CA1174865A

CA1174865A - Thiolcarbamate herbicides containing nitrogen containing antidote

Info

Publication number: CA1174865A
Application number: CA000139060A
Authority: CA
Inventors: Ferenc M. Pallos; Mervin E. Brokke; Duane R. Arneklev
Original assignee: Stauffer Chemical Co
Current assignee: Syngenta Crop Protection LLC
Priority date: 1971-04-16
Filing date: 1972-04-06
Publication date: 1984-09-25
Also published as: IT953649B; GB1396942A; CH577785A5; RO83877B; IL39219A; DE2218097A1; DK143583B; RO83875B; DK143583C; ES401779A1; FR2133793A1; BE782120A; NL7204894A; RO78996A; DE2218097C2; FR2133793B1; PL99481B1; DD102075A5; CS196241B2; TR18613A

Abstract

Herbicidal compositions consisting of an active herbicidal compound and an antidote therefor and the methods of use of the herbicide composition are described herein. The antidote compound corresponds to the formula:

(see formula I) 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; haloalkylcarbonylaoxyalkyl; alkyoxycarboalkyl;
haloalkenylcarbonyloxyalkyl;
hydroxyhaloalkyloxyalkyl; hydroxyalkylcarboalkyoxyalkyl;
hydroxyalkyl; alkoxysulfonoalkyl; furyl; thienyl;
alkyldithiolenyl; thienalkyl; phenyl and substituted phenyl wherein said substituents can be selected

Description

;;~.3..7~

Back round of the Invention y Among the many hdrbicidal compounds commercially avaii-able the thiolcarbamates alone ox 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. Patent Nos.

2,913,327, 3,037,853, 3,175,897, 3,135,720, 3,198,786 and

3,S82,314. 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 80il to control many broadleaf weeds and grasses, serious malformation and stunting of the crop plants result. This abnor-mal 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.
Description of the Invention 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

4 865 by adding to the soil an an~idote compound corresponding to the following ~ormula:

R_R_ 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-alkynylcarhamylalkoxyalkyl;
alkynoxy; haloalkoxy/,i thiocyanatoalkyl; alkenylaminoalkyl; alkyl-carboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminos~lfonoalkyl;
alkylthioalkyl; haloalkylcarbonyloxyalkyl, alkyoxycarboalkyl;
haloalkenylcarbonyloxyalkyl; hydroxyhaloalkyloxyalkyl; hydroxy-alkylcarboalkyoxyalkyl; hydroxyaikyl; alkoxysul~onoalkyl; 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; phenyl-alkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halophenyl-alkenoxy; halothiophenylalkyl; halophenoxyalkyl; bicycloalkyl;
alkenyLcarbamylpyridinyl; alkynylcarbamylpyridinyl; dialkenyl-carbamylbicycloalkenyl; alkynylcarbamylbicycloalkenyl; Rl and R2 can be the same or different and can be selected from the group consisting of alkenyl; haloalkenyl; hydrogen; alkyl; haloalkyl;
alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; haloalkyl-carboxyalkyl; alkyIcarboxyalkyl; alkoxycarboxyalkyl; thioalkyl-carboxyalkyl; alkoxycarboalkyl; alkylcarbamyloxyalkyl; amino;
formyl; haloalkyl-N-alkylamido; haloalkylamido; haloalkylamido-alkyl; haloalkyl-N-alkylamidoalkyl; haloalkylamidoalkenyl; alkyl-imino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxy-

- 5 -~174865 alkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarboalkenyl; halo-alkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxyalkyl; cycloalkyl-carbamyloxyalkyl; alkoxycarbonyl; haloalkoxycarbonyl; halophenyl-carbamyloxyalkyl; 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; halobenzothiazolyl;
furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofuryl-alkyl; 3-cyano, 4,5-polyalkylene-thienyl; O~-haloalkylacetamido-phenylalkyl; ~-haloalkylacetamidonitrophenylalkyl; ~-haloalkyl-acetamidohalophenylalkyl; cyanoalkenyl; Rl and R2 when taken to-gether can form a structure consisting of piperidinyl; alkylpiperi-dinyl; alkyltetrahydropyridyl; morpholyl; alkylmorpholyl; azo-bicyclon~onyl; benzoalkylpyrrolidinyl; oxazolidyl; alkyloxazolidyl;
perhydroquinolyl; alkylaminoalkenyl; provided that when Rl is hy-drogen R2 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 inven-tion, reference is made to the following examples:

.

`:
~174~36~i Example 1 ,CH2-CH-CH2 CHC12-C-N ~
CH2-CH=CH2 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 5C. in an ice bath. Then, 4.9 g.
(0.05 mole) of diallyl amine was added dropwise while the tempera-ture was maintained at below about 10C. 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., n30 _ 1.4990.

Example 2 CHC12-C-N ~ 3 7 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 10C. 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 10C. 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., n30 _ 1.4778.

~74~3~5 }~ample 3 CHCl2-C-N ~ H3 ~ H(CH3) C CH
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 10C. in an ice bath. Then, 4.2 g.
(0.05 mole) of N-methyl, N-l-methyl-3-propynylamine in 20 ml. of methylene dichloride was added dropwise while the temperature was maintained about lO~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., n30 _ 1.4980.

Example 4 CH2Cl -C -NH-CH2~

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 15C. 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.

1174~65 Example 5 CHC12-C-NH ~

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 10-15C. and then 5.2 ml. (0.~ 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 sulate and then filtered to remove the solvent.

Example 6 ~ ~H
CHC12- -N ~ ~ Br 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 15C. 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 40-50C.

. , .

~ - j 4 ~6~S

Example 7 C-N~
C(CH3)zC- CH

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

Example 8 `~CH-8-N ~ 2 2 H2~ ~ CH2-CH-CH2 A solutionWaS formed containing 5.9 g. of diallyl amine diæsolved in 15 ml. of methylene chloride and 6.5 g. of triethyl-amine. Then, 6.3 g. of cyclopropane carbonyl chloride~as added dropwlse with stirring and cooling in a water bath. When the react~onwascomplete the mixture wes washed with water, dried and the solvent stripped off to give 8.2 g. of product.

Example 9 ~ ~CH2-CH=CH2 F CH2-CH=CH2 A solutionwas formed containing 4.5 g. of diallyl amine dissolved in 15 ml. of methylene chl~ride and 5.0 g. of triethyl-amine. Then, 7.1 g. of ortho-fluorobenzoyl chloridewas added 1~74865 dropwise with stirring and cooling in a water bath. When the reac~ion was complete, the mixture was washed with water, dried and the solvent stripped off to give 8.5 g. of product.
Example 10 Q

CHC12,,~_N~CH2 CH2-0-~-NH-CH3 "CH2-CH2-0-~ NH CH3 N,N-bis(2-hydroxyethyl) dichloroacetamide wss prepared S ~ by reacting 26.3 g. of diethanolamine with 37 ~. 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) dichloro-acetamidewas 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 productwas stripped under vacuum to yield 8.4 g. of product.

Example 11 CH2=CH-CH2~ ~ R ,CH2-CH=CH2 ,~N- -CH2-c-N
CH2=CH-CH2 ~CH2-CH=CH2 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.

6 5 - -Example 12 CH =CH-CH R R CH -CH=CH
2 2~ N-~-CH2-CH2-C-N ~ 2 2 CH2=CH-CH2~ ~ CH2-CH=CH2

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.

Example 13 ~H3 ~ ~CH3 CH ~ C-CIH-N-~-CH2 CH2 ~ CH-C-= CH

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

Example 14 RC N ~CH2 CH CH2 e;~ ~CH2-CH=CH2 O=c-N(cH2-cH=cH2)2 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 1~74~365 cooling and stirring. When the reaction was complete, the m~xture was washed with water, dried over magnesium sulfate and stripped under vacuum to yield 10.9 g. of product.
Example 15 ~ R ~H3 CH- -N-CH-C- CH
~ CH3 3.3 g. of N-methyl-l-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 drop-w~se 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.

Example 16 ~C- ~ H2 CH CH2 -CH=CH2 O-C-OH
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.

Example 17 C-NH-I_C---- CH

O=C~ONa 9.2 g. of N(l,l-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 ~nd cooling.
The solvent was stripped or removed under vacuum to yield 9.0 g.
of product. The intermediate, N(l,l-dimethyl-3-propynyl)O-phthalamate was prepared from 29.6 g. o~ 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.

Example 18 CHCl -~-N ~ 2H5 2 ~C2H5 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.
o methylene chloride were charged to the flask and the mixture ~as 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 sul-fate and concentrated under vacuum to yield 16.8 g. of product.

~1'7~365 Example 19 C CH2-CH=CH2 CH3~C ~ C-CH2-0- -N
~CH2-CH=CH2 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 pro-duct was stirred at room temperature overnight, washed with water twice and dried over magnesium sulfate to yield 4.0 g. of pro-duct.

Example 20 ~ ~CH2-CH-CH2 N -C-S-CH2-C-N~
CH2-CH=CH2 9.7 g~ (0.1 mole) of potassium thiocyanate was dis-solved in 100 ml. of acetone. Then, 8.7 g. (0.05 mole) of N,N-diallyl chloroacetamide were added at room temperature ~Jith 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.

i:~L7~365 Example 21 CHC12-~C_NH_C--f 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 tri-ethylamine in 2 ml. of benzene at a temperature of 5-10C. A
precipitate was formed and the mixture was stirred for two hours at room temperature and one hour at 50-55C. The product was worked-up as in previous examples to yield 5.7 g. of the product.

Example 22 CHC12-~-NH-CH ~ ~H
0' 2 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 to 0C. The mixture was stirred ten more minutes around 0C., then allo~ed to warm to room temperature with stirring. The layers were separated and the organic layer washed with dilute hydrochloric acid-, 10~/o sodium carb~nate solution, water and dried to yie?d 5.9 g. of product.

~ ~' i 1~'74~365 Example 23 ~ ~H2-CH=CH2 ~ CH=CH- -N
~ CH2-CH=CH2 Cl In a solution of 75 ml. of benzene containing 5.7 g. of meta-chlorocinnamyl chloride was formed. To this solution was ad-ded 3.2 g. of diallyl amine and 3.3 g. of triethyl amine in 2 ml.
of benzene at a temperature of 5 to 10C. A precipitate was ; formed and the mLxture was stirred for two hours at room tempera-ture and one hour at 55C. The product was washed and worked up to yield 5.8 g. of product.

Example 24 CHCl2 ~ ~ CH3 A 500 cc. 4-necked flask was provided with a stirrer, thermometer and addition unnel. Then, 11.9 g. 2,4-dimethyl-piperidine, 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 ~mmersed 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.

.
Example 25 CHC12 ~

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 so$u-tion and 100 ml. of methylene chloride were added together. Then, 14.7 g. of dichloroacetyl chloride was added portionwise.
The reactio~ 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.

ExamPle 26 CHCl ~_N "CH2 CH2 CH2 NH 2 2 CH2-CH2-CH2-NH-~-CHC12 A 500 ml. 4-necked flask was provided with stirrer, thenmometer 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 ~ 7~
21.0 g. of product.

ample 27 CHC12_~_N~ H2 C3H7 n A S00 ml. 4-necked flask was provided with stirrer, thermometer and addition funnel, Then, 7.5 g. of tetrahydrofur-furyl-n-propylamine (0,0525 mole) and 2.0 g, sodium hydroxide ~ solution and 100 ml. of methylene c~loride 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 28 cHcl2BrO

~ Example 27 was repeated in its entirety except that

8,9 g, of piperidine was used as the amine.

Example 29 CHcl2-~-N3 Example 28 was essentially repeated in its entirety except 9,1 g. of morpholine was used as the amine, Example 30 CHC12- -NH-C ~

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 r~xed until water ceased to come over. On cooling the product crystallized from benzene yielding 7.0 g. of product.

Example 31 ~ C-NH-C-C~CH

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-l-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.

Example 32 N - C-Ç-NH-C
CH3 ~ ~ C-NH-C-C - N
N~C- -MH- CH3 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.

~ 7 ~
of benæene-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.

Example 33 C-N(CH2-CH=CH2)2 S-N(CH2-CH=CH2)2 o 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.

Example 34 CH -CH -3-N"'' 2 2 CH ~ CH2-CH=CH2 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.

~7486~ - -Example 35 CHC12-~-N

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 0C. 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 soiid that was washed with n-pentane to give 5.0 g. of product.

Example 36 CH C~ N ~ 3 7 2 ~, o 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 chloride was added portionwise. The mixture was stirred for about one additional hour, ~mmersed 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.

1~.74~
Example 37 CH2C~ N~C2H5 CH2~CH3 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.

ExamPle 38 CHC12-~-NH~

4.7 g. of amino pyridine were charged to a reaction vessel along with 100 ml. of acetone and stirred at 10-15C. Then, 7.0 ml. of triethylamine were added dropwise. Thereafter, 5.25 ml.
o 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.

74~

Example 39 CHC12-C-NH~ ~H

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 0-10C. over a period of 5 minutes.
Then, 7.0 ml. of triethylamine was added. The reaction mass was 5 , 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.

Example 40 -CH2-o-~ c3H7-i CH2-CH2-0-C-NH-C3H7 -i 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.

~74~6S
Example 41 o ~0~ ~,CH2-CH2-0-C-N~
CH2Cl-C-N
\CH2 -CH2 - O-C~ -~

The compound of this example was prepared by xeacting 3.6 g. of N,N-bis(2-hydroxyethyl) chl~oroacetamide with 5.0 g. of cyclohexyl isocyanate in the presence of 50 ml. of acetone and dibutyltin dilaurate and triethylenediamine catalysts. The reac-tion mass was heated to re~lux and stripped under vacuum to yield 6-9 g- of product.

Example 42 CHC12 C~o 15 g. of acetone and 12.2 g. of ethanol amine were com-bined in 150 ml. of benzene and refluxed until no additional water came over. The resulting solution was examined and found to con-tain 2,2-dimethyl-1,3-oxazolidine. A quarter of the benzene solu-tion (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 recrystal-lized from ether giving a white product.
.
~ 15 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 em-bodied by the present invention. Compound numbers have been assigned ~o them and are used for identification throughout the balance of the specification.

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~17486S

~ C~
~ æ c~
~ , , , . Z :C

Z C,~

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o=~
E~ ~Y
.

~o ~t~65 Il ~.. 51~1 Y Y

y ~ I I I I I
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U ~ ~ o ~ o~ o ~ o o o o 1~74865 The co~positions of this invention were tested in the following manner.

Test 1: Soil Incorporation 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 mi~ed in a five-gallon cement mixer. The follow~ng stock solutions were made up of each compound when the herbicide and antidote were applied separately. Stock solutions of the herbicide were diluted 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. act~ve ingredient or one pound per acre when this treated 50il was placed into 8 x 12 x 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 x 12 x 3"
flats where it was now ready for planting corn seed. A pint sample of soil was then removed fro~ each flat and reta~*ed for covering the seeds after planting. The æoil was leveled and rows one-half ~ncb deep ~ere made in each flat. Ehough seeds were planted to obtain good stands in esch 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 70-90F. The flats were watered by ! sprinkling as needed to assure good plant growth until rated. The crop tolerance was rated after three to s~x weeks. The results of these tests are set forth in Table II.

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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 solu-tion in lOO ~l. of water. One ml. of stock solution was applied to the soil in a volumetric pipet for each pound of herbicide de-sired. One ml. of stock solution contains seven mg of herbicide which equals one pound per acre when applied to soil in 8 x 12 x 311 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 rows one-half inches deep were made for planting seeds. Alternating rows of treated and un-treated crop seeds were sown. In each test six or more seeds were planted in eacb row. Rows were approximately l-l/2" apart in the flat. Seed treatment was applied by placing 50 mg, of the seed treatment compound with lO grams of seed in a suitable con-tainer 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 1~L74~65 - -70-90C. 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 combina-tion 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.

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1~74~365 The antidote compounds of the present invention can be used in any convenient form. Thus, the antidote compounds can be made into emulsifiable liquids, emulsifiable concentrates, li~uid, wettable powder, powders, granular or any other convenient form.
In its preferred form, the antidote 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 10 ; soil. Moreover, the seed can be treated with the antidote com-pound and planted into the soil which has been treated with herbi-cides 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 carba-mate compounds.

The amount of antidote composition present can range between about C.O~lto about 30 parts by weight per each part by weight of thiolcarbamate herbicide. The exact amount of antidote 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 thiol-carbamates alone or the thiolcarbamates admixed with other active compounds such as the s-triazines and 2,~-D, or the active acet-anilides and the like. Also, the active herbicidal compound is different from the antidote compound.

~ - 138 -1~7~65 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 compounds 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 10 ~ 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 herein-described herbicidal compounds to the area or plant locus where control is desired.

An herbicide as used herein means a compound ~hich con-trols or modifies the growth of vegetation or plants. Such con-trolling 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.

~17~36S

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 leas~
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 con-tain 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.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A herbicidal composition comprising an active herbicidal compound selected from the group consisting of thiol-carbamates, herbicidally active acetanilides, thiolcarbamates in combination with herbicides selected from the group consisting of triazines, 2,4-D and 2(4-chloro-6-ethyl-amino-5-triazine -2yl-amino)-2-methyl propionitrile and an antidote therefor corresponding to the formula:

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; alkyl-carboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminosulfonoalkyl;
alkylthioalkyl; haloalkylcarbonyloxyalkyl; alkyoxycarboalkyl; halo-alkenylcarbonyloxyall;yl;.hydroxyhaloalkyloxyalkyl; hydroxyalkyl-carboalkyoxyalkyl; 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, halo-alkylcarbamyl; phenylalkyl; phenylhaloalkyl; phenylalkenyl; substi-tuted phenylalkenyl wherein said substituents can be selected from halogen, alkyl, alkoxy; halophenoxy; phenylalkoxy; phenylalkyl-carboxyalkyl; phenylcycloalkyl; halophenylalkenoxy; halothiophenyl-alkyl; halophenoxyalkyl; bicycloalkyl; alkenylcarbamylpyridinyl;
alkynylcarbamylpyridinyl; dialkenylcarbamylbicycloalkenyl; alkynyl-carbamylbicycloalkenyl; Rl and R2 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; alkoxy-carboxyalkyl; thioallcylcarboxyalkyl; alkoxycarboalkyl; alkylcar-bamyloxyalkyl; amino; formyl; haloalkyl-N-alkylamido; haloalkyl-amido; haloalkylamidoalkyl; haloalkyl-N-allcylamidoalkyl; haloalkyl-amidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl;
alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarbo-alkenyl; 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, alkyl-carbamyloxy, alkenylcarbamyloxy, alkylamido, haloalkylamido, alkyl-carboalkenyl; phenylsulfonyl; phenylalkyl; substituted phenylalkyl wherein said substituents can be selected from halogen, alkyl, dioxyalkylene, halophenoxyalkylamidoalkyl; alkylthiodiazolyl;
piperidylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; halo-benzothiazolyl; furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl;
tetrahydrofurylalkyl; 3-cyano, 4,5-polyalkylene-thienyl; .alpha.-halo-alkylacetamidophenylalkyl; o( -haloalkylacetamidonitrophenylalkyl;
.alpha.-haloalkylacetamidohalophenylalkyl; cyanoalkenyl; Rl and R2 when taken together can form a structure consisting of piperidinyl;
alkylpiperidinyl; alkyltetrahydropyridyl; morpholyl; alkylmor-pholyl; azobicyclononyl; benzoalkylpyrrolidinyl; oxazolidyl; alkyl-oxazolidyl; perhydroquinolyl; alkylaminoalkenyl; provided that when Rl is hydrogen R2 is other than hydrogen and halophenyl provided than when R1 is allyl or propynyl then R is other than carbamyl allyl, carbamyl mono or di-propynyl, and methylene carbamyl propynyl, provided that said herbicidally active acetanilide is other than N- ( 2 ' -methoxyethyl) -2, 6-dimethyl-chloroacetanilide.

2. The composition as set forth in Claim 1 wherein R
can be selected from the groups consisting of hydrogen, halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, haloallcenyl, haloalkoxy, alkynoxy, hydroxyalkyl, alkylthioalkyl and hydroxy-haloalkoxyalkyl; R1 and R2 can be the same or different and can be selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, hydroxyalkyl, hydroxyhaloalkyl, cycloalkyl, alkylcycloalkyl, alkoxyalkyl and cycloalkenyl; pro-vided that when R1 is hydrogen R2 is other than hydrogen.

; 3. The composition as set forth in Claim 1 wherein R is haloalkyl and R1 and R2 taken together form a structure selected from piperidinyl, alkylpiperidinyl, alkyltetrahydro-pyridyl, morpholyl, alkylmorpholyl, azabicyclononyl, benzoalkyl-pyrrolidinyl, oxazolidyl, alkyloxazolidyl, perhydroquinolyl and alkylaminoalkenyl.

4. A herbicidal composition comprising an active herbicidal compound selected from the group consistsing of thiolcarbamates herbicidally active acetanilides, thiolcarbamates in combination with herbicides selected from the group consisting of triazines, 2,4-D and 2(4-chloro-6-ethyl-amino-5-triazine-2-yl-amino)-2-methyl propionitrile and an antidote therefor corresponding to the formula wherein is selected from phenyl; substituted phenyl wherein said substitu-ents can be selected from halogen, alkyl, haloalkyl, alkoxy, nitro, carboxylic acids and their salts, carbamyl and haloalkylcarbamyl;
phenylallcyl; phenylhaloalkyl; phenylalkenyl; substituted phenyl-alkenyl wherein said substituents can be selected from halogen, alkyl, and allcoxy; halophenoxy; phenylalkoxy; phenylalkylcarboxy-alkyl; phenylcycloalkyl; halophenylalkenoxy; halothiophenylalkyl;
and halophenoxyalkyl; Rl and R2 can be the same or different and can be selected from hydrogen; alkyl; alkenyl; and alkynyl; pro-vided that when Rl is hydrogen R2 is other than hydrogen.

5. A herbicidal composition comprising an active herbicidal compound selected from the group consisting of thiolcarbamates herbicidally active acetanilides, thiolcarbamates in combination with herbicides selected from the group consisting of triazines, 2,4-D and 2(4-chloro-6-ethyl-amino-5-triazine-2-yl-amino)-2-methyl propionitrile and an antidote therefor corresponding to the formula wherein R can be selected from N-alkenylcarbamylalkyl; N-alkenylcarbamyl;
N-alkyl-N-alkynylcarbamyl; N-alkyl-N-alkynylcarbamylalkyl; N-alkenylcarbamylalkoxyalkyl; N-alkyl-N-alkynylcarbamylalkoxyalkyl;
dialkenylcarbamylbicycloalkenyl; and alkynylcarbamylbicycloallcenyl;
R1 and R2 can be the same or different and can be selected from hydrogen, alkyl, alkenyl and alkynyl provided that when R1 is hydrogen R2 is other than hydrogen.

6. The composition as set forth in Claim 1 wherein R can be selected from haloalkyl and hydrogen; Rl and R2 can be the same or different and can be selected from alkyl; alkenyl;
hydrogen; alkoxyalkyl; phenyl; substituted phenyl wherein said substituents can be selected from alkyl, halogen, haloallcyl, allcoxy, haloalkylamido, phthalamido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, haloalkylamido, and alkylcarbo-alkenyl; phenylalkyl; substituted phenylalkyl wherein said substit-uents can be selected from halogen, alkyl, dioxyalkylene, and halo-phenoxyalkylamidoalkyl provided that when R1 is hydrogen, R2 is other than hydrogen.

7. The composition as set forth in Claim 1 wherein R
is selected from haloalkyl, alkyl, cyanoallcyl, thiocyanatoalkyl, cyanatoalkyl, cycloalkyl, bicycloalkyl, balophenyl, phenylalkenyl and halophenylalkenyl; R1 and R2 can be the same or different and can be selected from cyanoalkyl, hydrogen, alkenyl and alkyl, pro-vided that when R1 is hydrogen R2 is other than hydrogen.

8. The composition as set forth in Claim 1 wherein said active herbicidal compound is selected from EPTC, S-ethyl diiso-butyl thiolcarbamate, S-propyl dipropyl thiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl thiolcarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-1H-azepine-1-carbothioate, 2-chloro-N-isopropyl-acetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl di-ethyl thiolcarbamate and mixtures thereof.

9. The composition as set forth in Cla`im 2 wherein said active herbicidal compound is selected from EPTC, S-ethyl diiso-butyl thiolcarbamate, S-propyl dipropyl thiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl thiolcarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-1H azepine-1-carbothioate, 2-chloro-N-isopropyl-acetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl diethyl thiolcarbamate and mixtures thereof.

10. The composition as set forth in Claim 3 wherein said active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiolcarbamate, S-propyl dipropyl thiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl thiolcarbamate, S-ethyl cyclo-hexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-lH-azepine-l-carbothioate, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chloro-benzyl diethyl thiolcarbamate and mixtures thereof.

11. The composition as set forth in Claim 4 wherein said-active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiolcarbamate, S-propyl dipropylothiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl thiolcarbamate, S-ethyl cyclo-hexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-1H-azepine-1-carbothioate, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chloro-benzyl diethyl thiolcarbamate and mixtures thereof.

12. The composition as set forth in Claim 5 wherein said active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiolcarbamate, S-propyl dipropyl thiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl thiolcarbamate, S-ethyl cyclo-hexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-lH-azepine-l-carbothiozte, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chloro-benzyl diethyl thiolcarbamate and mixtures thereof.

13. The composition as set forth in Claim 6 wherein said active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiolcarbamate, S-propyl dipropyl thiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl thiolcarbamate, S-ethyl cyclo-hexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxy-methyl) acetanilide, S-ethyl hexahydro-lH-azepine-l-carbothioate, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl diethyl thiolcarbamate and mixtures thereof.

14. The composition as set forth in Claim 7 wherein said active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiolcarbamate, S-propyl dipropyl thiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl thiolcarbamate, S-ethyl cyclo-hexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-lH-azepine-l-carbothioate, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chloro-benzyl diethyl thiolcarbamate and mixtures thereof.

15. The composition as set forth in Claim 1 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

16. The composition as set forth in Claim 2 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

17. The composition as set forth in Claim 3 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

18. The composition as set forth in Claim 4 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

19. The composition as set forth in Claim 5 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

20. The composition as set forth in Claim 6 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

21. The composition as set forth in Claim 7 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

22. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 1.

23. A method of controlling weed pests comprising adding -to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 2.

24. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 3.

25. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 4.

26. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 5.

27. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 6.

28. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 7.

29. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 8.

30. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 9.

31. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 10.

32. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 11.

33. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 12.

34. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 13.

35. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 14.

36. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 15.

37. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 16.

38. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 17.

39. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim l8.

40. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 19.

41. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 20.

42. A method of controlling weed pests comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 21.

43. A herbicidal composition comprising an active herbicide compound selected from the group consisting of thiolcarbamates, herbicidally active acetanilides, thiolcarbamates in combination with herbicides selected from the group consisting of triazines, 2,4-D and 2(4-chloro-6-ethyl-amino-5-triazine-2yl-amino)-2-methyl propionitrile and an antidote therefor corresponding to the formula:

wherein R is haloalkyl and R1 and R2 are alkenyl, provided that said herbicidally active acetanilide is other than N(2'-methoxyethyl) -2,6-dimethyl chloroacetanilide.

44. A herbicidal composition comprising an active thiocarbamate herbicide compound and an antidote compound having the formula:

45. The herbicide composition as set forth in Claim 43 wherein said active herbicide is selected from an active thiocarbamate or an active acetanilide.

46. The herbicidal composition as set forth in Claim 45 wherein said active thiocarbamate is selected from the group consisting of EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichloroallyl-di-isopropyl thiocarbamate, S-ethyl cyclohexylethyl thiocarbamate or S-ethyl hexahydro-1H-azepine-1-carbothioate.

47. The herbicidal composition as set forth in Claim 45 wherein said active acetanilide is selected from the group consisting of 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide or 2-chloro-N-isopropylacetanilide.

48. The method of controlling weed pests and protecting crop plants comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 43.

49. The method of controlling weed pests and protecting crop plants comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 44.

50. The composition as set forth in Claim 43 wherein said antidote compound is present in an amount ranging between about 0.0001 to 30 parts by weight for each part by weight of the active herbicidal compound.

51. The composition as set forth in Claim 44 wherein said antidote compound is present in an amount ranging between about 0.0001 to about 30 parts by weight per each part by weight of the active herbicidal compound.

52. The method of protecting a plant crop from injury due to an active herbicidal compound, selected from the group consisting of thiolcarbamates, herbicidally active acetanilides, thiolcarbamates in combination with herbicides selected from the group consisting of triazines, 2,4-D and 2(4-chloro-6-ethyl-amino-5-triazine-2yl-amino)-2-methyl propionitrile comprising applying to the soil a non-phytotoxic antidotally effective amount of a compound corresponding to the formula:

provided that herbicidally active acetanilide is other than N(2'-methoxyethyl)-2,6-dimethylchloroacetanilide, wherein R is haloalkyl; Rl and R2 are alkenyl.

53. The method according to Claim 52 wherein R is -CHCl2 and R1 and R2 are -CH2-CH=CH2.

54. The method of controlling weed pests and protecting wheat plants comprising adding to the habitat thereof an herbicidally effective amount of the composition as set forth in Claim 44.

55. The method of protecting wheat from injury due to an active herbicidal thiocarbamate compound, comprising applying to the soil a non-phytotoxic antidotally effective amount of a compound corresponding to the formula:

wherein R is haloalkyl; R1 and R2 are alkenyl.

56. The method for protecting corn from injury due to an active S-alkyl thiocarbamate pre-emergent herbicide comprising applying to the soil in the vicinity of the corn seed an effective but non-phytotoxic amount of N,N-diisopropyl dichloroacetamide.

57. A herbicidal composition comprising an active thiocarbamate herbicide compound and a non-phytotoxic anei-dotally effective amount of a compound having the formula where each of Rl and R2 are alkenyl groups containing from 2 to 12 carbon atoms, inclusive; said compound being ancidotally aceive with said thiocarbamate herbicide compound and wherein said compound is present in an amount ranging between about 0.0001 to 30 parts by weight for each part by weight of the active herbic$dal compound.

58. A herbicidal composltion comprising an active thio-c-rbamate herbicide compourd and an antidoeally efective amount of an antidote compound have the formula wherein said antidote compound is present in an amount ranging between about 0.0001 to 30 ?arts by weight for each part by weight of the active herbicidal compound.

59. The herbicidal composition as set forth in C12iD 57 wherein said active thiocarbamate is selected fro3 the group consisting of EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichloroallyl-di-isopropyl thiocarbamate, S-4-chlorobenzyl diethyl thiocarbamate, S-ethyl cyclohexylethl thiocarbamate or S-ethyl hexahydro-1H-azepine-1-carbothioate.

60. The method of controlling weed pests and protecting crop plants comprising adding to the habitat thereof an herbi-cidally effective amount of the composition as set forth in claim 57.

61. The method of controlling weed pests and protecting crop plants comprising adding to the habitat thereof an herb-cidally effective amount of the composition as set forth in claim 58.

62. The method of protecting a plant crop from injury due to an active thiocarbamate herbicidal compound, comprising apply-ing to the soil, in which an herbicidally effective amount of said active thiocarbamate herbicidal compound is used, a non-phytotoxic antidotally effective amount of a compound correspond-ing to the formula wherein R1 and R2 are alkenyl groups containing from 2 to 12 carbon atoms, inclusive; said compound being antidotally active with said thiocarbamate herbicide compound.

63. The method according to claim 62 wherein each of R1 and R2 are -CH2-CH-CH2.

64. The herbicidal composition as set forth in claim 58 wherein said active thiocarbamate is selected from the group con-sisting of EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl di-propyl thiocarbamate, S-2,3,3-trichloroallyl-di-isopropyl thio-carbamate, 5-4-chlorobenzyl diethyl thiocarbamate S-ethyl cyclo-hexylethyl thiocarbamate and S-ethyl hexahydro-1H-azepine-1-car-bothioate.

65. The method of protecting a plant crop from injury due to the herbicidally active thiocarbamate compound EPTC, comprising applying to the soil a herbicidal composition, com-prising an herbicidally effective amount of EPTC and a non-phy-totoxic antidocally effective amount of a compound having the formula wherein each of R1 and R2 are alkenyl groups containing from 2 to 12 carbon atoms, inclusive; said compound being antidotally active with said EPTC and wherein said compound is present in an amount ranging between about 0.0001 to 30 parts by weight for each part by weight of the herbicidally active thiocarba-mate.

66. The method of protecting a plant crop from injury due to the herbicidally active thiocarbamate compound EPTC, com-prising applying to the soil a herbicidal composition, compris-ing an herbicidally effective amount of EPTC and an antidotally effective amount of an antidote compound having the formula wherein said antidote compound is present in an amount ranging between about 0.0001 to 30 parts by weight for each part by weight of the active herbicidal thiocarbamate.

67. The method according to claim 62in which said thio-carbamate herbicide compound is selected from EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3,-trichloroallyl-di-isopropyl thiocarbamate, S-4-chloro-benzyl diethyl thiocarbamate, S-ethyl cyclohexylethyl thiocar-bamte and S-ethyl hexahydro-1H-azepine-1-carbothioate.

68. The herbicidal composition as set forth in claim 58 wherein said active thiocarbamate is S-ethyl diisobutyl thio-carbamate.

69. The herbicidal composition as set forth in claim 58 wherein said active thiocarbamate is S-propyl dipropyl thiocar-bamate.

70. The herbicidal composition as set forth in claim 58 wherein said active thiocarbamate is S-2,3,3-trichloroallyl-diisopropyl thiocarbamate.

71. The herbicidal composition as set forth in claim 58 wherein said active thiocarbamate is S-ethyl cyclohexylethyl thiocarbamate.

72. The herbicidal composition as set forth in claim 58 wherein said active thiocarbamate is S-ethyl hexahydro-1H-azepine-1-carbothioate.

73. The herbicidal composition as set forth in claim 58 wherein said active thiocarbamate is S-4-chlorobenzyl diethyl thiocarbamate.

74. The method of protecting corn plants from injury due to EPTC, comprising applying to the soil in which an herbi-cidally effective amount of said EPTC is used, a non-phytotoxic antidotally effective amount of a compound corresponding to the formula

75. The method protecting corn plants from injury due to S-ethyl diisobueyl thiocarbamate comprising applying to the soil in which an herbicidally effective amount of said S-ethyl diisobutyl thiocarbamate is used, a non-phytotoxic anti-dotally effective amount of a compound corresponding to the formula

76. The method of protecting corn plants from injury due to S-propyl dipropyl thiocarbamate, comprising applying to the soil in which an herbicidally effective amount of said S-propyl dipropyl thiocarbamate is used, a non-phytotoxic antidotally effective amount of a compound corresponding to the formula

77. The herbicide composition as set forth in claim 57 wherein said active thiocarbamate is EPTC (S-ethyl N,N-di-n-propyl thiocarbamate).

78. The herbicide composition as set forth in claim 58 wherein said active thiocarbamate is EPTC (S-ethyl N,N-di-n-propyl thiocarbamate).

79. The method according to claim 63 in which the thio-carbamate herbicide compound is selected from EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichlorallyl-di-isopropyl thiocarbamate, S-4-chloro-benzyl diethyl thiocarbamate, S-ethyl cyclohexylethyl thiocar-bamate and S-ethyl hexahydro-1H-azepine-1-carbothioate.

80. A herbicidal composition comprising an active thiolcarbamate herbicide compound and a non-phytotoxic antidotally effective amount of an amide of a haloalkanoic acid, said haloalkanoic acid having from 2 to 7 carbon atoms, inclusive, said amide being antidotally active with said thiolcarbamate herbicide provided that the amide is other than a N,N-dihydro or a N-hydro, N-halophenyl amide of a haloalkanoic acid.

81. A herbicide composition comprising an active thiolcarbamate herbicide compound and a non-phytotoxic antidotally effective amount of an amide of a dichloro-acetic acid, said amide being antidotally active with said thiolcarbamate herbicide and provided that said amide is other than a N,N-dihydro or a N-hydro, N-halophenyl amide of dichloroacetic acid.
82. The herbicidal composition of Claim 80 wherein said amide has the formula wherein R is haloalkyl and R1 and R2 can be the same or different and can be selected from the group consisting of alkenyl;
haloalkenyl;
hydrogen;
alkyl;
haloalkyl;
alkynyl;
cyanoalkyl;
hydroxyalkl;
hydroxyhaloalkyl;
haloalkylcarboxyalkyl;
alkylcarboxyalkyl;
alkoxycarboxyalkyl;
thioalkylcarboxyalkyl;
alkoxycarboalkyl;

claim 82 continued alkylcarbamyloxyalkyl;
amino;
formyl;
haloalkyl-N-alkylamido;
haloalkylamido;
haloalkylamidoalkyl;
haloalkyl-N-alkylamidoalkyl;
haloalkylamidoalkenyl;
alkylamino;
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, alkenylcarbamyl-oxy, alkylamido, haloalkylamido, alkylcarboalkenyl;
phenylsulfonyl;
phenylalkyl;
substituted phenylalkyl wherein said substituents can be selected from halogen, alkyl, dioxyalkylene, halophenoxy-alkylamidoalkyl;
alkylthiodiazolyl;
piperidylalkyl;
thiazolyl;

alkylthiazolyl;
benzothiazolyl;
halobenzothiazolyl;
furylalkyl;
pyridyl;
alkylpyridyl;
alkyloxazolyl;
tetrahydrofurylalkyl;
3-cyano, 4,5-polyalkylene-thienyl;
.alpha.-haloalkylacetamidophenylalkyl;
.alpha.-haloalkylacetamidonitrophenylalkyl;
.alpha.-haloalkylacetamidohalophernylalkyl;
cyanoalkenyl;
R1 and R2 when taken together can form a structure consisting of piperidinyl;
alkylpiperidinyl;
alkyltetrahydropyridyl;
morpholyl;
alkylmorpholyl;
azo-bicyclononyl;
benzoalkylpyrrolidinyl;
perhydroquinolyl;
alkylaminoalkenyl;
provided that when R1 is hydrogen R2 is other than hydrogen and halophenyl.

83. The herbicidal composition of Claim82 wherein said R is dichloromethyl.

84. The herbicidal composition of Claim83 wherein Rl and R2 are selected from the group consisting of alkenyl, alkyl, cyanoalkyl, alkoxyalkyl, tetrahydrofurylalkyl or furylalkyl.

85. A herbicide composition according to Claim 80 wherein the haloalkanoic acid amide has two N-substituents, one of which is an alkenyl group.

86. A herbicide composition according to Claim 85 wherein the alkenyl group is allyl.

87. The method of controlling weed pests and pro-tecting a plant crop from injury due to an active thiol-carbamate herbicide compound, comprising applying to the soil a herbicidally effective amount of said herbicide and a non-phytotoxic antidotally effective amount of an amide of a haloalkanoic acid, said haloalkanoic acid having from 2 to 7 carbon atoms, inclusive, said amide being antidotally active with said thiolcarbamate herbicide providied that the amide is other than a N,N-dihydro or a N-hydro, N-halophenyl amide of a haloalkanoic acid.

88. The method of controlling weed pests and pro-tecting a plant crop from injury due to an active thiolcarbamate herbicide compound comprising applying to the soil a herbici-dally effective amount of said herbicide and a non-phytotoxic antidotally effective amount of an amide of a dichloroacetic acid, said amide being antidotally active with said thiol-carbamate herbicide and provided that said amide is other than a N,N-dihydro or a N-hydro, N-halophenyl amide of dichloro-acetic acid.
89. The method of Claim 87wherein said amide has the formula wherein R is haloalkyl and R1 and R2 can be the same or different and can be selected from the group consisting of alkenyl;
haloalkenyl;
hydrogen;
alkyl;
haloalkyl;
alkynyl;
cyanoalkyl;

claim 89 continued hydroxyalkyl;
hydroxyhaloalkyl;
haloalkylcarboxyalkyl;
alkylcarboxyalkyl;
alkylcarboxyalkyl;
thioalkylcarboxyalkyl;
alkoxycarboalkyl;
alkylcarbamyloxyalkyl;
amino;
formyl;
haloalkyl-N-alkylamido;
haloalkylamido;
haloalkylamidoalkyl;
haloalkyl-N-alkylamidoalkyl;
haloalkylamidoalkenyl;
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, alkenylcarbamyl-oxy, alkylamido, haloalkylamiao, alkylcarboalkenyl;
phenylsulfonyl;
phenylalkyl;

substituted phenylalkyl wherein said substitu nts can be selected from halogen, alkyl, dioxyalkylene, halophenoxy-alkylamidoalkyl;
alkylthiodiazolyl;
piperidylalkyl;
thiazolyl;
alkylthiazolyl;
benzothiazolyl;
halobenzothiazolyl;
furylalkyl;
pyridyl;
alkylpyridyl;
alkyloxazolyl;
tetrahydrofurylalkyl;
3-cyano, 4,5-polyalkylene-thienyl;
.alpha.-haloalkylacetamidophenylalkyl;
.alpha.-haloalkylacetamidonitrophenylalkyl;
.alpha.-haloalkylacetamidohalophenylalkyl;
cyanoalkenyl;
R1 and R2 when taken together can form a structure consisting of piperidinyl;
alkylpiperidinyl;
alkyltetrahydropyridyl;
morpholyl;
alkylmorpholyl;
azo-bicyc;ononyl;
benzoalkylpyrrolidinyl;
perhydroquinolyl;
alkylaminoalkenyl;
provided that when R1 is hydrogen R2 is other than hydrogen and halophenyl.

90. The method of Claim 89 wherein said R is dichloromethyl.

91. The method of Claim89 wherein Rl and R2 are selected from the group consisting of alkenyl, alkyl, cyano-alkyl, alkoxyalkvl, tetrahydrofurylalkyl or furylalkyl.

92. The method of Claim 87 wherein the haloalkanoic acid amide has two N-substituents, one of which is an alkenyl group.

93. The method of Claim 92 wherein the alkenyl group is allyl.