Herbicide Compositions

Among the many herbicidal compounds commercially available the thiolcarbamates alone or admixed with other herbicides, such as the triazines, have reached a relatively high degree of commercial success. These herbicides are immediately toxic to a large number of weed pests at different concentrations varying with the resistance of the weed pests. Some examples of these compounds are described and claimed in the U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314. It has been found in practice that the use of these thiolcarbamates as herbicides on crops sometimes causes serious injuries to the crop plant. When used in the recommended amounts in the soil to control many broadleaf weeds and grasses, serious malformation and stunting of the crop plants result. This abnormal growth in the crop plants results in loss of crop yield. Previous attempts to overcome this problem involves the treatment of the crop seed with certain antagonistic agents prior to planting, see U.S. Patent No. 3,131,509. These antagonistic agents have not been notably successful.

It has been discovered that plants can be protected against injury by the thiolcarbamates alone or mixed with other compounds and/or the tolerance of the plants can be substantially increased to the active compounds of the above-noted U.S. Patents by adding to the soil an antidote compound corresponding to the following formula: ##STR2## wherein R can be selected from the group consisting of haloalkyl; haloalkenyl; alkyl; alkenyl; cycloalkyl; cycloalkylalkyl; halogen; hydrogen; carboalkoxy; N-alkenylcarbamylalkyl; N-alkenylcarbamyl; N-alkyl-N-alkynylcarbamyl; N-alkyl-N-alkynylcarbamylalkyl; N-alkenylcarbamylalkoxyalkyl; N-alkyl-N-alkynylcarbamylalkoxyalkyl; alkynoxy; haloalkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminosulfonoalkyl; alkylthioalkyl; haloalkylcarbonyloxyalkyl; alkyoxycarboalkyl; haloalkenylcarbonyloxyalkyl; hydroxyhaloalkyloxyalkyl; hydroxyalkylcarboalkyoxyalkyl; hydroxyalkyl; alkoxysulfonoalkyl; furyl, thienyl, alkyldithiolenyl; thienalkyl; phenyl and substituted phenyl wherein said substituents can be selected from halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxylic acids and their salts, haloalkylcarbamyl; phenylalkyl; phenylhaloalkyl; phenylalkenyl; substituted phenylalkenyl wherein said substituents can be selected from halogen, alkyl, alkoxy; halophenoxy; phenylalkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halophenylalkenoxy; halothiophenylalkyl; halophenoxyalkyl; bicycloalkyl; alkenylcarbamylpyridinyl; alkynylcarbamylpyridinyl; dialkenylcarbamylbicycloalkenyl; alkynylcarbamylbicycloalkenyl; R.sub.1 and R.sub.2 can be the same or different and can be selected from the group consisting of alkenyl; haloalkenyl; hydrogen; alkyl; haloalkyl; alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; haloalkylcarboxyalkyl; alkylcarboxyalkyl; alkoxycarboxyalkyl; thioalkylcarboxyalkyl; alkoxycarboalkyl; alkylcarbamyloxyalkyl; amino; formyl; haloalkyl-N-alkylamido; haloalkylamido; haloalkylamidoalkyl; haloalkyl-N-alkylamidoalkyl; halogalkylamidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarboalkenyl; haloalkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxyalkyl; cycloalkylcarbamyloxyalkyl; alkoxycarbonyl; haloalkoxycarbonyl; halophenylcarbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl wherein said substituents can be selected from alkyl, halogen, haloalkyl, alkoxy, haloalkylamido, phthalamido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, haloalkylamido, alkylcarboalkenyl; phenylsulfonyl; phenylalkyl; substituted phenylalkyl wherein said substituents can be selected from halogen, alkyl; dioxyalkylene, halophenoxyalkylamidoalkyl; alkylthiodiazolyl; piperidylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; piperidylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; halo benzothiazolyl; furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofurylalkyl; 3-cyano, 4,5-polyalkylene-thienyl; .alpha.-haloalkylacetamidophenylalkyl; .alpha.-haloalkylacetamidonitrophenylalkyl; .alpha.-haloalkylacetamidohalophenylalkyl; cyanoalkenyl; R.sub.1 and R.sub.2 when taken together can form a structure consisting of piperidinyl; alkylpiperidinyl; alkyltetrahydropyridyl; morpholyl; alkylmorpholyl; azobicyclononyl; benzoalkylpyrrolidinyl; oxazolidyl; alkyloxazolidyl; perhydroquinolyl; alkylaminoalkenyl; provided that when R.sub.1 is hydrogen R.sub.2 is other than hydrogen and halophenyl.

The compounds represented by the above formula can be synthesized by mixing together an appropriate acid chloride with an appropriate amine. A solvent such as benzene can be used if desired. The reaction is preferably carried out at reduced temperatures. After the reaction is complete, the end-product is brought to room temperature and can be readily separated.

In order to illustrate the merits of the present invention, reference is made to the following examples:

A solution was made by dissolving 3.7 g. (0.025 mole) of dichloroacetyl chloride in 100 ml. of methylene dichloride which was then cooled to about 5.degree. C. in an ice bath. Then, 4.9 g. (0.05 mole) of diallyl amine was added dropwise while the temperature was maintained at below about 10.degree. C. The mixture was then stirred at room temperature for about 4 hours and washed twice with water and dried over magnesium sulfate, filtered and stripped. The yield was 4.0 g., n.sub.D.sup.30 -1.4990.

A solution was made by dissolving 3.7 g. (0.025 mole) of dichloroacetyl chloride in 100 ml. of methylene dichloride which was then cooled to about 10.degree. C. in an ice bath. Then, 5.1 g. (0.05 mole) of di-n-propylamine was added dropwise while the temperature was maintained at below about 10.degree. C. The mixture was then stirred at room temperature overnight and washed twice with water and dried over magnesium sulfate, filtered and stripped. The yield was 3.6 g., n.sub.D.sup.30 -1.4778.

A solution was made by dissolving 3.7 g. (0.025 mole) of dichloroacetyl chloride in 80 ml. of methylene dichloride which was then cooled to about 10.degree. C. in an ice bath. Then, 4.2 g. (0.05 mole) of N-methyl, N-1-methyl-3-propynylamine in 20 ml. of methylene dichloride was added dropwise while the temperature was maintained about 10.degree. C. The mixture was then stirred at room temperature for about 4 hours and washed twice with water and dried over magnesium sulfate, filtered and stripped. The yield was 2.9 g., n.sub.D.sup.30 -1.4980.

A solution was formed containing 100 ml. acetone, 5.05 g. furfuryl amine (0.1 mole), then stirred with the addition of 7 ml. triethylamine at 15.degree. C. Then, 5.7 g. of monochloro acetyl chloride was added and stirred for 15 more minutes, wherein 500 ml. of water was added. The reaction mass was filtered, washed with dilute hydrochloric acid in additional water, and then dried to constant weight.

A solution was formed consisting of 5.7 g. (0.05 mole) of amino methyl thiazole in 100 ml. of benzene with 7 ml. of triethylamine. This solution was stirred at 10.degree.-15.degree. C. and then 5.2 ml. (0.05 mole) of dichloro acetyl chloride was added dropwise. The reaction was stirred at room temperature for 10 minutes. Then, 100 ml. water was added and the solution was then washed with benzene solution, dried over magnesium sulfate and then filtered to remove the solvent.

A solution was formed containing 200 ml. acetone and 17.5 g. (0.05 mole) of 2-amino-6-bromo benzothiazole and 7 ml. of triethylamine. The solution was stirred 15.degree. C. with cooling. Then, 5.2 ml. (0.05 mole) of dichloroacetyl chloride was added slowly. This solution was stirred at room temperature for ten minutes. The solid form was filtered off, which solid was washed with ether, then cold water, and then filtered again and dried at 40.degree.-50.degree. C.

3.4 g. of 3-methyl-3-butynyl amine was dissolved in 50 ml. of methylene chloride, 4.5 g. of triethylamine was added and 7.6 g. of decanoyl chloride was added dropwise with stirring and cooling in a water bath. When the reaction was complete the mixture washed with water, dried and the solvent stripped off to give 7.1 g. of product.

A solution was formed containing 5.9 g. of diallyl amine dissolved in 15 ml. of methylene chloride and 6.5 g. of triethylamine. Then, 6.3 g. of cyclopropane carbonyl chloride was added dropwise with stirring and cooling in a water bath. When the reaction was complete the mixture was washed with water, dried and the solvent stripped off to give 8.2 g. of product.

A solution was formed containing 4.5 g. of diallyl amine dissolved in 15 ml. of methylene chloride and 5.0 g. of triethylamine. Then, 7.1 g. of ortho-fluorobenzoyl chloride was added dropwise with stirring and cooling in a water bath. When the reaction was complete, the mixture was washed with water, dried and the solvent stripped off to give 8.5 g. of product.

N,N-bis(2-hydroxyethyl)dichloroacetamide was prepared by reacting 26.3 g. of diethanolamine with 37 g. of dichloroacetyl chloride in the presence of 25.5 g. of triethylamine in 100 ml. of acetone. Then, 6.5 g. of the N,N-bis(2-hydroxyethyl)dichloroacetamide was dissolved in 50 ml. of acetone, then reacted with 4 g. of methyl isocyanate in the presence of dibutyl tin dilaurate and triethylamine catalysts. The reaction product was stripped under vacuum to yield 8.4 g. of product.

7.8 g. of diallyl amine was dissolved in 50 ml. of methylene chloride, with 8.5 g. of triethylamine added dropwise. Then, 5.6 g. of malonyl chloride was added dropwise with cooling and stirring. When the reaction was complete, the mixture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 7.0 g. of product.

7.9 g. of diallyl amine was dissolved in 50 ml. of methylene chloride with 8.5 g. of triethylamine added dropwise. Then, 6.2 g. of succinyl chloride was added dropwise with cooling and stirring. When the reaction was complete, the mixture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 9.7 g. of product.

6.7 g. of N-methyl-1-methyl-3-propynylamine was dissolved in 50 ml. of methylene chloride with 8.5 g. of triethylamine added dropwise. Then, 6.2 g. of succinyl chloride was added dropwise with cooling and stirring. When the reaction was complete, the mixture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 7.0 g. of product.

7.9 g. of diallyl amine was dissolved in 50 ml. of methylene chloride with 8.5 g. of triethylamine added dropwise. Then, 8.1 g. of o-phthaloyl chloride was added dropwise with cooling and stirring. When the reaction was complete, the mixture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 10.9 g. of product.

3.3 g. of N-methyl-1-methyl-3-propynylamine was dissolved in 50 ml. of methylene chloride with 4.5 g. of triethylamine added dropwise. Then, 9.2 g. of diphenyl acetyl chloride was added dropwise with cooling and stirring. When the reaction was complete, the mixture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 9.9 g. of the product.

4.9 g. of diallyl amine was dissolved in 50 ml. of acetone with 7.4 g. of phthalic anhydride added portionwise with stirring. The solvent was stripped off under vacuum to yield 13.0 g. of product.

9.2 g. of N(1,1-dimethyl-3-propynyl)O-phthalamic acid was dissolved in 50 ml. of methanol and 9.6 g. of sodium methoxide. 25% in methanol was added portionwise with stirring and cooling. The solvent was stripped or removed under vacuum to yield 9.0 g. of product. The intermediate, N(1,1-dimethyl-3-propynyl)O-phthalamate was prepared from 29.6 g. of phthalic anhydride and 16.6 g. of 3-amino-3-methylbutyne in 150 ml. of acetone. The intermediate was precipitated with petroleum ether as a white solid and used without further purification.

A 500 cc. 4-necked flask was provided with stirrer, thermometer and addition funnel. Then, 7.7 g. of diethylamine (0.105 mole), 4.0 g. of sodium hydroxide solution and 100 ml. of methylene chloride were charged to the flask and the mixture was cooled in a dry-ice-acetone bath. Then, 14.7 g. (0.10 mole) of dichloroacetyl chloride was added portionwise. The mixture was stirred for an additional hour and immersed in an ice bath. It was then phase separated and the lower organic phase was washed with two portions of 100 ml. of dilute hydrochloric acid, two 100 ml. of sodium carbonate solutions, dried over magnesium sulfate and concentrated under vacuum to yield 16.8 g. of product.

4.0 g. (0.025 mole) of N,N-diallylcarbamoyl chloride was added to 50 ml. of methylene dichloride. Then, 1.8 g. (0.025 mole) of 2-butyn-1-ol was added dropwise with 2.6 g. of triethylamine in 10 ml. methylene chloride. The reaction product was stirred at room temperature overnight, washed with water twice and dried over magnesium sulfate to yield 4.0 g. of product.

9.7 g. (0.1 mole) of potassium thiocyanate was dissolved in 100 ml. of acetone. Then, 8.7 g. (0.05 mole) of N,N-diallyl chloroacetamide were added at room temperature with 10 ml. of dimethyl formamide. The reaction product was stirred overnight. The reaction product was partially stripped. Water was added along with two portions of 100 ml. of ether. The ether was separated, dried and stripped to yield 7.2 g. of product.

A solution of 50 ml. of benzene containing 7.4 g. (0.05 mole) of dichloro acetylchloride was formed. To this solution was added 3.0 g. (0.05 mole) of cyclopropylamine and 5.2 g. of triethylamine in 2 ml. of benzene at a temperature of 5.degree.-10.degree. C. A precipitate was formed and the mixture was stirred for two hours at room temperature and one hour at 50.degree.-55.degree. C. The product was worked-up as in previous examples to yield 5.7 g. of the product.

To 4.7 g. (0.032 mole) of piperonylamine and 1.2 g. of sodium hydroxide in 30 ml. of methylene chloride and 12 ml. of water was added 4.4 g. (0.03 mole) of dichloroacetyl chloride in 15 ml. of methylene chloride at -5.degree. to 0.degree. C. The mixture was stirred ten more minutes around 0.degree. C., then allowed to warm to room temperature with stirring. The layers were separated and the organic layer washed with dilute hydrochloric acid, 10% sodium carbonate solution, water and dried to yield 5.9 g. of product.

In a solution of 75 ml. of benzene containing 5.7 g. of meta-chlorocinnamyl chloride was formed. To this solution was added 3.2 g. of diallyl amine and 3.3 g. of triethyl amine in 2 ml. of benzene at a temperature of 5.degree. to 10.degree. C. A precipitate was formed and the mixture was stirred for two hours at room temperature and one hour at 55.degree. C. The product was washed and worked up to yield 5.8 g. of product.

A 500 cc. 4-necked flask was provided with a stirrer, thermometer and addition funnel. Then, 11.9 g. 2,4-dimethylpiperidine, 4.0 g. of sodium hydroxide solution and 100 ml. of methylene chloride were charged to the flask and the mixture cooled in a dry-ice-acetone bath. Then, 14.7 g. (0.10 mole) of dichloroacetyl chloride were added in portions. The mixture was stirred for one hour and immersed in the ice bath, and then separated with the lower organic phase washed with two portions of 100 ml. of dilute hydrochloric acid and two portions of 100 ml. of 5% sodium carbonate solution, dried over magnesium sulfate and concentrated in a rotary evaporator under a water pump vacuum to yield 19.3 g. of product.

A 500 ml. 4-necked flask was provided with a stirrer, thermometer and addition funnel. Then, 14.6 g. (0.105 mole) of cis-trans-decahydroquinoline and 4.0 g. of sodium hydroxide solution and 100 ml. of methylene chloride were added together. Then, 14.7 g. of dichloroacetyl chloride was added portionwise. The reaction mixture was worked up by stirring for about an hour and immersed in an ice bath and then phase separated with the lower organic phase being washed with two portions of 100 ml. dilute hydrochloric acid, two portions of 100 ml. of 5% sodium carbonate, dried over magnesium sulfate and concentrated to yield 22.3 g. of product.

A 500 ml. 4-necked flask was provided with stirrer, thermometer and addition funnel. Then, 13.6 g. (0.104 mole) of 3,3'-iminobis-propylamine was added along with 12.0 g. of sodium hydroxide solution and 150 ml. of methylene chloride. Thereafter, the mixture was cooled in a dry ice-acetone bath and 44.4 g. (0.300 mole) of dichloroacetyl chloride was added portionwise. An oily product formed which was not soluble in methylene chloride and was separated and washed with two portions of 100 ml. of dilute hydrochloric acid and allowed to stand overnight. The next morning the product was washed with two portions of 100 ml. of 5% sodium carbonate and the product was taken up in 100 ml. of ethanol, dried over magnesium sulfate and concentrated to yield 21.0 g. of product.

A 500 ml. 4-necked flask was provided with stirrer, thermometer and addition funnel. Then, 7.5 g. of tetrahydrofurfuryl-n-propylamine (0.0525 mole) and 2.0 g. sodium hydroxide solution and 100 ml. of methylene chloride were charged thereto. Then, 7.4 g. (0.05 mole) of dichloroacetyl chloride were added portionwise. The mixture was stirred for one additional hour in an ice bath and then separated with the lower organic phase washed with two portions of 100 ml. of dilute hydrochloric acid and two portions of 100 ml. of 5% sodium carbonate solution, dried over magnesium sulfate and concentrated to yield 12.7 g. of product.

Example 27 was repeated in its entirety except that 8.9 g. of piperidine was used as the amine.

Example 28 was essentially repeated in its entirety except 9.1 g. of morpholine was used as the amine.

3.2 g. of benzaldehyde and 7.7 g. of dichloracetamide were combined with 100 ml. of benzene and approximately 0.05 g. of paratoluene sulfonic acid. The mixture was refluxed until water ceased to come over. On cooling the product crystallized from benzene yielding 7.0 g. of product.

2.5 g. of 3-amino-3-methylbutyne was dissolved in 50 ml. of acetone and 3.5 g. of triethylamine was added, followed by 6.0 g. of adamantane-1-carbonyl chloride added dropwise with stirring and cooling. The mixture was poured into water and the solid product collected by filtration and dried under vacuum to give 6.5 g. of product.

5.1 g. of 2-cyanoisopropylamine was dissolved in 50 ml. of acetone with 6.5 g. of triethylamine added, followed by 5.3 g. of benzene-1,3,5-tricarboxylic acid chloride added dropwise with stirring and cooling. The mixture was poured into water and the solid product collected by filtration and dried under vacuum to give 7.6 g. of product.

6.0 g. of diallylamine was dissolved in 50 ml. of methylene chloride, 6.5 g. of triethylamine was added and 6.6 g. of 3,6-endomethylene-1,2,3,6-tetrahydrophthaloyl chloride was added dropwise with stirring and cooling. When the reaction was complete the mixture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 9.3 g. of product.

4.0 g. of diallylamine was dissolved in 50 ml. of methylene chloride, 4.5 g. of triethylamine was added and 7.2 g. of trans-2-phenylcyclopropane carbonyl chloride was added dropwise with cooling and stirring. When the reaction was complete the mixture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 9.3 g. of product.

A solution was formed consisting of 4.0 g. (0.03 mole) of 2-methyl indoline, 7.0 ml. triethylamine and 100 ml. of methylene chloride. Then, 2.9 ml. of dichloroacetyl chloride was added thereto over a period of about one minute with dry ice cooling, keeping the temperature under 0.degree. C. The solution was allowed to warm to room temperature and stand for one hour and then washed with water and then with dilute hydrochloric acid, dried over magnesium sulfate and evaporated to give a solid that was washed with n-pentane to give 5.0 g. of product.

A 500 cc. 4-necked flask was provided with stirrer, thermometer and addition funnel. Then, 8.9 g. of cyclooctyl n-propylamine, 2.0 g. of sodium hydroxide solution and 100 ml. of methylene chloride were charged to the flask and the mixture was cooled in a dry ice-acetone bath. Then, 5.6 g. of chloroacetyl chlorine was added portionwise. The mixture was stirred for about one additional hour, immersed in the ice bath, then phase separated and the lower organic phase was washed with two portions of 100 ml. of dilute hydrochloric acid and two portions of 100 ml. 5% sodium carbonate solution, dried over magnesium sulfate and concentrated to yield 9.5 g. of product.

A 500 cc. 4-necked flask was provided with stirrer, thermometer and addition funnel. Then, 7.8 g. (0.0525 mole) of p-methylbenzyl ethylamine, 2.0 g. of sodium hydroxide solution and 100 ml. of methylene chloride were charged to the flask. The mixture was cooled in a dry ice-acetone bath. Then, 5.6 g. (0.05 mole) of chloroacetyl chloride was added portionwise. The mixture was stirred for about one additional hour, immersed in the ice bath, then phase separated with the lower organic phase being washed with two portions of 100 ml. of dilute hydrochloric acid and then two portions of 100 ml. of 5% sodium carbonate solution, dried over magnesium sulfate and concentrated to yield 9.5 g. of product.

4.7 g. of amino pyridine were charged to a reaction vessel along with 100 ml. of acetone and stirred at 10.degree.-15.degree. C. Then, 7.0 ml. of triethylamine were added dropwise. Thereafter, 5.25 ml. of dichloroacetyl chloride in 10 ml. of acetone was added over a period of five minutes and stirred at room temperature. The solids were filtered off, washed with acetone to yield 10.0 g. of product.

8.1 g. (0.05 mole) of 4-aminophthalimide was dissolved in 100 ml. of dimethylfuran, wherein 5.0 g. of dichloroacetyl chloride was stirred in at 0-10.degree. C. over a period of 5 minutes. Then, 7.0 ml. of triethylamine was added. The reaction mass was stirred for one-half hour at room temperature and then one liter of water was added. The reaction was filtered with water and dried to give 12.0 g. of product.

The compound of this example was prepared by reacting 5.4 g. of N,N-bis(2-hydroxyethyl) dichloroacetamide with 4.3 g. of isopropyl isocyanate in 50 ml. of acetone in the presence of dibutyltin dilaurate and triethylenediamine catalysts, to yield 8.2 g. of product.

The compound of this example was prepared by reacting 3.6 g. of N,N-bis(2-hydroxyethyl) chloroacetamide with 5.0 g. of cyclohexyl isocyanate in the presence of 50 ml. of acetone and dibutyltin dilaurate and triethylenediamine catalysts. The reaction mass was heated to reflux and stripped under vacuum to yield 6.9 g. of product.

15 g. of acetone and 12.2 g. of ethanol amine were combined in 150 ml. of benzene and refluxed until no additional water came over. The resulting solution was examined and found to contain 2,2-dimethyl-1,3-oxazolidine. A quarter of the benzene solution (0.05 mole) was reacted with 7.4 g. of dichloroacetyl chloride and 5.5 g. of triethylamine, washed with water, dried and stripped under vacuum to give a light tan solid. A portion was recrystallized from ether giving a white product.

Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above. The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification. ##STR45## Compound No. R R.sub.1 R.sub.2 1 CH(CH.sub.3)B r CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 2 C(CH.sub.3).sub.2 C Br CH.sub.2CHH.sub.2 CH.sub.2CHCH.sub.2 3 CCl.sub.2CH.sub.3 CH.sub.2CHCH .sub.2 CH.sub.2CHCH.sub.2 4 CClCCl.sub.2 CH.sub.2CHCH.sub.2 CH.sub.2CHCH. sub.2 5 CF.sub.2C.sub.2 F.sub.5 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 6 CHCl.sub.2 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 7 CH.sub.2 C Cl CH.sub.2CHH.sub.2 CH.sub.2CHCH.sub.2 8 CHCl.sub.2 CH.sub.2CN C N CH.sub.2 9 CHCl.sub.2 CH.sub.2CHCH.sub. 2 H 10 CHCl.sub.2 C.sub.3 H.sub.7 C.sub.3 H.sub.7 11 CHCl.sub.2 C(CH.sub.3).sub.2CN H 12 CH.sub.2 Cl C(CH.sub.3).sub.2CN H 13 CCl.sub.3 CH.sub.2CHCH.sub.2 H 14 CCl.sub.3 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 15 CH.sub.2 Cl C(CH.sub.3).sub.2CCH H 16 CHCl.sub.2 C(CH.sub.3).sub.2CCH H 17 CCl.sub.3 C(CH.sub.3).sub.2CCH H 18 CHCl.sub.2 CH.sub.3 CH(CH.sub.3)CCH 19 CHCl.sub.2 CH.sub.2CHCH.sub.2 ##STR46## 20 CH.sub.2 Cl H ##STR47## 21 CHCl.sub.2 H ##STR48## 22 CH.sub.2 Cl H ##STR49## 23 CHCl.sub.2 H ##STR50## 24 CHCl.sub.2 H ##STR51## 25 CHCl.sub.2 H ##STR52## 26 CHCl.sub.2 H ##STR53## 27 CHCl.sub.2 H ##STR54## 28 CHCl.sub.2 H ##STR55## 29 ##STR56## CH.sub.3 CH(CH.sub.3)CCH 30 ##STR57## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 31 CH.sub.2CH(CH.sub.3)CH.sub.2t-C.sub.4 H.sub.9 H C(CH.sub.3).sub.2CCH 32 C(CH.sub.3).sub.2C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 33 CH.sub.2t-C.sub.4 H.sub.9 CH.sub.3 CH(CH.sub.3)CCH 34 CH.sub.2t-C.sub.4 H.sub.9 H C(CH.sub.3).sub.2CN 35 CH(CH.sub.3)C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 36 CH(CH.sub.3)C.sub.3 H.sub.7 CH.sub.3 CH(CH.sub.3)C CH 37 CH(CH.sub.3)C.sub.3 H.sub.7 H C(CH.sub.3).sub.2CCH 38 i-C.sub.3 H.sub.7 CH.sub.3 CH(CH.sub.3)CCH 39 C.sub.13 H.sub.27 CH.sub.2CHCH.sub.2 CH.sub.2 CHCH.sub.2 40 C.sub.11 H.sub.23 CH.sub.2CHCH.sub.2 CH.sub.2 CHCH.sub.2 41 C.sub.11 H.sub.23 H C(CH.sub.3).sub.2CCH 42 C.sub.9 H.sub.19 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 43 C.sub.9 H.sub.19 H C(CH.sub.3).sub.2CCH 44 C.sub.6 H.sub.13 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.3 45 C.sub.6 H.sub.13 CH.sub.3 CH(CH.sub.3)CCH 46 C.sub.6 H.sub.13 H C(CH.sub.3).sub.2CCH 47 C.sub.4 H.sub.9 H C(CH.sub.3).sub.2CCH 48 C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 49 C.sub.3 H.sub.7 CH.sub.3 CH(CH.sub.3)CCH 50 C.sub.3 H.sub.7 H C(CH.sub.3).sub.2 CCH 51 CH.sub.3 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 52 CH.sub.3 H C(CH.sub.3). sub.2CCH 53 C(CH.sub.3)CH.sub.2 H C(CH.sub.3).sub.2CCH 54 CHCHCH.sub.3 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 55 CHCHCH.sub.3 H C(CH.sub.3).sub.2 CCH 56 CHC(CH.sub.3).sub.2 CH.sub.3 CH(CH.sub.3)CCH 57 CHC(CH.sub.3).sub. 2 H C(CH.sub.3).sub.2CCH 58 CHCHCHCHCH.sub.3 CH.sub.2CHCH.sub.2 CH.sub.2C HCH.sub.2 59 CHCHCHCHCH.sub.3 H C(CH.sub.3).sub.2 CCH 60 ##STR58## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 61 ##STR59## CH.sub.3 CH(CH.sub.3)CCH 62 ##STR60## H C(CH.sub.3).sub.2C CH 63 ##STR61## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 64 ##STR62## CH.sub.3 CH(CH.sub.3)CCH 65 ##STR63## H C(CH.sub.3).sub.2CCH 66 ##STR64## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 67 ##STR65## CH.sub.3 CH(CH.sub.3)CCH 68 ##STR66## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 69 ##STR67## CH.sub.3 CH(CH.sub.3)CCH 70 ##STR68## H C(CH.sub.3).sub.2CCH 71 ##STR69## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 72 CHCH.sub.2 CH.sub.3 CH(CH.sub.3)CCH 73 CHCH.sub.2 H C(CH.sub.3).sub.2C C H 74 ##STR70## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 75 ##STR71## CH.sub.3 CH(CH.sub.3)CCH 76 ##STR72## H C(CH.sub.3).sub.2CCH 77 ##STR73## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 78 ##STR74## CH.sub.3 CH(CH.sub.3)CCH 79 ##STR75## CH.sub.3 CH(CH.sub.3)CCH 80 ##STR76## H C(CH.sub.3).sub.2CCH 81 CBr.sub.3 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 82 CBr.sub.3 CH.sub.3 CH(CH.sub.3)CCH 83 CBr.sub.3 H C(CH.sub.3).sub.2CCH 84 CBr.sub.3 H C(CH.sub.3).sub.2CN 85 CBr.sub.3 H CH.sub.2CHCH.sub.2 86 CClCHCl CH.sub.3 CH(CH.sub.3)CCH 87 (CH.sub.2).sub.4 CH.sub.2Br CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 88 (CH.sub.2).sub.4CH.sub.2Br CH.sub.3 CH(CH.sub.3)CCH 89 ##STR77## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 90 ##STR78## CH.sub.3 CH(CH.sub.3)CCH 91 ##STR79## CH.sub.3 CH(CH.sub.3)CCH 92 ##STR80## CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 93 ##STR81## CH.sub.3 CH(CH.sub.3)CCH 94 ##STR82## H C(CH.sub.3).sub.2C CH 95 ##STR83## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 96 ##STR84## H C(CH.sub.3).sub.2CCH 97 ##STR85## CH.sub.3 CH(CH.sub.3)CCH 98 ##STR86## H C(CH.sub.3).sub.2CCH 99 ##STR87## CH.sub.3 CH(CH.sub.3)CCH 100 ##STR88## H C(CH.sub.3).sub.2CCH 101 ##STR89## CH.sub.3 CH(CH.sub.3)CCH 102 ##STR90## H C(CH.sub.3).sub.2CCH 103 ##STR91## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 104 ##STR92## CH.sub.3 CH(CH.sub.3)CCH 105 ##STR93## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 106 ##STR94## CH.sub.3 CH(CH.sub.3)CCH 107 ##STR95## H C(CH.sub.3).sub.2CCH 108 ##STR96## CH.sub.3 CH(CH.sub.3)CCH 109 ##STR97## H C(CH.sub.3).sub.2CCH 110 ##STR98## CH.sub.3 CH(CH.sub.3)CCH 111 ##STR99## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 112 ##STR100## CH.sub.3 CH(CH.sub.3)CCH 113 ##STR101## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 114 ##STR102## H C(CH.sub.3).sub.2CCH 115 ##STR103## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 116 ##STR104## H C(CH.sub.3).sub.2CCH 117 CHCl.sub.2 C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 OH 118 CHCl.sub.2 ##STR105## ##STR106## 119 CHCl.sub.2 CH.sub.2CH.sub.2OSO.sub.2CH.sub.3 CH.sub.2CHOSO.sub.2CH.s ub.3 120 ##STR107## CH.sub.3 CH(CH.sub.3)CCH 121 ##STR108## CH.sub.3 CH(CH.sub.3)CCH 122 CHBrCH.sub.3 CH.sub.3 CH(CH.sub.3)C CH 123 CHBrCH.sub.3 H C(CH.sub.3).sub.2CCH 124 CH.sub.2CH.sub.2 Cl CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 125 CH.sub.2CH.sub.2 Cl CH.sub.3 CH(CH.sub.3)CCH 126 CH.sub.2CH.sub.2 Cl H C(CH.sub.3).sub.2CCH 127 CBr(CH.sub.3).sub.2 H C(CH.sub.3).sub.2CCH 128 CH.sub.2 I CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 129 CH.sub.2 I CH.sub.3 CH(CH.sub.3)CCH 130 CH.sub.2 I H C(CH.sub.3).sub.2CCH 131 CHCl.sub.2 CH.sub.2CH.sub.2 Cl CH.sub.2CH.sub.2 Cl 132 CHCl.sub.2 ##STR109## ##STR110## 133 CHCl.sub.2 ##STR111## ##STR112## 134 CHCl.sub.2 ##STR113## ##STR114## 135 CHCl.sub.2 ##STR115## ##STR116## 136 ##STR117## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 137 ##STR118## CH.sub.3 CH(CH.sub.3)CCH 138 ##STR119## H C(CH.sub.3).sub.2CCH 139 ##STR120## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 140 ##STR121## CH.sub.3 CH(CH.sub.3)CCH 141 ##STR122## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 142 ##STR123## CH.sub.3 CH(CH.sub.3)CCH 143 ##STR124## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 144 ##STR125## CH.sub.3 CH(CH.sub.3)CCH 145 ##STR126## H C(CH.sub.3).sub.2CCH 146 ##STR127## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 147 ##STR128## CH.sub.3 CH(CH.sub.3)CCH 148 ##STR129## H C(CH.sub.3).sub.2CCH 149 ##STR130## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 150 ##STR131## CH.sub.3 CH(CH.sub.3)CCH 151 ##STR132## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 152 ##STR133## CH.sub.3 CH(CH.sub.3)CCH 153 ##STR134## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 154 ##STR135## CH.sub.3 CH(CH.sub.3)CCH 155 ##STR136## CH.sub.3 CH(CH.sub.3)CCH 156 ##STR137## H C(CH.sub.3).sub.2CCH 157 ##STR138## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 158 ##STR139## CH.sub.3 CH(CH.sub.3)CCH 159 ##STR140## CH.sub.2CHCH.sub.2 CH.sub. 2CHCH.sub.2 160 ##STR141## CH.sub.3 CH(CH.sub.3)CCH 161 ##STR142## H C(CH.sub.3).sub.2CCH 162 ##STR143## CH.sub.3 CH(CH.sub.3)CCH 163 ##STR144## CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 164 ##STR145## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 165 ##STR146## H C(CH.sub.3).sub.2CCH 166 ##STR147## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 167 ##STR148## H C(CH.sub.3).sub.2CCH 168 ##STR149## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 169 ##STR150## CH.sub.3 CH(CH.sub.3)CCH 170 ##STR151## H C(CH.sub.3).sub.2CCH 171 ##STR152## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 172 ##STR153## CH.sub.3 CH(CH.sub.3)CCH 173 ##STR154## H C(CH.sub.3).sub.2CCH 174 ##STR155## CH.sub.3 CH(CH.sub.3)CCH 175 ##STR156## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 176 ##STR157## H C(CH.sub.3).sub.2 CCH 177 ##STR158## H C(CH.sub.3).sub.2 CCH 178 ##STR159## H C(CH.sub.3).sub.2 CCH 179 CHCl.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 180 CHCl.sub.2 i-C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 181 CHCl.sub.2 C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 182 CHCl.sub.2 n-C.sub.4 H.sub.9 CH.sub.2CHCH.sub.2 183 CHCl.sub.2 CH.sub.2CHCH.sub.2 CH.sub.2CClCH.sub.2 184 CHCl.sub.2 C.sub.3 H.sub.7 CH.sub.2CClCH.sub.2 185 CHCl.sub.2 i-C.sub.4 H.sub.9 CH.sub.2CHCH.sub.2 186 CHCl.sub.2 CH.sub.2C(CH.sub.3)CH.sub.2 CH.sub.2CHCH.sub.2 187 CHCl.sub.2 n-C.sub.4 H.sub.9 sec-C.sub.4 H.sub.9 188 CHCl.sub.2 n-C.sub.4 H.sub.9 i-C.sub.4 H.sub.9 189 CHCl.sub.2 n-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 190 CHCl.sub.2 i-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 191 CHCl.sub.2 i-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 192 C HCl.sub.2 sec-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 193 CHCl.sub.2 n-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 194 CHCl.sub.2 C.sub.2 H.sub.5 i-C.sub.4 H.sub.9 195 CHCl.sub.2 H ##STR160## 196 CHCl.sub.2 CH.sub.3 NH.sub.2 197 Cl CH.sub.2CHCH.sub.2 CH.sub.2CHCH. sub.2 198 CHCl.sub.2 C[N(CH.sub.3).sub.2 ].sub.2 199 CH.sub.2 Cl C[N(CH.sub.3).sub.2 ].sub.2 200 OCH.sub.2CCCH.sub.3 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 201 OC.sub.2 H.sub.4 Cl CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 202 OCH.sub.2 CHCl.sub.2 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 203 ##STR161## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 204 CH.sub.2SCN CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 205 CH.sub.2N(CH.s ub.2CHCH.sub.2).sub.2 CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 206 CHCl.sub.2 H ##STR162## 207 CHCl.sub.2 CH.sub.3 ##STR163## 208 ##STR164## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 209 CH.sub.2CN CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 210 CH.sub.2OCN CH.sub.2 CHCH.sub.2 CH.sub.2CHCH.sub.2 211 CHCl.sub.2 C.sub.2 H.sub.5 ##STR165## 212 CHCl.sub.2 CH.sub.2CH.sub.2CN CH.sub.2CHCN 213 CHCl.sub.2 H ##STR166## 214 CHCl.sub.2 H ##STR167## 215 CHCl.sub.2 H ##STR168## 216 CHCl.sub.2 H ##STR169## 217 CH.sub.2 Cl H CH.sub.2CH(CH.sub.3).sub.2 218 CHCl.sub.2 H ##STR170## 219 CHCl.sub.2 H i-C.sub.4 H.sub.9 220 CH.sub.2 Cl H t-C.sub.4 H.sub. 9 221 CHCl.sub.2 H t-C.sub.4 H.sub.9 222 CH.sub.2 Cl H CH(CH.sub.3)CH.sub.2CH(CH.sub.3)CH.sub.3 223 CHCl.sub.2 H ##STR171## 224 CHCl.sub.2 H ##STR172## 225 CHCl.sub.2 H ##STR173## 226 CHCl.sub.2 H ##STR174## 227 CHCl.sub.2 H ##STR175## 228 ##STR176## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 229 ##STR177## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 230 ##STR178## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub. 2 231 ##STR179## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 232 CHCl.sub.2 ##STR180## CH.sub.2CHCH.sub.2 233 CHCl.sub.2 t-C.sub.4 H.sub.9 CHCHCH.sub.2CH.sub.3 234 CHCl.sub.2 C(CH.sub.3).sub.2CCH CHCHCH.sub.2CH.sub.3 235 CHCl.sub.2 C.sub.2 H.sub.5 ##STR181## 236 CHCl.sub.2 n-C.sub.4 H.sub.9 CHCHCH.sub.2CH.sub.3 237 CHCl.sub.2 ##STR182## n-C.sub.3 H.sub.7 238 CHCl.sub.2 C(CH.sub.3)CHCH.sub.2CH.sub.3 n-C.sub.3 H.sub.7 239 CH.sub.2SO.sub.2N(CH.sub.2CHCH.sub.2) CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 240 CH(SC.sub.2 H.sub.5).sub.2 CH.sub.2CHCH.sub.2 CH.sub.2 CHCH.sub.2 241 CHCl.sub.2 CH.sub.3 NC(CH.sub.3).sub.2 242 ##STR183## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 243 ##STR184## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 244 CHCl.sub.2 sec-C.sub.4 H.sub.9 C.sub.2 H.sub.5 245 CHCl.sub.2 t-C.sub.4 H.sub.9 C.sub.2 H.sub.5 246 CHCl.sub.2 sec-C.sub.5 H.sub.11 C.sub.2 H.sub.5 247 CHCl.sub.2 i-C.sub.3 H.sub.7 C.sub.2 H.sub.5 248 CHCl.sub.2 CH.sub.3 ##STR185## 249 CHCl.sub.2 C.sub.2 H.sub.5 ##STR186## 250 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR187## 251 CHCl.sub.2 CH.sub.3 sec-C.sub.5 H.sub.11 252 CHCl.sub.2 n-C.sub.3 H.sub.7 sec-C.sub.5 H.sub.11 253 CHCl.sub.2 n-C.sub.3 H.sub.7 n-C.sub.5 H.sub.11 254 CHCl.sub.2 i-C.sub.4 H.sub.9 sec-C.sub.4 H.sub.9 255 CHCl.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 256 CHCl.sub.2 CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)CH.sub.3 257 CHCl.sub.2 C.sub.2 H.sub.5 ##STR188## 258 CHCl.sub.2 C.sub.2 H.sub.5 ##STR189## 259 CHCl.sub.2 C.sub.2 H.sub.5 ##STR190## 260 CHCl.sub.2 CH.sub.3 sec-C.sub.4 H.sub.9 261 CHCl.sub.2 C.sub.2 H.sub.5 n-C.sub.6 H.sub.13 262 CHCl.sub.2 n-C.sub.3 H.sub.7 t-C.sub.4 H.sub.9 263 CHCl.sub.2 n-C.sub.3 H.sub.7 CH(CH.sub.3)CH(CH.sub.3)CH.sub.3 264 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR191## 265 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR192## 266 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR193## 267 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR194## 268 CHCl.sub.2 C.sub.2 H.sub.5 ##STR195## 269 CHCl.sub.2 ##STR196## 270 CHCl.sub.2 ##STR197## 271 CHCl.sub.2 ##STR198## 272 CHCl.sub.2 ##STR199## 273 CHCl.sub.2 ##STR200## 274 CHCl.sub.2 ##STR201## 275 CHCl.sub.2 ##STR202## 276 CHCl.sub.2 ##STR203## 277 CHCl.sub.2 ##STR204## 278 CHCl.sub.2 ##STR205## 279 CHCl.sub.2 ##STR206## 280 CHCl.sub.2 ##STR207## 281 CHCl.sub.2 CH.sub.3 ##STR208## 282 CHCl.sub.2 CH.sub.3 ##STR209## 283 CHCl.sub.2 CH.sub.3 ##STR210## 284 CHCl.sub.2 C.sub.2 H.sub.5 ##STR211## 285 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR212## 286 CHCl.sub.2 ##STR213## 287 CHCl.sub.2 ##STR214## 288 CHCl.sub.2 H ##STR215## 289 CHCl.sub.2 C.sub.2 H.sub.5 ##STR216## 290 CHCl.sub.2 ##STR217## ##STR218## 291 CHCl.sub.2 ##STR219## ##STR220## 292 CHCl.sub.2 CH.sub.2CHCH.sub.2 ##STR221## 293CHCl.sub.2 C.sub.2 H.sub.5 ##STR222## 294 CHCl.sub.2 n-C.sub.3 H.sub.5 ##STR223## 295 CHCl.sub.2 ##STR224## n-C.sub.3 H.sub.7 296 CHCl.sub.2 ##STR225## n-C.sub.3 H.sub.7 297 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR226## 298 CHCl.sub.2 n-C.sub.3 H.sub.7 n-C.sub.6 H.sub.13 299 CHCl.sub.2 C.sub.2 H.sub.4OCH.sub.3 C.sub.2 H.sub.4OCH.sub.3 300 CHCl.sub.2 C.sub.2 H.sub.4OC.sub.2 H.sub.5 C.sub.2 H.sub.4OC.sub.2 H.sub.5 301 CHCl.sub.2 C.sub.2 H.sub.5 ##STR227## 302 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR228## 303 CHCl.sub.2 i-C.sub.3 H.sub.7 ##STR229## 304 CHCl.sub.2 n-C.sub.4 H.sub.9 ##STR230## 305 CHCl.sub.2 ##STR231## 306 CHCl.sub.2 ##STR232## 307 CHCl.sub.2 ##STR233## 308 CHCl.sub.2 ##STR234## 309 CHCl.sub.2 CH.sub.3 ##STR235## 310 CHCl.sub.2 C.sub.2 H.sub.5 ##STR236## 311 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR237## 312 CHCl.sub.2 i-C.sub.3 H.sub.7 ##STR238## 313 CHCl.sub.2 n-C.sub.4 H.sub.9 ##STR239## 314 CHCl.sub.2 sec-C.sub.4 H.sub.9 ##STR240## 315 CHCl.sub.2 t-C.sub.4 H.sub.9 CH.sub.2CH.sub.2 OH 316 CHCl.sub.2 CH.sub.3 ##STR241## 317 CHCl.sub.2 ##STR242## 318 CHCl.sub.2 n-C.sub.6 H.sub.13 n-C.sub.6 H.sub.13 319 CHCl.sub.2 CH.sub.3 CH.sub.2CH.sub.2 OH 320 CHCl.sub.2 ##STR243## 321 CHCl.sub.2 CH.sub.2CH.sub.2SH ##STR244## 322 CHCl.sub.2 H C(C.sub.2 H.sub.5).sub.2CN 323 CH.sub.2 Cl H C(C.sub.2 H.sub.5).sub.2CN 324 CHCl.sub.2 H ##STR245## 325 CHCl.sub.2 H ##STR246## 326 CHCl.sub.2 H ##STR247## 327 CH.sub.2 Cl H ##STR248## 328 CHCl.sub.2 H ##STR249## 329 CHCl.sub.2 H ##STR250## 330 CHCl.sub.2 H ##STR251## 331 CHCl.sub.2 H ##STR252## 332 CHCl.sub.2 H CH.sub.2C(CH.sub.3)CH.sub.2 333 CH.sub.2 Cl H C CH.sub.2(CH.sub.3)CH.sub.2 334 CHCl.sub.2 H CH.sub.2CH.sub.2OCH.sub.3 335 CHCl.sub.2 H ##STR253## 336 CH.sub.2 Cl CH.sub.3 CH.sub.2CCH 337 CHCl.sub.2 CH.sub.3 CH.sub.2CCH 338 CHCl.sub.2 H ##STR254## 339 CHCl.sub.2 H CH.sub.2CH.sub.2N(C.sub.2 H.sub.5).sub.2 340 CHCl.sub.2 H CH.sub. 2CH(OCH.sub.3).sub.2 341 CHCl.sub.2 H ##STR255## 342 ##STR256## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 343 CHCl.sub.2 H ##STR257## 344 CHCl.sub.2 H ##STR258## 345 CHCl.sub.2 H ##STR259## 346 CHCl.sub.2 H ##STR260## 347 CHCl.sub.2 H ##STR261## 348 CHCl.sub.2 H ##STR262## 349 ##STR263## H C(CH.sub. 3).sub.2CN 350 ##STR264## H C(CH.sub.3).sub.2CCH 351 ##STR265## H C(CH.sub.3).sub.2 CN 352 ##STR266## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 353 ##STR267## H C(CH.sub.3).sub.2C N 354 ##STR268## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 355 ##STR269## H C(CH.sub.3).sub.2CCH 356 ##STR270## H C(CH.sub.3).sub.2CN 357 ##STR271## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 358 ##STR272## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 359 ##STR273## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 360 ##STR274## H C(CH.sub.3).sub.2CCH 361 ##STR275## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 362 ##STR276## H C(CH.sub.3).sub.2CCH 363 ##STR277## H C(CH.sub.3).sub.2CCH 364 CHCl.sub.2 H C(CH.sub.3)CHCN 365 ##STR278## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 366 CHCl.sub.2 H ##STR279## 367 CHCl.sub.2 ##STR280## 368 CHCl.sub.2 ##STR281## CH.sub.2CH(CH.sub.3).sub.2 369 CHCl.sub.2 CHO CH.sub.2CH(CH.sub.3).sub.2 370 ##STR282## H C(CH.sub.3).sub.3 371 ##STR283## H C(CH.sub.3).sub.3 372 ##STR284## H C(CH.sub.3).sub.2CCH 373 ##STR285## CH.sub.3 CH(CH.sub.3)CCH 374 ##STR286## H C(CH.sub.3).sub.2CN 375 ##STR287## H C(CH.sub.3).sub.2CN C N 376 CH.sub.2C(CH.sub.3).sub.3 H C(CH.sub.3).sub.2 377 ##STR288## H C(CH.sub.3).sub.2CCH 378 ##STR289## H C(CH.sub.3).sub.2CCH 379 ##STR290## H C(CH.sub.3).sub.2CCH 380 ##STR291## H C(CH.sub.3).sub.2CN 381 ##STR292## CH.sub.3 CH(CH.sub.3)CCH 382 ##STR293## H C(CH.sub.3).sub.2CCH 383 ##STR294## H C(CH.sub.3).sub.2CN 384 H H ##STR295## 385 ##STR296## CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 386 CHCl.sub.2 ##STR297## 387 CH.sub.2 Cl H ##STR298## 388 CCl.sub.3 H ##STR299## 389 CHCl.sub.2 H ##STR300## 390 CHCl.sub.2 H ##STR301## 391 CHCl.sub.2 H ##STR302## 392 CHCl.sub.2 H ##STR303## 393 CHCl.sub.2 H ##STR304## 394 CH.sub.3 H C(CF.sub.3).sub.2OH 395 CHCl.sub.2 H ##STR305## 396 CHCl.sub.2 H ##STR306## 397 CH.sub.2OC(CHCl.sub.2).sub.2OH CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 398 CH.sub.2OC(CHCl.sub.2)(CCl.sub.3)OH CH.sub.2CHCH.sub.2 CH.sub.2CHCH. sub.2 399 CH.sub.2 Cl H ##STR307## 400 ##STR308## H ##STR309## 401 ##STR310## H ##STR311## 402 CH.sub.2 Cl n-C.sub.4 H.sub.9 CHCH.sub.2 403 ##STR312## H ##STR313## 404 CH.sub.2 Cl CH.sub.3 CH.sub.2CH.sub.2CN 405 CH.sub.2 Cl n-C.sub.6 H.sub.13 n-C.sub.6 H.sub.13 406 CH.sub.2 Cl C.sub.2 H.sub.5 ##STR314## 407 CH.sub.2 Cl n-C.sub.3 H.sub.7 ##STR315## 408 CH.sub.2 Cl i-C.sub.3 H.sub.7 ##STR316## 409 CH.sub.2 Cl CH.sub.3 ##STR317## 410 CH.sub.2 Cl CH.sub.3 ##STR318## 411 CH.sub.2 Cl C.sub.2 H.sub.5 ##STR319## 412 CH.sub.2 Cl n-C.sub.3 H.sub.7 ##STR320## 413 CH.sub.2 Cl ##STR321## 414 CH.sub.2 Cl ##STR322## 415 CH.sub.2 Cl ##STR323## 416 CH.sub.2 Cl CH.sub.3 i-C.sub.3 H.sub.7 417 CH.sub.2 Cl CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)CH.sub.3 418 CH.sub.2 Cl C.sub.2 H.sub.5 ##STR324## 419 CH.sub.2 Cl n-C.sub.3 H.sub.7 i-C.sub.4 H.sub.9 420 CH.sub.2 Cl n-C.sub.3 H.sub.7 sec-C.sub.5 H.sub.11 421 CH.sub.2 Cl n-C.sub.3 H.sub.7 t-C.sub.4 H.sub.9 422 CH.sub.2 Cl i-C.sub.4 H.sub.9 sec-C.sub.4 H.sub.9 423 CH.sub.2 Cl C.sub.2 H.sub.5 sec-C.sub.4 H.sub.9 424 CH.sub.2 Cl i-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 425 CH.sub.2 Cl n-C.sub.4 H.sub.9 i-C.sub.3 H.sub.7 426 CH.sub.2 Cl n-C.sub.4 H.sub.9 i-C.sub.4 H.sub.9 427 CH.sub.2 Cl CH.sub.2CH.sub.2OCH.sub.3 CH.sub.2CH.sub.2OCH.sub.3 428 CH.sub.2 Cl CH.sub.2CH.sub.2OC.sub.2 H.sub.5 CH.sub.2CH.sub.2OC.sub.2 H.sub.5 429 CH.sub.2 Cl ##STR325## n-C.sub.3 H.sub.7 430 CH.sub.2 Cl ##STR326## n-C.sub.3 H.sub.7 431 CH.sub.2 Cl n-C.sub.3 H.sub.7 ##STR327## 432 CH.sub.2 Cl n-C.sub.3 H.sub.7 ##STR328## 433 CH.sub.2 Cl n-C.sub.3 H.sub.7 ##STR329## 434 CH.sub.2 Cl C.sub.2 H.sub.5 ##STR330## 435 CH.sub.2 Cl C.sub.2 H.sub.5 ##STR331## 436 CH.sub.2 Cl n-C.sub.3 H.sub.7 ##STR332## 437 CH.sub.2 Cl C.sub.2 H.sub.5 ##STR333## 438 CH.sub.2 Cl CH.sub.3 ##STR334## 439 CHCl.sub.2 CH.sub.3 ##STR335## 440 CHCl.sub.2 C.sub.2 H.sub.5 ##STR336## 441 CHCl.sub.2 n-C.sub.3 H.sub.7 ##STR337## 442 CHCl.sub.2 C.sub.2 H.sub.5 ##STR338## 443 CHCl.sub.2 C.sub.2 H.sub.5 ##STR339## 444 CHCl.sub.2 CH.sub.3 n-C.sub.4 H.sub.9 445 CH.sub.2 Cl CH.sub.3 n-C.sub.4 H.sub.9 446 CHCl.sub.2 CH.sub.3 sec-C.sub.4 H.sub.9 447 CH.sub.2 Cl CH.sub.3 sec-C.sub.4 H.sub.9 448 CHCl.sub.2 CH.sub.3 n-C.sub.3 H.sub.7 449 CH.sub.2 Cl CH.sub.3 n-C.sub.3 H.sub.7 450 CHCl.sub.2 n-C.sub.4 H.sub.9 t-C.sub.4 H.sub.9 451 CHCl.sub.2 i-C.sub.3 H.sub.7 sec-C.sub.4 H.sub.9 452 CH.sub.2 Cl i-C.sub.3 H.sub.7 sec-C.sub.4 H.sub.9 453 CHCl.sub.2 i-C.sub.3 H.sub.7 n-C.sub.5 H.sub.11 454 CH.sub.2 Cl i-C.sub. 3 H.sub.7 n-C.sub.5 H.sub.11 455 CHCl.sub.2 i-C.sub.3 H.sub.7 sec-C.sub.5 H.sub.11 456 CHCl.sub.2 H ##STR340## 457 CHCl.sub.2 H ##STR341## 458 CHCl.sub.2 H ##STR342## 459 CHCl.sub.2 H ##STR343## 460 CHCl.sub.2 H ##STR344## 461 CHCl.sub.2 CH.sub.2OCH.sub.3 ##STR345## 462 CHCl.sub.2 H ##STR346## 463 CHCl.sub.2 H ##STR347## 464 CHCl.sub.2 CHO ##STR348## 465 CHCl.sub.2 CH.sub.2CH(CH.sub.3).sub.2 ##STR349## 466 CHCl.sub.2 H (CH.sub.2).sub.3OCH(CH.sub.3).sub.2 467 CHCl.sub.2 H ##STR350## 468 CHCl.sub.2 H C(C.sub.2 H.sub.5)(CH.sub.3).sub.2 469 CHCl.sub.2 H ##STR351## 470 CH.sub.2 Cl H C(C.sub.2 H.sub.5)(CH.sub.3).sub.2 471 CH.sub.2 Cl H C .sub.2 H.sub.4OCH.sub.3 472 CH.sub.2 Cl H CH.sub.2CH(OCH.sub.3).sub.2 473 ##STR352## H C(CH.sub.3).sub.2CN 474 ##STR353## H C(CH.sub.3).sub.2C CH 475 CHCl.sub.2 ##STR354## ##STR355## 476 CHCl.sub.2 ##STR356## ##STR357## 477 CHCl.sub.2 ##STR358## ##STR359## 478 CHCl.sub.2 ##STR360## ##STR361## 479 CHCl.sub.2 ##STR362## ##STR363## 480 CH.sub.2 Cl ##STR364## ##STR365## 481 CH.sub.2 Cl ##STR366## ##STR367## 482 CH.sub.2 Cl ##STR368## ##STR369## 483 CH.sub.2 Cl ##STR370## ##STR371## 484 CHCl.sub.2 H CH.sub.2CH.sub.2OH 485 CH.sub.2 Cl CH.sub.2CH.sub.2OH C H.sub. 2CH.sub.2OH 486 CHCl.sub.2 H CH.sub.2CH(OH)(CH.sub.3) 487 CHCl.sub.2 H (CH.sub.2).sub.3OH 488 CHCl.sub.2 CH.sub.2CH(OH)(CH.sub.3) CH.sub.2CH(OH)(CH.sub.3) 489 CHCl.sub.2 ##STR372## 490 CH.sub.2 OH C.sub.2 H.sub.5 C.sub.2 H.sub.5 491 CH.sub.3 ##STR373## ##STR374## 492 ##STR375## H CH.sub.2CH(CH.sub.3).sub.2 493 CH.sub.2SO.sub.2OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 494 C.sub.3 H.sub.6 Br H SO.sub.2 Cl 495 CHCl.sub.2 ##STR376## 496 CCl.sub.3 C.sub.3 H.sub.7 C.sub.3 H.sub.7 497 CCl.sub.3 ##STR377## 498 CCl.sub.3 ##STR378## 499 CH.sub.2 Cl ##STR379## 500 CCl.sub.3 CH.sub.3 CH.sub.3 501 CH.sub.2 Cl H C.sub.2 H.sub.4 Br 502 CCl.sub.3 H C.sub.2 H.sub.4 Br 503 CHCl.sub.2 H C.sub.2 H.sub.4 Br 504 CHCl.sub.2 C.sub.2 H.sub.5 n-C.sub.4 H.sub.9 505 CHCl.sub.2 i-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 506 CHCl.sub.2 n-C.sub.4 H.sub.9 n-C.sub.4 H.sub.9 507 CCl.sub.3 C.sub.2 H.sub.5 n-C.sub.4 H.sub.9 508 CCl.sub.3 i-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 509 CCl.sub.3 i-C.sub.4 H.sub.9 i-C.sub.4 H.sub.9 510 CHCl.sub.2 H ##STR380## 511 CCl.sub.3 H C(CH.sub.3)(C.sub.2 H.sub.5)CN 512 CH.sub.2 Cl H C(CH.sub.3)(C.sub.2 H.sub.5)CN 513 CHCl.sub.2 H C(CH.sub.3)(C.sub.2 H.sub.5)CN

The compositions of this invention were tested in the following manner.

Small flats were filled with Felton loamy sand soil. The herbicide and herbicide antidote were applied separately or in combination to the soil as it is mixed in a five-gallon cement mixer. The following stock solutions were made up of each compound when the herbicide and antidote were applied separately. Stock solutions of the herbicide were ddiluted with 100 ml. of water. For the antidote, 700 mg. of technical material was diluted with 100 ml. of acetone. One ml. of these stock solutions is equivalent to 7 mg. active ingredient or one pound per acre when this treated soil was placed into 8.times.12.times.3" flats. After the soil was treated with the herbicide and the antidote at the desired rates, the soil was transferred from the cement mixer back into 8.times.12.times.3" flats where it was now ready for planting corn seed. A pint sample of soil was then removed from each flat and retained for covering the seeds after planting. The soil was leveled and rows one-half inch deep were made in each flat. Enough seeds were planted to obtain good stands in each treatment. Seeds were then covered up with the one pint of soil which had been removed just prior to planting.

The flats were then placed on greenhouse benches where temperatures were between 70.degree.-90.degree. F. The flats were watered by sprinkling as needed to assure good plant growth until rated. The crop tolerance was rated after three to six weeks. The results of these tests are set forth in Table II.

Small flats were filled with Felton loamy sand soil. Soil incorporated herbicides were applied at this time. The soil from each flat was placed into a five-gallon cement mixer where the soil was mixed as the herbicides were applied as a stock solution in 100 ml. of water. One ml. of stock solution was applied to the soil in a volumetric pipet for each pound of herbicide desired. One ml. of stock solution contains seven mg of herbicide which equals one pound per acre when applied to soil in 8.times.12.times.3" flats. After the herbicide incorporation, the soil was placed back into the flats.

Flats of herbicide-treated and untreated soil were then ready to be planted. A pint sample of soil was then removed from each flat and placed next to each flat for later use in covering up the seeds. The soil was leveled and raws one-half inches deep were made for planting seeds. Alternating rows of treated and untreated crop seeds were sown. In each test six or more seeds were planted in each row. Rows were approximately 11/2" apart in the flat. Seed treatment was applied by placing 50 mg. of the seed treatment compound with 10 grams of seed in a suitable container and shaking them until the seeds were uniformly covered with the seed treatment. Seed treatment compounds were applied as liquid slurries and powder or dust treatments. In some cases acetone was used to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.

After flats were seeded they were covered with the one pint of soil which had been removed just prior to planting. Flats were placed on greenhouse benches where temperatures ranged from 70.degree.-90.degree. C. Flats were watered by sprinkling as needed to assure good plant growth. Percent injury ratings were taken two to four weeks after treatments were applied.

In each test, the herbicide is applied alone, in combination with the seed protectant and the seed protectant is applied alone to check for phytotoxicity. The results of these tests are tabulated in Table III.

The antidoate compounds of the present invention can be used in any convenient form. Thus, the antidoate compounds can be made into emulsifiable liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form. In its preferred form, the antidoate compounds are admixed with the thiolcarbamates and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the thiolcarbamate herbicide can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the seed can be treated with the antidoate compound and planted into the soil which has been treated with herbicides or untreated with the herbicide and subsequently treated with the herbicide. The method of addition of the antidote compound does not affect the herbicidal activity of the carbamate compounds.

The amount of antidote composition present can range between about 0.0001 to about 30 parts by weight per each part by weight of thiolcarbamate herbicide. The exact amount of antidoate compound will usually be determined on economic ratios for the most effective amount usable.

When used in the claims of this application, the phrase "active herbicidal compound" is meant to include the active thiolcarbamates alone or the thiolcarbamates admixed with other active compounds such as the s-triazines and 2,4-D, or the active acetanilides and the like. Also, the active herbicidal compound is different from the antidoate compound.

It is clear that the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbicidal activity varies among specific compound and among combinations of specific compounds within the classes. Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus, selection of a specific herbicidal compound or combination to control undesirable plant species readily may be made. Within the present invention the prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by this method is not intended to be limited by the specific crops employed in the examples.

The herbicidal compounds employed in the method of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effective against a wide range of plant species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the hereindescribed herbicidal compounds to the area or plant locus where control is desired.

An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants" it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions.

The herbicides indicated in the tables are used at rates which produce effective control of undesirable vegetation. The rates are within the recommended amounts set forth by the supplier. Therefore, the weed control in each instance is commercially acceptable within the desired amount.

In the above description of the antidote compounds, the following embodiments are intended for the various substituent groups; alkyl includes, unless otherwise provided for, those members which contain from 1 to 20 carbon atoms, inclusive, in both straight and branched chain configurations; alkenyl includes, unless otherwise provided for, those members which contain at least one olefinic double bond and contain from 2 to 20 carbon atoms, inclusive, preferably from 2 to 12 carbon atoms, inclusive, in both straight and branched chain configurations; and alkynyl includes, unless otherwise provided for, those members which contain at least one acetylenic triple bond and contain from 2 to 20 carbon atoms, inclusive, preferably from 2 to 12 carbon atoms, inclusive, in both straight and branched chain configurations.