.3 CH.sub.3 NO H H H OH Cl CH.sub.3 CHO H CH.sub.3 H OH CH.sub.3 CH.sub.3 CHO CH.sub.3 H H OH OCH.sub.3 CH(OCH.sub.3).sub.2 CHO CH.sub.3 CH.sub.3 H OH F OCH.sub.3 CHO CH.sub.3 H H OH CH.sub.3 OCH.sub.3 CHS H CH.sub.3 H OH OCF.sub.2 H OCH.sub.3 CHS H H H OH CH.sub.2 F OCH.sub.3 CHS H CH.sub.3 CH.sub.3 OH OCH.sub.2 CH.sub.3 CH.sub.2 SCH.sub.3 NS H H H OH CF.sub.3 OCH.sub.2 CH.sub.3 CHS CH.sub.3 CH.sub.3 H OH OCH.sub.3 OCH.sub.3 CHS CH.sub.3 H H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHS CH.sub.3 CH.sub.3 H OH OCH.sub.3 OCH.sub.3 NNH H H H OH OCH.sub.3 OCH.sub.3 NNH CH.sub.3 CH.sub.3 H OH OCH.sub.3 OCH.sub.3 NNH H H H OH OCH.sub.3 OCH.sub.3 CHNCH.sub.3 H CH.sub.3 H OH OCH.sub.2 CH.sub.3 CH.sub.3 CHNCH.sub.3 CH.sub.3 H H OH CH.sub.3 CH.sub.3 CHNCH.sub.3 CH.sub.3 CH.sub.3 H OH CH.sub.3 CH.sub.3 NNCH.sub.3 CH.sub.3 H H OH CH.sub.3 CH.sub.3 N__________________________________________________________________________
TABLE 9__________________________________________________________________________ ##STR59## m.p.L m R.sub.13 R.sub.16 R R' X Y Z (.degree.C.)__________________________________________________________________________L-10 0 H CH.sub.3 H OH CH.sub.3 CH.sub.3 CHL-10 1 H CH.sub.3 H OCON(CH.sub.3).sub.2 OCH.sub.3 CH.sub.3 NL-10 0 H CH.sub.3 H OH Cl CH.sub.3 CHL-11 0 CH.sub.3 -- H OH CH.sub.3 CH.sub.3 CHL-11 0 CH.sub.3 -- H OH OCH.sub.3 CH(OCH.sub.3).sub.2 CHL-11 0 CH.sub.3 -- H OH F OCH.sub.3 CHL-11 0 H -- H OH CH.sub.3 OCH.sub.3 CHL-12 1 H -- H OH OCF.sub.2 H OCH.sub.3 CHL-12 0 H -- H OH CH.sub.2 F OCH.sub.3 CHL-12 1 H -- CH.sub.3 OH OCH.sub.2 CH.sub.3 CH.sub.2 SCH.sub.3 NL-13 0 CH.sub.3 -- H OH CF.sub.3 OCH.sub.2 CH.sub.3 CHL-13 1 H -- H OH OCH.sub.3 OCH.sub.3 CHL-13 0 H -- H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHL-13 1 H -- H OH OCH.sub.3 OCH.sub.3 NL-14 0 H -- H OH OCH.sub.3 OCH.sub.3 NL-14 1 H -- H OH OCH.sub.3 OCH.sub.3 NL-14 0 CH.sub.3 -- H OH OCH.sub.3 OCH.sub.3 CHL-10 1 H CH.sub.3 H OH OCH.sub.2 CH.sub.3 CH.sub.3 CHL-10 0 H C.sub.2 H.sub.5 H OH CH.sub.3 CH.sub.3 CHL-10 1 H C.sub.2 H.sub.5 H OH CH.sub.3 CH.sub.3 NL-10 0 H C.sub.2 H.sub.5 H OH CH.sub.3 CH.sub.3 N__________________________________________________________________________
TABLE 10__________________________________________________________________________ ##STR60## m.p.L R.sub.17 R.sub.18 R R' X Y Z (.degree.C.)__________________________________________________________________________L.sub.15 H -- H OH CH.sub.3 CH.sub.3 CHL.sub.15 H -- H OCON(CH.sub.3).sub.2 OCH.sub.3 CH.sub.3 NL.sub.15 H -- H OH C1 CH.sub.3 CHL.sub.15 H -- H OH CH.sub.3 CH.sub.3 CHL.sub.15 H -- H OH OCH.sub.3 CH(OCH.sub.3).sub.2 CHL.sub.15 H -- H OH F OCH.sub.3 CHL.sub.15 H -- H OH CH.sub.3 OCH.sub.3 CHL.sub.15 CH.sub.3 -- H OH OCF.sub.2 H OCH.sub.3 CHL.sub.15 CH.sub.3 -- H OH CH.sub.2 F OCH.sub.3 CHL.sub.15 CH.sub.3 -- CH.sub.3 OH OCH.sub.2 CH.sub.3 CH.sub.2 SCH.sub.3 NL.sub.16 CH.sub.3 -- H OH CF.sub.3 OCH.sub.2 CH.sub.3 CHL.sub.16 CH.sub.3 -- H OH OCH.sub.3 OCH.sub.3 CHL.sub.16 CH.sub.3 -- H OCO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 CHL.sub.16 CH.sub.3 -- H OH OCH.sub.3 OCH.sub.3 NL.sub.16 H -- H OH OCH.sub.3 OCH.sub.3 NL.sub.16 H -- H OH OCH.sub.3 OCH.sub.3 NL.sub.16 H -- H OH OCH.sub.3 OCH.sub.3 CHL.sub.17 CH.sub.3 CH.sub.3 H OH OCH.sub.2 CH.sub.3 CH.sub.3 CHL.sub.17 CH.sub.3 H H OH CH.sub.3 CH.sub.3 CHL.sub.17 CH.sub.3 CH.sub.3 H OH CH.sub.3 CH.sub.3 NL.sub.17 CH.sub.3 CH.sub.3 H OH CH.sub.3 CH.sub.3 N__________________________________________________________________________
TABLE 11______________________________________ ##STR61##R.sub.5 R.sub.6 R R' A______________________________________CH.sub.3 H H OH A.sub.2 : Y.sub.1 = CH.sub.2 ; X.sub.1 = CH.sub.3 .sub.-i-C.sub.3 H.sub.7 H H OH A.sub.2 : Y.sub.1 = O; X.sub.1 = OCH.sub.3OC.sub.2 H.sub.5 H H OH A.sub.2 : Y.sub.1 = CH.sub.2 ; X.sub.1 = OCF.sub.2 HO -n-C.sub.4 H.sub.9 H H OH A.sub.3 : X.sub.1 = CH.sub.3F 3-CF.sub.3 H OCO.sub.2 CH.sub.3 A.sub.3 : X.sub.1 = OCH.sub.2 CH.sub.3C1 H H OCO.sub.2 CH.sub.3 A.sub. 4 : X.sub.1 = OCH.sub.3 ; Y.sub.2 = HNO.sub.2 H CH.sub.3 OCO.sub.2 CH.sub.3 A.sub.4 : X.sub.1 = CH.sub.3 ; Y.sub.2 = CH.sub.3CF.sub.3 H H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = OCH.sub.3CO.sub.2 CH.sub.3 H H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = SCH.sub.3CO.sub.2 CH.sub.2 CH.sub.3 3-CH.sub.3 H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = C.sub.2 H.sub.5SO.sub.2 N(CH.sub.3).sub.2 H H OCO.sub.2 CH.sub.3 A.sub.6 : X.sub.3 = CH.sub.3SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H H OCO.sub.2 CH.sub.3 A.sub.6 : X.sub.3 = OCH.sub.3OSO.sub.2 CH.sub.2 CH.sub.3 H CH.sub.3 OCO.sub.2 CH.sub.3 A.sub.2 : Y.sub.1 = O; X.sub.1 = OCH.sub.2 CH.sub.3SCH.sub.3 6-Cl H OCO.sub.2 CH.sub.3 A.sub.2 : Y.sub.1 = CH.sub.2 ; X.sub.1 = OCH.sub.3SO.sub.2 CF.sub.3 H H OH A.sub.2 : Y.sub.1 = O; X.sub.1 = CH.sub.3OCHF.sub.2 H H OCOCH.sub.3 A.sub.3 : X.sub.1 = OCF.sub.2 HOCH.sub.2 CHCH.sub.2 H H OH A.sub.3 : X.sub.1 = OCH.sub.3C.sub.6 H.sub.5 H H OH A.sub.4 : X.sub.1 = OCH.sub.3 ; Y.sub.2 = CH.sub.3 ##STR62## H H OH A.sub.4 : X.sub.1 = OCF.sub.2 H; Y.sub.2 = H ##STR63## H H OH A.sub.5 : X.sub.2 = CH.sub.2 CF.sub.3 ; Y.sub.3 = CH.sub.3CH.sub.2 OCH.sub.3 H H OH A.sub.6 : X.sub.3 = OCH.sub.3CH.sub.2 OCH.sub.3 H H OH A.sub.6 : X.sub.3 = CH.sub.3______________________________________
TABLE 12______________________________________ ##STR64##L R R' A______________________________________L-2: R.sub.7 = SO.sub.2 N(CH.sub.3).sub.2 H OH A.sub.2 : Y.sub.1 = CH.sub.2 ; X.sub.1 = CH.sub.3L-2: R.sub.7 = OSO.sub.2 CH.sub.3 H OH A.sub.2 : Y.sub.1 = O; X.sub.1 = OCH.sub.3L-2: R.sub.7 = Cl H OH A.sub.2 : Y.sub.1 = CH.sub.2 ; X.sub.1 = OCF.sub.2 HL-2: R.sub.7 = Br H OH A.sub.3 : X.sub.1 = CH.sub.3L-3: R.sub.8 = CH.sub.3 H OCO.sub.2 CH.sub.3 A.sub.3 : X.sub.1 = OCH.sub.2 CH.sub.3L-3: R.sub.8 = OCH.sub.3 H OCO.sub.2 CH.sub.3 A.sub.4 : X.sub.1 = OCH.sub.3 ; Y.sub.2 = HL-3: R.sub.8 = SO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 OCO.sub.2 CH.sub.3 A.sub.4 : X.sub.1 = CH.sub.3 ; Y.sub.2 = CH.sub.3L-4: R.sub.9 = CO.sub.2 CH.sub.3 H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = OCH.sub.3L-5: R.sub.9 = CO.sub.2 - .sub.-i-C.sub.3 H.sub.7 H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = SCH.sub.3L-6: R.sub.9 = Cl H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = C.sub.2 H.sub.5L-4: R.sub.9 = NO.sub.2 H OCO.sub.2 CH.sub.3 A.sub.6 : X.sub.3 = CH.sub.3L-5: R.sub.9 = SO.sub.2 N(CH.sub.3).sub. 2 H OCO.sub.2 CH.sub.3 A.sub.6 : X.sub.3 = OCH.sub.3L-6: R.sub.9 = C.sub.2 H.sub.5 CH.sub.3 OCO.sub.2 CH.sub.3 A.sub.2 : Y.sub.1 = O; X.sub.1 = OCH.sub.2 CH.sub.3L-7: R.sub.10 = CO.sub.2 CH.sub.3 H OCO.sub.2 CH.sub.3 A.sub.2 : Y.sub.1 = CH.sub.2; X.sub.1 = OCH.sub.3L-7: R.sub.10 = SO.sub.2 N(CH.sub.3).sub.2 H OH A.sub.2 : Y.sub.1 = O; X.sub.1 = CH.sub.3L-7: R.sub.10 = OSO.sub.2 CH.sub.3 H OCOCH.sub.3 A.sub.3 : X.sub.1 = OCF.sub.2 HL-8: H OH A.sub.3 : X.sub.1 = OCH.sub.3R.sub.11 = R.sub.12 = R.sub.13 = CH.sub.3 ;m = 0; Q.sub.1 = SL-9: R.sub.14 = CH.sub.3 ; H OH A.sub.4 : X.sub.1 = OCH.sub.3 ;R.sub.15 = H; Y.sub.2 = CH.sub.3Q.sub.2 = NCH.sub.3L-10: R.sub.16 = C.sub.2 H.sub.5 ; H OH A.sub.4 : X.sub.1 = OCF.sub.2 H;R.sub.13 = H; M = 1 Y.sub.2 = HL-11: R.sub.13 = H; m = 0 H OH A.sub.5 : X.sub.2 = C.sub.2 H.sub.5 ; Y.sub.3 = OC.sub.2 H.sub.5L-12: R.sub.13 = CH.sub.3 ; m = 0 H OH A.sub.5 : X.sub.2 = CH.sub.2 CF.sub.3 ; Y.sub.3 = CH.sub.3L-13: R.sub.13 = CH.sub.3 ; m = 0 H OH A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = C.sub.2 H.sub.5L-14: R.sub.16 = CH.sub.3 H OH A.sub.6 : X.sub.3 =OCH.sub.3L-15: R.sub.17 = H H OH A.sub.2 : Y.sub.1 = CH.sub.2 ; X.sub.1 = CH.sub.3L-15: R.sub.17 = H H OH A.sub.2 : Y.sub.1 = O; X.sub.1 = OCH.sub.3L-15: R.sub.17 = H H OH A.sub.2 : Y.sub.1 = CH.sub.2 ; X.sub.1 = OCF.sub.2 HL-16: R.sub.17 = CH.sub.3 H OH A.sub.3 : X.sub.1 = CH.sub.3L-16: R.sub.17 = CH.sub.3 H OCO.sub.2 CH.sub.3 A.sub.3 : X.sub.1 = OCH.sub.2 CH.sub.3L-16: R.sub.17 = CH.sub.3 H OCO.sub.2 CH.sub.3 A.sub.4 : X.sub.1 = OCH.sub.3 ; Y.sub.2 = HL-17: R.sub.17 = H; CH.sub.3 OCO.sub.2 CH.sub.3 A.sub.4 : X.sub.1 = CH.sub.3 ;R.sub.18 = CH.sub.3 Y.sub.2 = CH.sub.3L-17: R.sub.17 = H; H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ;R.sub.18 = CH.sub.3 Y.sub.3 = OCH.sub.3L-17: R.sub.17 = H; H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ;R.sub.18 = CH.sub.3 Y.sub.3 = SCH.sub.3L-8: R.sub.11 = R.sub.12 = H OCO.sub.2 CH.sub.3 A.sub.5 : X.sub.2 = CH.sub.3 ;R.sub.13 = 1; H; Y.sub.3 = C.sub.2 H.sub.5m = 1; Q.sub.1 = SO.sub.2L-8: R.sub.11 = R.sub.12 = H OCO.sub.2 CH.sub.3 A.sub.6 : X.sub.3 = CH.sub.3R.sub.13 = H;m = 1; Q.sub.1 = SO.sub.2L-8: R.sub.11 = R.sub.12 = H OCO.sub.2 CH.sub.3 A.sub.6 : X.sub.3 = OCH.sub.3R.sub.13 = H;m = 1; Q.sub.1 = SO.sub.2L-9: R.sub.14 = R.sub.15 = H; CH.sub.3 OCO.sub.2 CH.sub.3 A.sub.2 : Y.sub.1 = O;Q.sub.2 = S X.sub.1 = OCH.sub.2 CH.sub.3L-9: R.sub.14 = R.sub.15 = H; H OCO.sub.2 CH.sub.3 A.sub.2 : Y.sub.1 = CH.sub.2 ;Q.sub.2 = S X.sub.1 = OCH.sub.3L-9: R.sub.14 = R.sub.15 = H; H OH A.sub.2 : Y.sub.1 = O;Q.sub.2 = S X.sub.1 = CH.sub.3L-10: R.sub.13 = R.sub.16 = CH.sub.3 ; H OCOCH.sub.3 A.sub.3 : X.sub.1 = OCF.sub.2 Hm = 0L-10: R.sub.13 = R.sub.16 = CH.sub.3 ; H OH A.sub.3 : X.sub.1 = OCH.sub.3m = 0L-10: R.sub.13 = R.sub.16 = CH.sub.3 ; H OH A.sub.4 : X.sub.1 = OCH.sub.3 ;m = 0 Y.sub.2 = CH.sub.3L-11: R.sub.13 = CH.sub.3 ; m = 0 H OH A.sub.4 : X.sub.1 = OCF.sub.2 H; Y.sub.2 = HL-11: R.sub.13 = CH.sub.3 ; m = 0 H OH A.sub.5 : X.sub.2 = C.sub.2 H.sub.5 ; Y.sub.3 = OC.sub.2 H.sub.5L-11: R.sub.13 = CH.sub.3 ; m = 0 H OH A.sub.5 : X.sub.2 = CH.sub.2 CF.sub.3 ; Y.sub.3 = CH.sub.3L-12: R.sub.13 = H; m = 1 H OH A.sub.5 : X.sub.2 = CH.sub.3 ; Y.sub.3 = C.sub.2 H.sub.5L-13: R.sub.13 = H; m = 1 H OH A.sub.6 : X.sub.3 = OCH.sub.3L-14: R.sub.16 = H H OH A.sub.6 : X.sub.3 = CH.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 diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
TABLE 13______________________________________ Active Weight Percent* Ingredient Diluent(s) Surfactant(s)______________________________________Wettable Powders 20-90 0-74 1-10Oil Suspensions, 3-50 40-95 0-15Emulsion, 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, N.J., 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, N.Y., 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, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., N.Y., 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, 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 the active 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, N.Y., 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 through Col. 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, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Jun. 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., N.Y., 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 7
Wettable Powder
______________________________________2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy- 80%imino)methyl]aminosulfonyl]benzoic acid, methylestersodium 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 8
Wettable Powder
______________________________________2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1- 50%(hydroxyimino)methyl]aminosulfonyl]benzoic acid,methyl estersodium 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 9
Granule
______________________________________Wettable Powder of Example 8 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 granules are dried and packaged.
EXAMPLE 10
Extruded Pellet
______________________________________N',N'--dimethyl-N--[[1-(4,6-dimethyl-1,3,5-triazin-2-yl)- 25%amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfon-amideanhydrous 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 (0.42 mm openings) may be packaged for use and the fines recycled.
EXAMPLE 11
Oil Suspension
______________________________________N',N' --dimethyl-N--[[1-(4-methoxy-6-methylpyrimidin-2- 25%yl)amino]-1-(hydroxyimino)methyl]-1,2-benzenedi-sulfonamidepolyoxyethylene 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 12
Wettable Powder
______________________________________2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy- 20%imino)methyl]aminosulfonyl]benzoic acid, methylestersodium 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 13
Low Strength Granule
______________________________________N',N'--dimethyl-N--[[1-(4,6-dimethyl-1,3,5-triazin-2-yl)- 1%animo]-1-(hydroxyimino)methyl]-1,2-benzenedisulfon-amideN,N--dimethylformamide 9%attapulgit 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 of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
EXAMPLE 14
Aqueous Suspension
______________________________________N',N'--dimethyl-N--[[1-(4-methoxy-6-methylpyrimidin-2- 40%yl)amino]-1-(hydroxyimino)methyl]-1,2-benzenedi-sulfonamidepolyacrylic 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 15
Solution
______________________________________2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1- 5%(hydroxyimino)methyl]aminosulfonyl]benzoic acid,methyl esterwater 95%______________________________________
The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
EXAMPLE 16
Low Strength Granule
______________________________________2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy- 0.1%imino)methyl]aminosulfonyl]benzoic acid, methylesterattapulgite granules 99.9%(U.S.S. 20-40 mesh)______________________________________
The active ingredient is dissolved in a solvent and the solution is sprayed upon 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 17
Granule
______________________________________2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1- 80%(hydroxyimino)methyl]aminosulfonyl]benzoic acidmethyl esterwetting 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 the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-1490microns), and packaged for use.
EXAMPLE 18
High Strength Concentrate
______________________________________N',N'--dimethyl-N--[[1-(4-methoxy-6-methylpyrimidin-2- 99%yl)amino]-1-(hydroxyimino)methyl]-1,2-benzenedi-sulfonamidesilica 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.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
EXAMPLE 19
Wettable Powder
______________________________________N',N'--dimethyl-N--[[1-(4,6-dimethyl-1,3,5-triazin-2-yl)- 90%amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfon-amidedioctyl 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 20
Wettable Powder
______________________________________2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy- 40%imino)methyl]aminosulfonyl]benzoic acid, methylestersodium 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 21
Oil Suspension
______________________________________N',N'--dimethyl-N--[[1-(dimethyl-1,3,5-triazin-2-yl)- 35%amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfon-amideblend 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.
EXAMPLE 22
Dust
______________________________________2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1- 10%(hydroxyimino)methyl]aminosulfonyl]benzoic acidmethyl esterattapulgite 10%Pyrophyllite 80%______________________________________
The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.
EXAMPLE 23
Emulsifiable Concentrate
______________________________________N',N'--dimethyl-N--[[1-(4-methoxy-6-methylpyrimidin-2- 20%yl)amino]-1-(hydroxyimino)methyl]-1,2-benzenedi-sulfonamidechlorobenzene 74%sorbitan monostearate and polyoxyethylenecondensates thereof 6%______________________________________
The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
Utility
The compounds of the present invention are active herbicides. They have utility for broad-spectrum pre-and/or post-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, drivein theaters, around billboards, highway and railroad structures. Alternatively, the subject compounds are useful for the selective pre- or post-emergence weed control in crops, such as wheat and barley.
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 subject compounds should be applied at levels of around 0.03 to 5 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low 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.
The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow.
Test A
Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia), morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum), sorghum, corn, soybean, sugar beet, rice, wheat, and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with the test chemicals 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/foliage application. At the time of treatment, the plants ranged in height 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 the following meanings:
C=chlorosis/necrosis;
E=emergence inhibition;
G=growth retardation;
H=formative effect;
U=unusual pigmentation; and
6Y=abscised buds or flowers.
Note that compounds tested are highly active herbicides at the low rates of application selected for this test. ##STR65##
TABLE A______________________________________ Cmpd. 1 Cmpd. 1 Cmpd. 2 Cmpd. 3Rate kg/ha .05 0.4 .05 .05______________________________________POST-EMERGENCEBush bean 3C,7H,6Y 9C 9C 9CCotton 5C,7H 6C,9G 4C,9G 3C,9GMorningglory 3C 4C,8G 2C,9G 3C,8HCocklebur 3G 8G 3C,9G 3C,8HSicklepod 2C 3C,8G 2C,8G 4C,9GNutsedge 2C,6G 10C 4C,9G 9CCrabgrass 0 2C,8G 1C,3H 2C,3GBarnyardgrass 2C,6H 9C 5C,9H 2C,9HWild Oats 1C 1C,7G 0 2C,4GWheat 1C 1C,9G 0 3GCorn 2U,8H 6U,9G 3U,9G 2U,9GSoybean 1C,3H 4C,9G 2C,9H 3C,9HRice 2C,8H 5C,9G 3C,9G 4C,9GSorghum 1U,9G 5U,9G 2C,9G 2C,9GSugar beet -- -- -- --PRE-EMERGENCEMorningglory 3C 8G 9G 9GCocklebur 2C,7H 8H 9H --Sicklepod 2C,5G 3C,9G 2C,8G 9GNutsedge 5G 3C,9G 2C,5G 10ECrabgrass 0 3C 1C,3G 1C,5GBarnyardgrass 3C,6H 3C,9H 5C,9H 9HWild Oats 0 2C,7G 5C,9G 8GWheat 3G 2C,8G 4C,9G 2C,8GCorn 2C,6G 1C,9G 2C,9G 2C,9HSoybean 2C 3C,6G 3C,8H 7HRice 4C,6G 10E 5C,9G 10ESorghum 2C,7H 3C,9H 4C,9G 1C,9HSugar beet -- -- -- --______________________________________ Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7Rate kg/ha .05 .05 .05 0.5______________________________________POST-EMERGENCEBush bean 1C 5C,9G,6Y 3C,6H,6Y 9CCotton 4C,8G 4C,8H 2C,5G 6C,9GMorningglory 3C,8G 3C,5G 3G 2C,7GCocklebur 2C 5G 4G 4C,9HSicklepod 5c,9G 1C 3G 9CNutsedge 0 3C,8G 7C,9G 10CCrabgrass 3C 2H 10C 4C,9GBarnyardgrass 2C,5H 3C,8H 4H 9CWild Oats 0 2C 0 5C,9HWheat 0 1C 0 5C,9GCorn 2G 3C,8H 2C,8H 5C,9GSoybean 3C,8G 2C,7H 2C,2H 5C,9GRice 3G 3C,9H 2C,8H 5C,9GSorghum 3G 3C,9G 2C,9H 4U,9GSugar beet -- -- 2C 10CPRE-EMERGENCEMorningglory 9G 3C 2C,4G 8HCocklebur 9H 9H 9H 8HSicklepod 9G 3C,8H 2C,5G 2C,9GNutsedge 9G 3C,8G 2C,5G 10ECrabgrass 3G 2C 1C 2CBarnyardgrass 2C,5G 5C,9H 2H 4C,9HWild Oats 1C 2C,8G 2C,8G 3C,9GWheat 1C 3C,9G 9G 2C,9HCorn 2C,8G 4C,9H 9G 3C,9HSoybean 8H 3C,5H 4C,7G 3C,7HRice 6G 5C,9H 3C,8H 10ESorghum 2C,5G 4C,9H 2C,9H 2C,9GSugar beet -- -- 2C,9G 9C______________________________________ Cmpd. 8 Cmpd. 9Rate kg/ha .05 .05______________________________________POST-EMERGENCEBush bean 5C,9G,6Y 5C,9G,6YCotton 9C --Morningglory 5C,9G 5C,9GCocklebur 4C,9G 4C,9GSicklepod 3C,8G 4C,3HNutsedge 2C,7G 5GCrabgrass 2C,9G 2C,8GBarnyardgrass 2C,9H 5C,9HWild Oats 2C,8G 0Wheat 5C,9G 0Corn 3U,9H 9CSoybean 2C,9H 9CRice 5C,9G 5C,9GSorghum 2C,9G 9CSugar beet 3C,9G 9CPRE-EMERGENCEMorningglory 9C 9CCocklebur 9H --Sicklepod 5C,9G 2C,9GNutsedge 10E 6GCrabgrass 3C,9G 2C,6GBarnyardgrass 4C,9H 3C,9HWild Oats 3C,9G 3C,9GWheat 10C 1C,6GCorn 9G 5C,9HSoybean 3C,9H 9HRice 10E 10ESorghum 5C,9H 5C,9HSugar beet 5C,9G 9C______________________________________
Test B
Two plastic bulb pans were filled with fertilized and limed Woodstown sandy loam. 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), pigweed (Amaranthus retroflexus), 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 preemergence 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 1 Compound 2Rate kg/ha 0.120 0.500 0.030 0.120______________________________________Crabgrass 2G 5G 2G 4GBarnyardgrass 8G,3H 10C 7G,3H 9G,5HSorghum -- -- 7G,5H 9G,5HWild Oats 2G 5G 4G 5GJohnsongrass 5G,3H 8G,3H 4G,3H 6G,2HDallisgrass 6G 8G,5H 2G 4GGiant foxtail 6G,5H 8G,5H 4G 6G,3HKy. bluegrass 8G,8C 10C 6G 7GCheatgrass 6G,3C 10C 8G,8C 8G,9CSugar beets 8G,8C 10C 8G,8C 10CCorn 7G,5H 9G,8C 6G,3H 7G,3HMustard 9G,9C 10C 9G,8C 9G,9CCocklebur 6G 7G,3H 6G 5GPigweed 8G 10C -- --Nutsedge 7G 10E 7G 7GCotton 3G 8G 3G 5G,3HMorningglory 0 6G,5H 4G 9G,5CSicklepod 6G 7G 7G 8G,3HTeaweed 5G 8G,3H 5G 10CVelvetleaf 6G,5H 9G,9C 5G,5H 8G,9CJimsonweed 6G 7G 7G 8G,8CSoybean 3G 6G,5H 3G,3H 6G,5HRice 9G,9C 10C 7G,8C 10CWheat 4G 6G 0 4G______________________________________ Compound 3 Compound 4Rate kg/ha 0.030 0.120 0.007 0.030______________________________________Crabgrass 0 6G 0 0Barnyardgrass 6G,2H 8G,5H 0 3GSorghum 6G,3H 9G,5H 0 0Wild Oats 3G 6G 0 0Johnsongrass 4G,2H 7G,5H 0 0Dallisgrass 0 5G 0 0Giant foxtail 3G 7G,3H 0 0Ky. bluegrass 5G,3H 7G,3H 4G 0Cheatgrass 8G,8C 8G,9C 0 0Sugar beets 10C 10C 6G 8GCorn 5G,3H 7G,3H 2G 3GMustard 9G,5H 9G,9C 9G 9G,9CCocklebur 0 3G 0 2GPigweed 10E 10E -- --Nutsedge 9G,9E 10E 0 5GCotton 2G 4G 2G 5GMorningglory 3G 3G 0 7GSicklepod 8G 8G 5G 6GTeaweed 7G 8G 6G 9GVelvetleaf 7G,5H 9G,8C 5G,5H 8GJimsonweed 5G 6G 0 4GSoybean 3G 6G,5H 5G 8GRice 8G,8C 10E 0 5GWheat 2G 4G 0 0______________________________________ Compound 5Rate kg/ha 0.030 0.120______________________________________Crabgrass 0 0Barnyardgrass 2G 3H,8GSorghum 2G 3H,8GWild Oats 0 2GJohnsongrass 0 2H,4GDallisgrass 4G 8GGiant foxtail 3H,4G 5H,8GKy. bluegrass 6G 10ECheatgrass 5G 8GSugar beets 5G 8GCorn 3G 3H,7GMustard 9G,9C 9G,9CCocklebur 2G 2GPigweed -- --Nutsedge 2G 6GCotton 3G 5GMorningglory 2G 2GSicklepod 2G 5GTeaweed 0 0Velvetleaf 0 5GJimsonweed 0 4GSoybean 3G 3GRice 8G 9G,9CWheat 2G 3G______________________________________
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 checked 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 as 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 greenhouse. The following species were grown in soil contained in plastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), morningglory (Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria spp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii), and wild oats (Avena fatua). The following species were grown in soil in a paper cup (12 cm diameter by 13 cm deep): sunflower, sugar beets, and rape. All plants were sprayed approximately 14 days after planting. Additional plant species, such as johnsongrass and field bindweed, are sometimes added to this test in order to evaluate unusual selectivity.
TABLE C______________________________________Over-the-Top Soil/Foliage Treatment Compound 2 Compound 5Rate, kg/ha 0.015 0.004 0.06 0.015______________________________________Soybeans 8G,6C 6G 3G 0Velvetleaf 0 0 4G 0Sesbania 0 -- 0 0Sicklepod 0 0 0 0Cotton 3G 3G 3G 3GMorningglory 2G 0 4G 3GAlfalfa 7G 5G 4G 3GJimsonweed 3G 0 0 0Cocklebur 0 -- 2G 3GSunflower 2G 0 3G 1GRape 2G 0 5G 0Sugar beets 2G 0 -- --Corn 2G 0 1C 0Crabgrass 4G 0 0 0Rice 6G 2G 6G 6GNutsedge 0 0 0 0Barnyardgrass 0 3G 0 0Wheat 0 0 0 0Giant Foxtail 2G 4G 0 0Wild Oats 0 0 0 0Sorghum 3G 5G 8G 6GJohnsongrass 0 0 0 0Field Bindweed 3G 0 0 0______________________________________
Test D
Two ten-inch in diameter plastic pans lined with polyethylene liners were filled with prepared Woodstown sandy loam soil. One pan was planted with seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), downy brome (Bromus tectorum), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), quackgrass (Agropyron repens), Italian ryegrass (Lolium multiflorum) and ripgut brome (Bromus rigidus). The other pan was planted with seeds of Russian thistle (Salsola kali), tansy mustard (Descuraina pinnata), cleavers (Galium aparine), tumble mustard (Sisymbrium altissium), kochia (Kochia scoparia), shepherd's purse (Capsella bursa-pastoris), Matricaria inodora, black nightshade (Solanum nigrum), yellow rocket (Barbarea vulgaris), rapeseed (Brassica napus), and wild buckwheat (Polygonum convolvulus). The above two pans were treated preemergence. At the same time, two pans in which the above plant species were growing were treated postemergence. Plant height at the time of treatment ranged from 1-15 cm depending on plant species.
The compounds applied were diluted with a nonphytotoxic solvent and sprayed over the top of the pans. An untreated control and a solvent-alone control were included for comparison. All treatments were maintained in the greenhouse for 19-21 days at which time the treatments were compared to the controls and the effects visually rated. The recorded data are presented in Table D. Some of the compounds tested have utility for selective weed control in cereal crops such as wheat and barley.
TABLE D______________________________________ Compound 2 Pre-Emergence Post-EmergenceRate kg/ha 0.060 0.015 0.060 0.015______________________________________wheat 7G 2G 6G 3Gbarley 1C,7G 2G 6G 3Gwild oats 1C,7G 5G 5G 2Gdowny brome 2C,9G 8G 8G 7Gcheatgrass 1C,9G 8G 8G 7Gblackgrass 2C,8G 7G 5G 3Gannual bluegrass 8G 7G 7G 3Ggreen foxtail 2C,8G 2C,4G 2C,8G 4Gquackgrass 9G 8G 8G 6GItalian ryegrass 1C,8G 7G 4C,8G 7Gripgut brome 8G 8G 2C,8G 7GRussian thistle 2C,3G 2G 8C,8G 4C,5Gtansy mustard 2C,9G 9G 8C,8G 5C,7GGalium aparine 6G 8G 7G 4Gtumble mustard 1C,8G 9G 10C 7Gkochia 7G 5G 3C,8G 4Gshepherd's purse 2C,9G 9G 4C,9G 7GMatricaria inodora 7G 7G 8C,8G 2C,7Gblack nightshade 8G 5G 6G 6Gyellow rocket 9G 8G 7G 5Grapeseed 2C,9G 9G 10C 2C,8Gwild buckwheat 7G 6G 7G 4G______________________________________ Compound 3 Pre-Emergence Post-EmergenceRate kg/ha 0.060 0.015 0.060 0.015______________________________________wheat 3G 0 3G 0barley 3G 0 5G 0wild oats 5G 0 4G 0downy brome 9G 8G 9G 7Gcheatgrass 2C,9G 7G 8G 6Gblackgrass 7G 6G 6G 3Gannual bluegrass 7G 6G 2C,8G 3Ggreen foxtail 2C,6G 3G 2C,6G 6Gquackgrass 9G 8G 8G 7GItalian ryegrass 8G 8G 2C,8G 6Gripgut brome 8G 6G 7G 6GRussian thistle 1C,2G 0 8C,8G 0tansy mustard 9G 9G 10C 9GGalium aparine 10E 8G 6G 5Gtumble mustard 2C,9G 9G 10C 9Gkochia 8G 2C,5G 2C,8G 5Gshepherd's purse 9C,9G 9C,9G 10C 2C,8GMatricaria inodora 8G 9G 8C,8G 8C,8Gblack nightshade 6G 3G 7G 6Gyellow rocket 9G 7G 8C,8G 8C,8Grapeseed 3C,9G 9G 10C 10Cwild buckwheat 6G 4G 2C,8G 7G______________________________________ Compound 5 Pre-Emergence Post-EmergenceRate kg/ha 0.060 0.250 0.060 0.250______________________________________wheat 1C,2G 5G 2G 7Gbarley 6G 2C,8G 3G 7Gwild oats 5G 7G 3G 5Gdowny brome 5G 8G 5G 6Gcheatgrass 6G 8G 5G 7Gblackgrass 5G 1C,7G 6G 2C,7Gannual bluegrass 6G 1C,8G 4G 3C,8Ggreen foxtail 0 2C,6G 0 2C,5Gquackgrass 4G 8G 2G 6GItalian ryegrass 8G 2C,9G 2C,6G 2C,8Gripgut brome 6G 1C,8G 5G 7GRussian thistle 0 2C,5G 0 10Ctansy mustard 8G 2C,9G 5G 8GGalium aparine 9G 10E 0 3Gtumble mustard 7G 9G 0 6Gkochia -- -- -- 0shepherd's purse 2C,9G 10C 5G 10CMatricaria inodora 8G 9G 3G 9Gblack nightshade 0 5G 0 4Gyellow rocket 8G 9G 0 6Grapeseed 2C,8G 9G 7G 9C,9Gwild buckwheat 0 6G 0 3G______________________________________

Number	Name	Date
4310346	Levitt et al.	Jan 1982
4544401	Levitt	Oct 1985
4559079	Shiokawa	Dec 1985
4568381	Saito	Feb 1986
4602938	Moriya	Jul 1986
4721785	Moriya et al.	Jan 1988
4725303	Moriya et al.	Feb 1988

Number	Date	Country
027482	Apr 1981	EPX
792657	Jun 1980	ZAX

	Number	Date	Country
Parent	60212	Jun 1987
Parent	736950	May 1985

	Number	Date	Country
Parent	551381	Nov 1983
Parent	455504	Jan 1983

Herbicidal N-hydroxy-N'-sulfonylguanidines

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