Herbicidal Sulfonamides

This invention relates to herbicidal sulfonamides, and, more particularly, to (dimethoxymethyl)pyrimidinyl sulfonylurea compounds which are selective pre-emergence and/or post-emergence herbicides.

U.S. Pat. Nos. 4,127,405 and 4,169,719 disclose herbicidal methoxymethylpyrimidine sulfonylurea compounds of the type which contain a --CH.sub.2 OCH.sub.3 heterocyclic substituent.

European Pat. No. 7687 discloses herbicidal sulfonylurea compounds such as, among others, ##STR1## where X is CH.sub.3 or OCH.sub.3 ;

Z is CH or N; and

Y is C.sub.1 -C.sub.4 alkyl substituted with OCH.sub.3, OC.sub.2 H.sub.5, CN, C(O)L, or 1-3 atoms of F, Cl, or Br, where L is NH.sub.2, OH, N(OCH.sub.3)CH.sub.3, NH(C.sub.1 -C.sub.4 alkyl), N(C.sub.1 -C.sub.4 alkyl) or C.sub.1 -C.sub.6 alkoxy.

U.S. application Ser. No. 116,920, discloses herbicidal substituted benzenesulfonylureas which contain as the heterocyclic substituent ##STR2## where X is CH.sub.3 or OCH.sub.3 ;

Z is CH or N; and

Y is (among others) C.sub.1 -C.sub.4 alkyl substituted with OC.sub.2 H.sub.5, CN, CO.sub.2 H, CO.sub.2 H.sub.3 or CO.sub.2 C.sub.2 H.sub.5.

J. Am. Chem. Soc., 69, 3072 (1947) teaches compounds of the formula: ##STR3## where A is H or ##STR4## X is Cl, CH.sub.3, CH.sub.3 O, CH.sub.2 OCH.sub.3, or H; and Y is CH(OCH.sub.3).sub.2 or CH(OC.sub.2 H.sub.5).sub.2 ;

and their use as antibacterial agents.

This invention relates to novel compounds of Formula I, suitable agricultural compositions containing them, and their method of use as general and/or selective pre-emergence and/or post-emergence herbicides or plant growth regulants. ##STR5## wherein X is CH.sub.3, OCH.sub.3, Cl, C.sub.2 H.sub.5 or OC.sub.2 H.sub.5 ;

Z is CH or N;

Y is CH.sub.2 OR, CH.sub.2 S(O).sub.m R.sub.1, CH(QR.sub.1).sub.2, R.sub.1 CHS(O).sub.m R.sub.1, ##STR6## R is H, C(O)R.sub.3, CO.sub.2 R.sub.4, C(O)NR.sub.5 R.sub.6 or ##STR7## R.sub.1 is C.sub.1 -C.sub.2 alkyl; R.sub.2 is --CH.sub.2 CH.sub.2 --, --CH(CH.sub.3)CH.sub.2 -- or --CH.sub.2 CH.sub.2 CH.sub.2 --;

R.sub.3 is C.sub.1 -C.sub.3 alkyl;

R.sub.4 is C.sub.1 -C.sub.3 alkyl;

R.sub.5 is H or CH.sub.3 ;

R.sub.6 is C.sub.1 -C.sub.3 alkyl;

Q is O or S;

m is 0, 1 or 2;

A is ##STR8## R.sub.7 is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, F, Cl, I, Br, NO.sub.2, CF.sub.3, CO.sub.2 R.sub.9, SO.sub.2 NR.sub.10 R.sub.11, SO.sub.2 N(OCH.sub.3)CH.sub.3, OSO.sub.2 R.sub.12, S(O).sub.n R.sub.13, LCF.sub.3, LCHF.sub.2, LCF.sub.2 CF.sub.2 H, CH.sub.2 Cl, CHCl.sub.2, CH.sub.2 OCH.sub.3 or CH.sub.2 OCH.sub.2 CH.sub.3 ;

R.sub.8 is H, F, Cl, Br, CF.sub.3, NO.sub.2, C.sub.1 -C.sub.3 alkyl C.sub.1 -C.sub.3 alkoxy, OCF.sub.2 H or SCF.sub.2 H;

R.sub.9 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.10 and R.sub.11 are independently C.sub.1 -C.sub.3 alkyl;

R.sub.12 is C.sub.1 -C.sub.4 alkyl, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 or C.sub.1 -C.sub.4 alkyl substituted with 1-3 atoms of F, Cl or Br;

R.sub.13 is C.sub.1 -C.sub.4 alkyl or CH.sub.2 CH.dbd.CH.sub.2 ;

n is 0 or 2;

L is O, S or SO.sub.2 ;

R.sub.14 is H, CH.sub.3, OCH.sub.3, F, Cl, Br, NO.sub.2, SO.sub.2 N(CH.sub.3).sub.2, OSO.sub.2 R.sub.1 or S(O).sub.n R.sub.1 ;

R.sub.15 is H, Cl, Br, CH.sub.3, OCH.sub.3 or NO.sub.2 ;

R.sub.16 is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, F, Cl, Br, CF.sub.3, CO.sub.2 R.sub.9, SO.sub.2 NR.sub.10 R.sub.11, SO.sub.2 N(OCH.sub.3)CH.sub.3 or S(O).sub.n R.sub.13 ;

R.sub.17 is H, F, Cl, Br, CH.sub.3 or OCH.sub.3 ;

W is O or S;

W.sub.1 is O or S;

R.sub.18 is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, F, Cl, Br, NO.sub.2, CO.sub.2 R.sub.9, SO.sub.2 NR.sub.10 R.sub.11, SO.sub.2 N(OCH.sub.3)CH.sub.3 or S(O).sub.n R.sub.13 ;

R.sub.19 is Cl, NO.sub.2, CF.sub.3, CO.sub.2 R.sub.9, SO.sub.2 N(OCH.sub.3)CH.sub.3, SO.sub.2 NR.sub.10 R.sub.11, OSO.sub.2 R.sub.12, S(O).sub.n R.sub.13, C.sub.1 -C.sub.3 alkyl, or C.sub.1 -C.sub.3 alkoxy optionally substituted with 1-5 atoms of Cl or F;

R.sub.20 is Cl, NO.sub.2, CF.sub.3, CO.sub.2 R.sub.9, SO.sub.2 N(OCH.sub.3)CH.sub.3, C.sub.1 -C.sub.3 alkyl, OSO.sub.2 R.sub.12 or C.sub.1 -C.sub.3 alkoxy optionally substituted with 1-5 atoms of Cl or F;

R.sub.21 is H or CH.sub.3 ;

and their agriculturally suitable salts; provided that

(1) the total number of carbon atoms of R.sub.10 and R.sub.11 is less than or equal to 4;

(2) when X is Cl, then Z is CH;

(3) when W is O, then R.sub.18 is H, Cl, Br, CH.sub.3 or CO.sub.2 R.sub.9 ;

(4) when W is O and R.sub.18 is H, Cl, Br, or CH.sub.3, then A is ##STR9## and (5) when W.sub.1 is S, then R.sub.21 is H and A is ##STR10##

Preferred for their higher herbicidal activity and/or more favorable ease of synthesis are:

(1) Compounds of Formula I where W.sub.1 is O, X is CH.sub.3, OCH.sub.2 CH.sub.3 or OCH.sub.3 and R.sub.21 is H;

(2) Compounds of Preferred 1 where Y is CH(QR.sub.1).sub.2, CH.sub.2 SR.sub.1, CR.sub.1 (QR.sub.1).sub.2, ##STR11## (3) Compounds of Preferred 2 where Y is CH(QR.sub.1).sub.2, CH.sub.2 SR.sub.1 or ##STR12## and Q is O; (4) Compounds of Preferred (3) wherein

A is ##STR13## R.sub.7 is C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, Cl, NO.sub.2, CO.sub.2 R.sub.9, SO.sub.2 (C.sub.1 -C.sub.3 alkyl), SO.sub.2 NR.sub.10 R.sub.11, SO.sub.2 N(OCH.sub.3)CH.sub.3, OSO.sub.2 R.sub.13, CH.sub.2 OCH.sub.3 or LCF.sub.2 H;

R.sub.14 is CH.sub.3, OCH.sub.3, Cl, OSO.sub.2 CH.sub.3 or SO.sub.2 (C.sub.1 -C.sub.3 alkyl);

R.sub.16 is CH.sub.3, OCH.sub.3, Cl, SO.sub.2 CH.sub.3 or SO.sub.2 N(CH.sub.3).sub.2 ;

R.sub.18 is CH.sub.3, Cl, Br, CO.sub.2 R.sub.9 or SO.sub.2 CH.sub.3 ;

(5) Compounds of Preferred (4) where A is ##STR14## and (6) Compounds of Preferred (5) where

R.sub.7 is CO.sub.2 CH.sub.3, CO.sub.2 CH.sub.2 CH.sub.3, SO.sub.2 CH.sub.3, SO.sub.2 CH.sub.2 CH.sub.3, SO.sub.2 N(CH.sub.3).sub.2, OSO.sub.2 CH.sub.3, OSO.sub.2 CH.sub.2 CH.sub.3 ; and

R.sub.8 is H, F, Cl, CF.sub.3, CH.sub.3 or OCH.sub.3.

Specifically preferred are:

3-[[(4-dimethoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl]- 2-thiophenecarboxylic acid, methyl ester;

2-chloro-N-[(4-dimethoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]benzene sulfonamide;

2-[[(4-dimethoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl]b enzoic acid, methyl ester;

N-[(4-dimethoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]-2-methylsulfony lbenzenesulfonamide;

N-[(4-dimethoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]-2-nitrobenzenes ulfonamide;

2-[[(4-dimethoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl]b enzoic acid, 2-propyl ester;

2-[[[4-methyl-6-(tetrahydropyran-2-yloxymethyl)pyrimin-2-yl]aminocarbonyl]a minosulfonyl]benzoic acid, methyl ester;

2-[[[4-(hydroxymethyl)-6-methylpyrimidin-2-yl]aminocarbonyl]aminosulfonyl]b enzoic acid, methyl ester;

2-[[[4-(acetyloxymethyl)-6-methylpyrimidin-2-yl]aminocarbonyl]aminosulfonyl ]benzoic acid, methyl ester;

2-[[(4-dimethoxymethyl-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl] benzoic acid, methyl ester;

5-chloro-2-[[(4-dimethoxymethyl-6-methylpyrimidin-2-yl)aminocarbonyl]aminos ulfonyl]benzoic acid, methyl ester;

5-chloro-2-[[(4-dimethoxymethyl-6-methoxypyrimidin-2-yl)aminocarbonyl]amino sulfonyl]benzoic acid, methyl ester;

2-[[(4-(1,3-dioxan-2-yl)-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfony l]benzoic acid, methyl ester; and

2-[[(4-(1,3-dioxolan-2-yl)-6-methoxypyrimidin-2-yl)aminocarbonyl]aminosulfo nyl]benzoic acid, methyl ester.

The compounds of this invention are highly active pre-emergence and/or post-emergence herbicides. Certain compounds of this invention are useful for selective weed control in crops such as cotton, soybeans, wheat or corn.

The compounds of Formula I may be prepared by the reaction of an appropriately substituted sulfonyl isocyanate of Formula II with an appropriate 2-aminoheterocycle of Formula III according to Equation 1: ##STR15## wherein A, X, R.sub.21 and Z(O).sub.m are as previously defined;

Y is CH.sub.2 OR, CH.sub.2 SR.sub.1, CH(QR.sub.1).sub.2 CH(QR.sub.2 Q), CH(R.sub.1)S(O).sub.m R.sub.1, C(R.sub.1)(QR.sub.1).sub.2 or C(R.sub.1)(QR.sub.2 Q);

R is ##STR16## and m, R.sub.1 and R.sub.2 are as previously defined.

The reaction of Equation 1 is best carried out in an inert aprotic solvent such as methylene chloride, tetrahydrofuran, acetonitrile at a temperature between 20.degree. and 80.degree.. A catalytic amount of DABCO (1,4-diazabicyclo[2.2.2]octane) may be used to accelerate the reaction. In the cases in which the products are insoluble in the reaction solvent, they may be isolated by simple filtration. When the products are soluble in the reaction solvent they are isolated by evaporation of the solvent and trituration of the residue with solvents such as 1-chlorobutane, ethyl ether or methanol and filtration.

Preparation of isocyanates (II) is described in the following: U.S. Pat. No. 4,127,405, U.S. Pat. No. 4,169,719, Eur. Pat. No. 7,687, Eur. Pat. No. 13,480, Eur. Pat. No. 23,141, Eur. Pat. No. 23,422, Eur. Pat. No. 30,141, and Brit. 2,065, 116-A, the disclosures of which are herein incorporated by reference. Furthermore, the sulfonyl isocyanates of Formula IIa, which are disclosed in European Patent Pub. 44,212, may be prepared analogously to the teachings of U.S. Pat. No. 4,127,405. ##STR17## wherein R.sub.8 and R.sub.12 are as previously defined.

Certain compounds of Formula III are known in the art. For example, the compounds IIIa shown below: ##STR18## wherein X=CH.sub.3, Cl or OCH.sub.3 ; and

R.sub.1 =CH.sub.3 or C.sub.2 H.sub.5 ;

are described by W. Braker, et al., J. Amer. Chem. Soc., 69, 3072 (1947), the disclosures of which are herein incorporated by reference.

Triazines of Formula IIIb may be prepared according to the methods outlined in Equations 2 and 3. ##STR19## wherein R.sub.1 and R.sub.2 are as previously defined; and

Y is as defined in Equation 1, with m=0 or 2.

The reaction of Equation 2a is carried out according to the teachings of J. M. McElvain and R. L. Clarke, J. Amer. Chem. Soc., 69, 2657 (1947), in which the preparation of ethyl diethoxyiminoacetate is described. The intermediate N-cyanoimidates of Formula VI may be prepared according to the teaching of D. Lwowski in Synthesis, 1971, 263, by reacting V with cyanamide at pH 5.5, and these may be condensed according to reaction 2c with the appropriate compound of Formula VII in an alcoholic solvent at 25.degree. to 80.degree. C. to provide the appropriate triazines. Alternatively, the reaction of Equation 3a, described for substituted acetonitriles by F. C. Schaefer and G. A. Peters in J. Org. Chem., 26, 412 (1961), may be used to convert nitriles of Formula IV to the corresponding iminoesters. The free base may be carried on through reactions 2b and 2c, or, alternatively, converted to the amidinium hydrochloride salts (VIII) as described in the aforementioned reference. The compounds of Formula VIII may be converted to the compounds IIIb by the reaction of Equation 3c, in which VIII is contacted with a compound of Formula IX at 0.degree. to 30.degree. C. in the presence of 3-4 equivalents of the appropriate sodium alkoxide in the appropriate alcohol. The product may be isolated by evaporation of solvent, neutralization with aqueous acetic acid, and filtration. ##STR20## wherein Y is as defined in Equation 1 with m=0;

X is R.sub.1 or SCH.sub.3 ; and

R.sub.1 and R.sub.2 are as previously defined.

The compounds of Formula IIIc may be prepared by the sequence of reactions outlined in Equation 4. ##STR21## wherein Y, m, R.sub.1 and R.sub.2 are as defined in Equation 3.

The reactions of Equations 4a and 4b are carried out as described by W. Braker, et al., loc. cit.

The compounds of Formula IIId may be prepared by similar methods shown in Equation 5. ##STR22## wherein R.sub.21, R.sub.1 and Y are as defined in Equation 1.

The reactions of Equations 5a and 5b are conducted as described for 2-amino-4-hydroxy-6-dimethoxymethylpyrimidine (J. I. De Graw and V. H. Brown, J. Het. Chem., 13, 439 (1976)). The silver salt of XIII may be prepared by addition of ammonia to an aqueous solution of XIII and an equivalent amount of silver nitrate. The dried silver salt may be contacted with one equivalent of methyl or ethyl iodide in a nonpolar solvent such as benzene at 25.degree. to 80.degree. C. to provide pyrimidines of Formula IIId after purification by column chromatography or recrystallization.

Alternatively, the compounds of Formula IIId may be prepared via the corresponding chloropyrimidines (IIIe). These may be obtained by the reaction of Equation 6a, in which a compound of Formula XIII is contacted with 2-5 equivalents of phosphorous oxychloride at 20.degree.-90.degree. C. for 3-30 hours. The product is isolated by removal of excess POCl.sub.3 in vacuo, treatment of the residue with ice-water, extraction into an organic solvent, concentration, crystallization or column chromatography. The chloropyrimidines may then be converted to the compounds of Formula IIId by contacting with one equivalent of the appropriate sodium alkoxide in alcohol at 0.degree.-30.degree. C. followed by concentration and precipitation with ice-water. ##STR23## wherein Y is CH(QR.sub.1).sub.2, CH.sub.2 SR.sub.1, CH(QR.sub.2 Q), C(R.sub.1)(QR.sub.1).sub.2, CH(R.sub.1)S(O).sub.m R.sub.1 or C(R.sub.1)(QR.sub.2 Q);

R.sub.1, R.sub.2 and R.sub.21 are as defined in Equation 1; and

m=0 or 2.

The ketoesters of Formula XII may be prepared by the methods of Equation 7. ##STR24## wherein m, Y and R.sub.1 are as defined in Equation 3.

The reaction of Equation 7a is carried out by the slow addition of the appropriate dialkyl carbonate to a solution of the appropriate methyl ketone of Formula XV in an inert solvent (such as toluene) at 30.degree.-110.degree. in the presence of 1-2 equivalents of sodium hydride. The product may be isolated by concentration, neutralization, and extraction from water into an organic solvent, such as diethyl ether. The product may then be purified by distillation. Compounds of Formula XIIa may be obtained by the well-known reaction of a .gamma.-chloroacetoacetic ester (XVI) with the appropriate sodium mercaptide or alkylsulfinate in a hydroxylic or dipolar aprotic solvent.

Cyclic acetals of formula IIIe may be prepared from compounds of Formula IIIa according to Equation 8 by acetal exchange. ##STR25## wherein X, Q, Z, R.sub.1 and R.sub.2 are defined in Equation 1; and

R.sub.22 is H, CH.sub.3 or C.sub.2 H.sub.5.

The reaction of Equation 8 is carried out by heating the acyclic acetal in a inert solvent in the presence of one equivalent of a compound of Formula XVII and slightly more than one equivalent of an acidic catalyst, such as p-toluenesulfonic acid or boron trifluoride etherate with distillation of the by-product alcohol. The compound of Formula IIIe may be isolated by extraction with an organic solvent, and purified by crystallization or column chromatography.

The synthesis of N-methyl compounds of Formula IIIg may be accomplished by the procedure shown in Equation 9. ##STR26## wherein Z, R.sub.1 and Q are as previously defined;

Y is as defined in Equation 1; and

X is CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3 or OC.sub.2 H.sub.5.

The reaction of Equation 9a may be carried out by stirring a mixture of IIIf with one equivalent each of sodium hydride and dimethyl carbonate for 1-3 days in an inert solvent such as tetrahydrofuran or dimethylformamide. The product of Formula XVIII may be isolated by evaporation of solvent, neutralization with aqueous acetic acid, and filtration of the product. The reaction of Equation 8b is performed by adding XVI to a slurry of one equivalent of sodium hydride in tetrahydrofuran at 0.degree.-30.degree., stirring for 1/2 hour, and adding methyl iodide, heating to reflux for 1-20 hours, and stirring with water and aqueous sodium hydroxide for 1-20 hours at 20.degree.-30.degree.. The product is isolated by evaporating the solvent, adding ice-water, and filtering.

The acetals and ketals of Formula IIIi may be prepared from the corresponding thioethers of Formula IIIh by the reaction of Equation 10. ##STR27## wherein X, R.sub.1, R.sub.21 and Z are as previously defined; and

R.sub.22 is H, CH.sub.3 or C.sub.2 H.sub.5.

The reaction of Equation 10 may be carried out by adding 2 to 2.3 equivalents of N-chlorosuccinimide to an alcoholic solution of a sulfide of Formula IIIh in the presence of 0.01 to 0.2 equivalents of a strong acid, such as H.sub.2 SO.sub.4, at -20.degree. to 20.degree. C. After 10 to 100 minutes, the reaction mixture is concentrated, diluted with water, and the reaction product is isolated by crystallization or extraction into an organic solvent.

Thioacetals and thioketals of Formula IIIj may be prepared by the reaction of Equation 11. ##STR28## wherein X is CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3 or OC.sub.2 H.sub.5 ; and

Z, R.sub.1, R.sub.21 and R.sub.22 are as defined in Equation 10.

The reaction of Equation 11a may be carried out by contacting a carbamate of Formula XVIIIa with 2-2.5 equivalents of lithium diisopropylamide in a solvent such as tetrahydrofuran at -78.degree. and then with 1 to 2 equivalents of the appropriate dialkyl disulfide and allowing the mixture to warm to 20.degree.. The product of Formula XVIIIb may be isolated by concentration, neutralization, and extraction into an organic solvent. Purification may be accomplished by column chromatography or recrystallization. The reaction of Equation 11b is carried out by contacting with aqueous alkali for 10-100 minutes at 20.degree.-80.degree. and extracting the product into an organic solvent. The product may be isolated by concentration and crystallization.

The preparation of compounds of Formula IIIk is shown in Equation 12. ##STR29## wherein Z, R.sub.1 and X are as defined in Equation 11.

The reaction of Equation 12a is carried out as described for Equation 11a, only using one equivalent of the appropriate alkyl iodide, rather than a disulfide. The reaction of Equation 12b is carried out as described for Equation 11b.

Sulfoxides and sulfones of Formula IIIl and IIIo, respectively, may be prepared from the corresponding sulfides of Formula IIIh as shown in Equation 13. ##STR30## wherein Z, X, R.sub.1, R.sub.21 and R.sub.22 are as defined in Equation 10.

The reaction of Equation 13a is carried out by contacting IIIh with 0.9 to 1.1 equivalents of m-chloroperbenzoic acid in an inert solvent at -20.degree. to 0.degree. for 1 to 2 hours, concentration, and trituration with ether. If the product is ether-soluble, it is isolated by washing an ether solution with aqueous bicarbonate and concentration of the dried ether phase. The preparation of the corresponding sulfones is accomplished in the same way except that 2 to 2.2 equivalents of MCPBA are used at 0.degree.-30.degree. for 1-24 hours.

Compounds of Formula Ib may be prepared by acidic hydrolysis of compounds of Formula Ia according to Equation 14: ##STR31## wherein A, X, R.sub.21 and Z are as defined in Equation 1.

The reaction of Equation 14 is carried out by stirring a solution or suspension of Ia in aqueous acetone containing a catalytic amount of a strong mineral acid, such as hydrochloric or sulfuric acid, at 0.degree. to 30.degree. C., followed by concentration and filtration of the product.

The compounds of Formula Ib may be in turn converted to compounds of Formulae Ic, Id, or Ie according to Equation 15: ##STR32## wherein A, X, Z, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.21 are as previously defined.

The reactions of Equation 15 are carried out by contacting a compound of Formula Ib with at least one equivalent of an alkyl carboxylic anhydride, carbonyl chloride, chloroformate or carbamoyl chloride in an inert solvent in the presence of an excess of an acid acceptor such as pyridine, triethylamine, or aqueous sodium carbonate, followed by isolation of the product by acidification and crystallization or extraction into an organic solvent. Alternatively, compounds of Formula Ie wherein R.sub.5 =H may be prepared by contacting the appropriate compound of Formula Ib with one equivalent of an appropriate alkyl isocyanate in an inert solvent and filtration of the product.

Certain compounds of Formula I may also be prepared by the reactions of Equation 16. ##STR33## wherein R.sub.21, X and A are as previously defined, provided that R.sub.7, R.sub.16, R.sub.18 and R.sub.19 are not CO.sub.2 R.sub.9.

The reaction of Equation 16a is conducted in the same manner as described for Equation 1. The resulting compounds of Formula XIX may be converted to compounds of Formula If by contacting them with 3-5 equivalents of diisobutyl aluminum hydride in an ethereal solvent at -20.degree. to 20.degree., after which the reaction mixture is quenched with aqueous mineral acid and extracted with an organic solvent. The product may be isolated by evaporation of solvent and crystallization.

Equation 17 outlines the preparation of the compounds of Formula XX. ##STR34## wherein R.sub.1 and R.sub.21 are as previously defined.

The pyrimidine of Formula XXII is described by Z. Budesinsky and F. Roubinek, in Coll. Czech. Chem. Comm., 26, 2871 (1961). This may be heated in an autoclave at 80.degree. to 140.degree. with ammonia or methyl amine to afford the amino acids of Formula XXIII. These may be esterified in the usual manner with methanol and acid, followed by evaporation of solvent, neutralization and filtration to afford the compounds of Formula XXa.

The preparation of XXb (R.sub.21 =H) is reported in J. Org. Chem., 26, 2755, by G. Davies, et al., and the N-methyl compounds (R.sub.21 =CH.sub.3) may be prepared in an analogous fashion. The reaction of Equation 17c is conducted according to the procedure described for Equation 6b.

To 6.9 g of sodium pellets in 120 ml of toluene containing 50 g of methyl dimethoxyacetate was added 20 g of acetone dropwise over 30 minutes at 0.degree.-20.degree.. The mixture was stirred overnight at room temperature, concentrated at reduced pressure, and the product was precipitated with ether and filtered. Ten ml of acetic acid in ice-water was added, and the .beta.-diketone was extracted with methylene chloride. The residue from concentration of the organic extract was heated with 25 g of guanidine carbonate at 80.degree.-90.degree. for 30 minutes, cooled, digested with methylene chloride, filtered, dried with sodium sulfate, filtered, concentrated at reduced pressure, and triturated with petroleum ether to provide 11 g of 2-amino-4-dimethoxymethyl-6-methylpyrimidine, m.p. 69.degree.-71.degree. (lit, m.p. 71.degree.-74.degree.).

NMR (CDCl.sub.3).delta.: 2.3 (s, 3), 3.3 (s, 6), 5.0 (s, 1), 5.9 (br s, 2), 6.7 (s, 1).

A solution of 0.3 g of 2-amino-4-dimethoxymethyl-6-methylpyrimidine in 50 ml of ether was stirred overnight at room temperature with 0.46 g of o-chlorobenzenesulfonyl isocyanate. The product was filtered and washed with hexane to provide 0.5 g of the title compound, m.p. 150.degree.-153.degree..

NMR (CDCl.sub.3).delta.: 2.5 (s, 3), 3.4 (s, 6), 5.2 (s, 1), 7.1 (s, 1), 7.4 (m, 3), 7.9 (br s, 1), 8.3 (m, 1).

A solution containing 30 g of methyl glycolate, 33 g of dihydropyran, and 0.2 g of p-toluenesulfonic acid in 100 ml of toluene was stirred at room temperature overnight. After cooling to -5.degree., 6.8 g of sodium pellets was added, followe by 24 ml of acetone at -5.degree. to 8.degree.. Stirring was continued for 20 hours at room temperature, after which time hexane was added, and the solution was poured into ice-water and partitioned. The aqueous phase was washed with ether and acidified with 20 ml of acetic acid, extracted with 600 ml of methylene chloride, the organic layer was dried (MgSO.sub.4) and concentrated, and the residue was heated at 80.degree.-90.degree. with 28 g of guanidine carbonate for 1 hour. Addition of ice-water to the cooled reaction mixture precipitated the product, which was filtered and dried to afford the title compound, m.p. 109.degree.-110.5.degree..

NMR (CDCl.sub.3).delta.: 1.7 (br s, 6), 2.3 (s, 3), 3.6 (br m, 2), 4.5 (d, 2), 4.7 (m, 1), 5.4 (br s, 2), 6.6 (br s, 1).

To a solution of 3.25 g of the product from Example 3 in 50 ml of ether was added 3.75 g of 2-methoxycarbonylbenzenesulfonyl isocyanate and the mixture was stirred for 3 hours under nitrogen. The precipitated product was filtered and washed with ether to afford 6.0 g of the title compound, m.p. 126.degree.-128.degree. (d).

A solution of 6 g of the product prepared in Example 4 in 50 ml of acetone was stirred with 3 ml of 1N aqueous HCl for 3 days at room temperature, concentrated at reduced pressure, and the residue was thoroughly washed with water to provide 4 g of the title compound, m.p. 140.degree.-141.degree..

NMR (CDCl.sub.3 +DMSO-d.sub.6).delta.: 2.5 (s, 3), 3.9 (s, 3), 4.6 (br s, 2), 7.0 (br s, 1), 7.6 (m, 3), 8.3 (m, 1), 9.6 (br s, 1).

To 0.5 g of the compound from Example 5 was added 1 ml of acetic anhydride and 1 ml of pyridine. After 1 hour at room temperature, ice-water was added, the precipitated oil was triturated, filtered, and washed with water to afford 0.4 g of the title compound, m.p. 145.degree.-150.degree..

NMR (CDCl.sub.3).delta.: 2.2 (s, 3), 2.6 (s, 3), 3.9 (s, 3), 5.2 (s, 2), 6.9 (s, 1), 7.7 (m, 3), 8.3 (br s, 1), 8.4 (m, 1), 13.1 (br s, 1).

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, can contain from about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

Lower or higher levels of active ingredients 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, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0.degree. C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, 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, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 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, June 3, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 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.

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.

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.

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.

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.

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.

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 openings) and packaged.

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.

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

The salt is added directly to the water with stirring to produce the solution, which may then be

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.

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 (1410-149 microns), and packaged for use.

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.

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.

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.

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.

The compounds of the present invention are highly 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, drive-in theaters, around billboards, highway and railroad structures. Alternatively, the subject compounds are useful for selective pre- or post-emergence weed control in crops, such as cotton, soybeans and wheat.

The rates of application for the compounds of the invention are influenced by a number of factors, including their use whether as selective or general herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulation ingredients, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.01 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 commerical herbicide, such as, for example those listed below.

The compounds of this invention may be used in combination with other commercial herbicides such as:

The compounds of this invention may particularly be useful in combination with the following herbicides for use as pre-emergent treatments for control of weeds in soybeans:

Also preferred are mixtures of some of the compounds of this invention with other sulfonylurea herbicides which may be useful for controlling weeds in soybeans. An example of such a sulfonylurea herbicide is:

2-hydroxy-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesu lfonamide, 1-propanesulfonate.

The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results are shown below.

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia), morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rice, wheat and nutsedge tubers (Cyperus rotundus) were planted in a growth medium and treated pre-emergence with the chemicals dissolved in a non-phytotoxic solvent. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the third trifoliolate leaf expanding, crabgrass, barnyardgrass and wild oats with two leaves, cassia with three leaves (including cotyledonary ones), morningglory and cocklebur with four leaves (including the cotyledonary ones), sorghum and corn with four leaves, soybean with two cotyledonary leaves, rice with three leaves, wheat with one leaf, and nutsedge with three to five leaves were sprayed. Treated plants and controls were maintained in a greenhouse for sixteen days, whereupon all species were compared to controls and visually rated for response to treatment. The ratings 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 or necrosis;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

S=albinism;

U=unusual pigmentation;

X=axillary stimulation; and

6Y=abscised buds or flowers.

The ratings for the compounds tested by this procedure are presented in Table A.

Two plastic bulb pans were filled with fertilized and limied Fallsington silt loam soil. One pan was planted with corn, sorghum, Kentucky bluegrass and several grass weeds. The other pan was planted with cotton, soybeans, purple nutsedge (Cyperus rotundus), and several broadleaf weeds. The following grass and broadleaf weeds were planted: crabgrass Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium pensylvanicum), 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 pre-emergence with several test compounds within the scope of the invention.

Twenty-eight days after treatment, the plants were evaluated and visually rated for response to the chemical treatments utilizing the rating system described previously for Test A. The data are summarized in Table B. At least one compound exhibits utility for pre-emergence weed control in soybeans and cotton. PRE-EMERGENCE ON FALLSINGTON SILT LOAM Compound 2 Compound 3 Compound 4 Compound 20 Compound 21 Cmpd. 22 Compound 23 Compound 24 Compound 26 Compound 30 Rate kg/ha 0.03 0.12 0.03 0.12 0.03 0.12 0.25 0.063 0.125 0.031 0.125 0.125 0.062 0.031 0.015 0.125 0.031 0.062 0.031 0.125 0.031 Crabgrass 0 0 6G,3C 9G,9C 0 0 9G 6G 2G 0 9G 7G 3G 0 0 0 0 8G 5G 7G,2H 7G Barnyardgrass 3G 6G,3H 8G,3H 10C 0 0 9G,9C 8G 3G 0 5G 7G 2G 2G 0 0 0 9G 5G 9G,9C 9G,5H Sorghum 10C 10C 10E 10E 3G 9G,9C 9G,9C 8G 10C 4G 10C 10C 10C 10C 9G 3C 2C 9G,9C 9G 10E 10E Wild Oats 5G 7G 8G,8C 8G,8C 0 6G 8G 6G 8G 4G 8G 9G 7G 5G 4G 0 0 8G 5G 7G 7G Johnsongrass 8G,7C 9G,9C 9G,8C 10C 0 7G,3H 8G 6G 8G 2G 8G 8G 8G 7G 7G 2C 0 9G,9C 7G 9G,9C 8G,7C Dallisgrass 4G 6G,3H 8G,3H 10C 0 3G 9G 6G 8G 0 9G 9G,9C 8G 5G 3G 0 0 9G 8G 10C 8G,5H Giant foxtail 0 8G,5H 7G,3H 10C 0 3G 9G 2G 0 2G 2G 9G,9C 5G 0 0 0 0 9G,9C 5G 10C 9G,3H Ky. bluegrass 6G 8G,8C 10C 10C 4G 6G,3C 9C,9G 8G 9G 0 9G 9G,9C 8G 3G 3G 0 0 9G,9C 9G 10C 10C Cheatgrass 9G,9C 9G,9C 8G,8C 10C 0 0 9G 7G 8G 4G 9G 9G 8G 6G 4G 0 0 9G,9C 8G 8G,8C 7G Sugar beets 0 3G 8G,8C 10C 0 0 8G 6G 3G 2G 8G 6G 5G 5G 4G 2G 0 9G 5G 10C 7G,5H Corn 3G 8G,5H 4G 10C 0 0 8G,7H 5G 6G,5H 0 9G,9C 8G,7H 6G,5H 2G 2G 0 0 9G 9G 10C 3H,8G Mustard 7G,3H 9G,8C 10C 10C 0 6G,3H 9G 9G 9G 7G 9G,9C 9G 9G 7G 5G 0 0 9G,9C 9G 10C 9G,9C Cocklebur 5G 5G 9G,8C 9G,9C 0 0 -- -- 2G 0 5G 6G 3G 3G 2G 0 0 4G 0 8G,8C 7G,5H Pigweed 0 5G,5C 10C 10C 5G,5C 10C -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- Nutsedge 0 3G 7G 10E 0 0 9G 4G 7G 2G 10C 10C 10C 9G 8G 0 0 10C 9G 10E 9G Cotton 0 2G 5G,3H 7G,5H 0 0 5G 2G 2G 0 6G 6G 2G 2G 2G 0 0 4G 0 8G,5H 6G,3H Morningglory 0 4G 2G 3G 0 2G 8G 5G 0 0 6G 4G 3G 2G 0 0 0 7G 4G 9G,7C 6G,5H Sicklepod 0 4G 3G 3G 0 0 5G 2G 5G 2G 2G 0 0 2G 0 0 0 4G 2G 7G,4C 3G Teaweed 0 0 4G,3H 6G,5H 0 0 0 0 0 0 0 2G 0 0 0 0 0 5G 0 7G,3H 4G Velvetleaf 0 0 3G,5H 7G,5H 0 0 7G 2G 0 0 4G 0 0 0 0 0 0 5G 3G 8G,9C 3G Jimsonweed 0 0 3G 7G 0 0 3G 0 0 0 8G 0 0 0 0 0 0 5G 0 9G,8C 3G Soybean 0 0 3G,3H 6G,5H 0 0 3G,3H 0 0 0 7G,7H 2G 2G 0 0 0 0 4G 2G 6G,5H 2C Rice 7G,4C 10C 9G,9C 10C 4G 6G,3H 10C 8G 7G 4G 10C 10C 9G 6G 6G 2G 0 10E 10E 10E 10E Wheat 5G 7G,3C 8G,5C 10C 0 6G,3C 8G 7G 5G 2G 9G 9G 7G 4G 3G 0 0 5G 3G 9G,9C 7G Compound 31 Compound 32 Compound 33 Compound 35 Compound 38 Compound 39 Compound 42 Rate kg/ha 0.125 0.031 0.125 0.008 0.031 0.003 0.0015 0.125 0.031 0.125 0.008 0.031 0.003 0.0015 0.25 0.062 0.25 0.062 0.125 0.031 Crabgrass 4G 3G 9G,9C 8G 8G 7G 6G 7G 6G 9G 6G 8G 2G 2G 2G 0 2G 0 2G 2G Barnyardgrass 9G,5H 7G,3H 9G,9C 6G,3C 7G 3G 2G 5H,7G 3H,6G 8G,8C 3G 5H,7G 2G 2G 6G 3G 5G 0 0 0 Sorghum 10E 10C 10C 10C 10C 10C 10C 10C 10C 10C 8G 10C 4G 2G 8G,8C 8G,5H 8G,5H 2G 10C 2G Wild Oats 7G 7G 7G 6G 6G 6G 5G 6G 2G 6G 0 2G 0 0 0 0 0 0 2G 0 Johnsongrass 8G,3H 6G,3H 9G 6G 8G 6G 6G 7G 5G 10C 0 9G 0 0 5G 4G 0 0 2G 0 Dallisgrass 8G,3H 7G,3H 9G,9C 8G 9G,9C 7G 6G 8G 8G 9G,9C 7G 9G 7G 0 0 0 0 0 0 0 Giant foxtail 9G,9C 8G,5H 10C 6G,2H 9G 6G 6G 5G 4G 10C 2G 8G 2G 0 3G 0 0 0 0 0 Ky. bluegrass 10C 7G,3H 10C -- 10C -- -- 9G,9C 9G,9C 9G,9C 4G 9G,9C 2G 0 -- -- -- -- 4G 0 Cheatgrass 8G,9C 6G 10C 9G,5C 10C 9G 5C,8G 10C 10C 9G,9C 9G 10C 8G 4G 3G 0 0 0 2G 0 Sugar beets 7G,5H 4G 10C 10C 9G,9C 9G 8G,8C 9G,9C 7G 10C 9G 10C 8G 7G 4G 2G 4G 0 3G 0 Corn 9G,9C 5H,7G 9G,9C 9G,9C 9G,9C 7H 5G 8G 5G 8G 7G,5H 6G 3G 2G 8G,8C 5G 7G 0 3G 0 Mustard 9G,9C 10C 9G,9C 9G,7C 9G,9C 9G 9G 8G 6G 9C 9G 9G 9G 8G 0 0 0 0 8G 7G Cocklebur 2G 0 8C 6G,2H 7G -- 5G,2H 6G 3G 8G,8C 0 6G 3G 0 0 0 0 0 2G 0 Pigweed -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- Nutsedge 10E 7G 10C 10C 10C 10C 10C 5G 3G 10C 10C 10C 10C 2G 5G 0 0 0 0 0 Cotton 4G 0 8G,8C 8G 7G 8G 6G,3H 6G,3C 3G 8G,8C 6G 7G 3G 0 0 0 2G 0 2G 2G Morningglory 8G,3H 5G 7G 3G,2C 2G 3C 0 6G 0 8G,8C 7G 4G 3G 0 4G 0 2G 0 0 0 Sicklepod 7G 4G 8G,8C 8G,5C 7G,7C 3G 7G 8G,8C 7G,7C 9G,9C 7G 8G,8C 2G 0 0 0 0 0 0 0 Teaweed 8G,3H 3G 8G 8G,3C 8G 8G 7G 8G 7G 10C 3G 9G 0 0 2G 2G -- 2G -- -- Velvetleaf 4G,3H 3G 10C 8G 9G 7G 6G 7G 10C 10C 5G 10C 2G 0 0 0 7G 0 0 2G Jimsonweed 5G,5C 3G 9G,9C 7G,7H 8G,8C 4G 3G 5G 5G 8G 7G 7G 3G 0 0 0 0 0 0 0 Soybean 2G 0 8G,8C 8G,7H 6G,5C 7G 6G,2C 6G,3C 4G 8G,8C 7G,5H 7G,5C 6G 2G 2G 2G 0 0 2G 2G Rice 10C 8G,5H 10C 10C 10C 10C 10C 10C 10C 10C 10C 10C 10C 9G 6G 3G 5G 0 7G 0 Wheat 7G 5G 8G 8G 3G 7G 6G 6G 2G 5G 4G 0 2G 0 0 0 0 0 0 0 Compound 43 Compound 44 Compound 46 Compound 47 Compound 48 Rate kg/ha 0.125 0.031 0.125 0.031 0.125 0.031 0.015 0.125 0.031 0.015 0.125 0.031 0.015 Crabgrass 3G 2G 5G 2G 9G,7C 8G,7C 7G,7C 5G,3C 2C,2G 0 4G 2G 0 Barnyardg rass 0 0 0 0 9G,7C 8G,7C 5G,3C 6G,3C 2G,2C 0 6G,5C 4G,3C 2G Sorghum 7G,3H 2G 0 0 10C 10C 10C 9G,9C 7G,5H 3G,3H 9G,9C 9G,9C 8G,8C Wild Oats 0 0 0 0 7G,3C 7G,3C 5G,3C 6G 3G 2G 6G 5G 4G Johnsongrass 0 0 0 0 9G,5C 8G,5C 2G 8G,7C 2G 0 8G 8G 3G,3H Dallisgrass 3G 0 2G 0 9G 9G 8G 8G 5G 0 7G 5G 0 Giant foxtail 0 0 0 0 9G,9C 9G,9C 7G 8G,8C 2G,3C 0 8G,8C 4G,3C 0 Ky. bluegrass 2G 0 0 0 -- -- -- -- -- -- -- -- -- Cheatgrass 4G 2G 0 0 8G 8G 2G 8G 5G 0 8G 6G 0 Sugar beets -- -- -- -- 9G,5C 8G,5C 7G 8G 4G,3H 3G 6G 4G 3G Corn 2G 0 0 0 8G,8C 7G,7H 2G,2C 7G,7H 3G,3C 2G,2H 7G,5C 2G,2C 0 Mustard 7G 5G 5G 0 9G,9C 8G,8C 8G,8C 9G,8C 7G 6G 9G,9C 8G,5C 7G Cocklebur 2G 0 0 0 6G,3C 2G 2G 6G,7C 0 0 5G,5C 3C,2G 0 Pigweed -- -- -- -- -- -- -- -- -- -- -- -- -- Nutsedge 0 0 0 0 10C 9G 6G -- 0 0 -- 2G 2G Cotton 5G 2G 3G 0 4G,7H 3G,5H 3G. 7G,3C 3G 3G 3G,3H 2G 2G Morningglory 2G 0 0 0 7G 5G,5H 3G,3H 5G,3H 0 0 5G 3G 0 Sicklepod 0 0 0 0 -- 5G,5H 3G,3H 2G,3C 0 0 2G 0 0 Teaweed -- -- -- -- -- -- -- -- -- -- -- -- -- Velvetleaf 0 0 0 0 -- 2G,2H 2G 5G,3H 0 0 7G,5C 0 0 Jimsonweed 0 0 0 0 -- 4G 2G 2G,2C 0 0 2G,2C 0 0 Soybean 0 0 0 0 7H 5G,5H 5G,5H 2G,3C 0 0 2G,3C 0 0 Rice 5G 2G 3G 0 10C 10C 10C 10C 4G 2G 9G 5G 3G Wheat 0 0 0 0 7G 3G 0 7G 4G 2G 5G 4G 4G

Two ten-inch in diameter plastic pans lined with polyethylene liners were filled with prepared Fallsington silt 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), annula 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), Galium aparine, tumble mustard (Sisymbrium altissium) kochia (Kochia scoparia), shepherd's purse (Capsella bursapastoris), Matricaria inodora, black nightshade (Solanum nigrum), yellow rocket (Barbarea vulgaris), wild mustard (Brassica kaber) and wild buckwheat (Polygonum convolvulus). In certain tests, rapeseed was substituted for wild mustard and Veronica persica was included. The above two pans were treated pre-emergence. At the same time two pans in which the above plant species were growing were treated post-emergence. Plant height at the time of treatment ranged from 1-15 cm depending on plant species.

The test compounds were diluted with a non-phytotoxic 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 20 days at which time the treatments were compared to the controls and the effects visually rated. The recorded data are presented in Table C. Several of the compounds tested exhibit utility for post-emergence weed control in wheat. Compound 1 Compound 35 Compound 35 Compound 43 Compound 46 Pre-Emergence Post-Emergence Pre-Emergence Post-Emergence Pre-Emergence Post-Emergence Pre-Emergence Post-Emergence Rate kg/ha 0.015 0.06 0.015 0.06 0.25 0.06 0.015 0.004 0.25 0.06 0.015 0.004 0.25 0.06 0.25 0.06 0.015 0.004 0.015 0.004 wheat 0 0 2G 1C,3G 7G 5G 1G 0 7G 3G 1G 0 8G 0 7G 2G 4G 1G 6G 4G barley 0 0 4G 6G 8G -- 3G 0 8G 5G 1G 0 2G 2G 3C,5G 5G 8G 5G 8G 6G wild oats 0 0 2G 1G 6G 5G 2G 0 7G 5G 2G 0 5G 2G 2C,4G 2G 8G 5G 3C,8G 6G downy brome 0 2G 2G 3G 2C,9G 2C,8G 7G 5G 3C,9G 7G 7G 5G 8G 4G 4G 4G 9G 7G 3C,8G 8G cheatgrass 0 1C,2G 6G 2C,8G 10E 10C 1C,8G 5G 2C,9G 8G 7G 5G 3C,8G 2G 4G 2G 2C,8G 6G 3C,8G 7G blackgrass 0 0 3G 2C,6G 4C,9G 2C,8G 3C,7G 5G 9C,9G 5C,9G 7C,8G 1C,5G 3C,8G 2H 8G 2C,5G 3C,9G 2C,8G 10C 3C,8G annual bluegrass 0 2G 1C,4G 8C,9G 3C,9G 2C,8G 8G 4G 2C,8G 3C,8G 7G 3G 2C,8G 4G 4G 2G 4C,9G 2C,9G 9C,9G 3C,8G green foxtail 0 0 3G 5G 9G 5C,8G 2C,7G 3C,6G 2C,8G 2C,8G 1C,6G 3G 2C,5G 1C,2G 2C,7G 2C,4G 3C,9G 7G -- -- quackgrass 0 0 0 5G 2C,9G 2C,8G 8G 5G 1C,6G 1C,7G 6G 3G 5G 2G -- -- 9G 7G 6G 8G Italian ryegrass 0 1G 3G 9C,9G 10E 1C,8G 7G 1C,4G 2C,7G 8G 5G 2G 2C,8G 1C,2G 1C,2G 5G 4C,9G 7G 3C,8G 7G ripgut brome 0 0 2G 2C,6G 3C,9G 1C,8G 7G 4G 2C,8G 7G 5G 5G 2C,7G 2G 5G 2G 2C,8G 6G 2C,8G 6G Russian thistle 0 0 3C,3G 4G 5C,7G 2C,6G 1C,3G 1C,3G 9C,9G 10C 7C,8G 5C,7G 1C 0 0 0 3G 0 0 0 tansy mustard 0 -- 9G 5G 9C,9G 7C,9G 2C,9G 9G 10C 10C 7C,8G 5C,7G 9C 9C 2C 1C,2G -- -- 10C 10C Galium aparine 0 0 2G 2G 3C,9G 7G 7G 6G 2C,7G 7G 4G -- 7C 3C 3C 3G 5G 5G 6G 3G tumble mustard 0 0 5G 10C 10C 5C,9G 9G 8G 10C 10C 10C 5C,8G 8G 4G 10C 6G 10C 9G 10C 10C kochia 0 0 2G 4G 2C,9G 9G 8G 6G 10C 9C,9G 2C,7G 2C,2G 0 0 -- -- 8G 0 0 -- shepherd's purse 0 0 10C 2C,2G 10C 10C 2C,9G 9G 10C 10C 9C,9G 7C,9G 9G 8G 2C,2G 5G 10C 9G 10C 8G Matricaria inodora 0 0 3G 8C,8G 9G 9G 8G 7G 7C,9G 7C,8G 5C,9G 3C,8G 9G 6G 5G 1C,3G 9G 8G 2C,6G 3G black nightshade 0 0 0 0 3C,9G 8G 6G 4G 5C,8G 2C,7G 2C,7G 2G 5G 0 3C,8G 7G 9G 5G 2C,8G 6G yellow rocket 0 0 0 0 3C,9G 9G 8G 8G 5C,9G 1C,7G 2G 0 9G 8G 7G 2G 9G 8G 8G 4G wild mustard 0 0 10C 9G 2C,9G 9G 1C,9G 7G 7C,8G 5C,9G 2C,7G 6G 9G 7G 8G 3G 9G 8G 6G 5G wild buckwheat 0 0 1G 0 2C,8G 8G 5G 2G 10C 6G 3G -- 2G 0 5G 0 7G 5G 10C 2G Veronica persica -- -- 6G 4G

The test chemicals, dissolved in a non-phytotoxic solvent, were applied in an overall spray to the foliage and surrounding soil of selected plant species. One day after treatment, plants were observed for rapid burn injury. Approximately fourteen days after treatment, all species were visually compared to untreated controls and rated for response to treatment. The rating system was as described previously for Test A. The data are presented in Table D.

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), cockelbur (Xanthium pensylvanicum), crabgrass (Digitaria sp.), 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 mustard. All plants were sprayed approximately 14 days after planting. Additional plant species such as johnsongrass, rape and bindweed are sometimes added to this standard test in order to evaluate unusual selectivity.

Several of the compounds tested by this procedure exhibit post-emergence control of weeds in wheat, cotton and soybeans.

For a greenhouse test, a set of 25-cm diameter plastic pots filled with Woodstown sandy loam were planted to Williams soybeans. Similar pots were used to plant the following weed species, three different species per pot: cocklebur (Xanthium pensylvanicum), sicklepod (Cassia obtusifolia), pitted morningglory (Ipomoea lacunosa), johnsongrass (Sorghum halepense), barnyarngrass (Echinochloa crusgalli) and giant foxtail (Setaria faberi). Immediately after planting, the pots were treated pre-emergence with Compound No. 30, dissolved in a non-phytotoxic solvent. The rates of application extended from 4 to 125 g/ha. The treated pots were held in the greenhouse for 27 days and the plants were then rated for response to the chemical treatments. The data are summarized in Table E. Note that Compound No. 30 has potential utility for weed control--particularly grass control--in soybeans.