IL45583A - Herbicide compositions containing a mixture of a herbicide of the thiocarbamate or substituted acetanilide type and a sulfide antidote - Google Patents

Description

45583/2 nam a T» »3SOSK TK oasanpiK'n o mo a o»as7y Herbicide compositions containing a mixture of a herbicide of the thiocarbamte or. substituted acetanilide type and a sulfide antidote STAOFFER CHEMICAL COMPANY C:- 43466 IN THE UNITED STATES PATENT OFFICE SULFIDE HERBICIDE ANTIDOTE COMPOSITIONS AND METHOD OF USE Abstract of the Disclosure Herbicidal compositions comprising an active herbicidal compound and an antidote therefor and the methods of use of the herbi cide compositions are described herein; the antidote compound corresponds to substituted sulfides having the formula wherein R^ is selected from the group consisting of di-p-chlorophenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxymethyl, N-aIkylcarbamoylinethyl, mono-chlorobenzamidoethy1, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, -S-ethylthiocarboxylaminoethyl and dichloro-acetamidoethyl; and R is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, ?-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanoalkyl, cyanochloroalkyl, mono-chlorobenzyamidoeth l, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, ^^-S-ethylthiocarboxylaminoethyl and dichloroacetamidoethyl.

Background of the Invention Among the many herbicidal compounds commercially avail able, the thiocarbamates 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. Patents No. 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 thiocarbamates as herbicides on crops sometimes causes serious injuries to the crop plant. When used in the recommended amount in the soil 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. Patents No. 3,131,509 and 3,564,768. These antagonistic agents have not been notably successful. The afore mentioned patent specifically exemplifies the treatment of seeds employing compounds of a different chemical class no suggestive of the present invention.

Description of the Invention _ It has been discovered that plants can be protected against injury by various herbicides of the thiocarbamate-type or substituted acetanilide-type, 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: Rl"S"¾ wherein is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxymethyl, N-alkyl-carbamoylmethyl, haloalkyl, mono-chlorobenzamidoethyl, dichloro-benzamidoethyl, mono-bromobenzamidoe h l, ^-S-ethylthiocarboxyl aminoethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, C^'^V droxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyano-alkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichloro-benzamidoethyl, mono-bromobenzamidoethyl, aminoethyl and dichloroacetamidoethyl.

In the above description, the following embodiments are intended for the various substituent groups: For R^, alkenyl preferably includes those members containing at least one olefini double bond and from 3 to 6 carbon atoms, inclusive, in both branched and straight chain configurations; chloroalkenyl include mono-, di-, tri- and tetra-chloro substitution in alkenyl moietie having 3 to 6 carbon atoms, inclusive; the term aminoalkyl includes those members having at least one amino group (Nl^-) and an alkyl moiety having from 1 to 6 carbon atoms, inclusive. For I^, alkyl preferably includes those members having from 1 to 8 carbon atoms, inclusive, in both branched and straight chain configurations; alkenyl preferably includes those members containing at least one olefinic double bond and from 3 to 6 carbon atoms, inclusive, in both branched and straight chain configurations; chloroalkenyl includes mono-, di-, tri- and tetra-chloro substitution in alkenyl moieties having 3 to 6 carbon atoms, inclusive; aminoalkyl includes those members having at least one amino group ( H2"*) and an alkyl moiety having from 1 to 6 carbon atoms, inclusive; cyanoalkyl includes those members having at least one cyano group (-CN) and an alkyl moiety having from 1 to 4 carbon atoms; cyanochloroalkyl includes those members having at least one cyano group, from 1 to 4 chlorine atoms, inclusive, and an alkyl moiety having from 2 to 6 carbon atoms, inclusive. The term haloalkyl preferably includes those alkyl members substituted with at least one halogen, selected from chlorine and bromine and having from 1 to 4 carbon atoms.

As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate-type and other herbicides to render them selective in their action. Whichever mode of action is present, the corresponding beneficial and desirable effect is the continue herbicidal effect of the thiocarbamate or other herbicide with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

Therefore, the terms herbicide, antidote or amount, is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, safening agent, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soil in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpos The compounds of this invention represented by the above formula can be prepared by several different procedures depending upon the starting materials.

General Procedure for Preparation of Allyl and Benzyl Sulfides The active halide (allyl or benzyl type) is dissolved in isopropyl alcohol or other suitable solvent, and sodium sulfide nona-hydrate which had been coarsely ground was added. The addition is at reduced temperature, approximately 15°C. At the end of the reaction, the precipitated sodium chloride is removed by filtration and the solvent removed in vacuo . The residue is taken up in benzene and ether and washed with three portions of water. The solution is dried and the solvent distilled in vacuo .

General Procedure for Preparation of Mixed Sulfides An organo mercaptan is dissolved in a suitable solvent, such as dioxane, isopropyl alcohol or the like. Sodium hydroxide solution is added and the reaction mixture heated. An active organo halide is added and the mixture refluxed. Work-up is by normal procedures of extraction, solvent removal, distillation or The compounds and the present invention and their preparation are more particularly illustrated by the following examples. Following the examples of preparation is a table of compounds which may be prepared according to the procedures described herein. Compound numbers have been assigned to them and are used for identification through the balance of the specification.

EXAMPLE I Preparation of bis- (3 , 3-dichloroallyl) -sulfide 1, 1,3-trichloropropene-l (1100 g., 7.5 M) was dissolved in one liter of isopropanol and sodium sulfide nona-hydrate (900 g., 3.75 M) which had been coarsely powdered, was added at one time at 15°C. The mixture was stirred at 25-30°C. for 3 hours an at 50°C. for 2 hours. It was allowed to stand overnight at room temperature. The precipitated sodium chloride was filtered off and the solvent removed in vacuo . The residual oil was taken up in a mixture of one liter of benzene and one liter of ether and washed with three 400 ml. portions of water. The solution was dried over magnesium sulfate and the solvent removed in vacuo The residual solvent was removed at about 0.5 mm. There was obtained a red brown liquid, yield: 853 g. (90%). Struc ure was confirmed by NMR spectroscopy. The product distilled at b.p. 75-77°/35mm.

EXAMPLE II ((22..55 gg..,, 0.021M) and sodium hydroxide (1.6 g., 0.04 M) in 20 ml. of water and 40 ml. of ether was added a solution of m-chlorobenzoyl chloride (7.0 g., 0.04 M) in 15 ml. of ether at 10-20°C. A precipitate appeared. The mixture was stirred 45 minutes at room temperature and the solid filtered, washed with water and dried. The product was a white solid, m.p. 150-152°C. Its structure was confirmed by IR spectroscopy. Yield: 7.0 g. (8870) .

TABLE I COMPOUND NUMBER (Cl-phenyl)9CH p-Cl-phenyl 1.6460 0 0 II CH9C-NHCH9CH(CH ) p-Cl-phenyl 107-112 :N-CHr CH2CH CH3 1.5561 7 8 CC12=CHCH2 CC12=CHCH2 75-77/35mm, 9 phenyl CCI2CH2C≡≡N 1.6073 10 CC12=CC1CH2 CH2CH3 1.5325 0 11 12 CH C-OH CH C— 1.5217 TABLE I (continued) COMPOUND NUMBER Ri 13 CHC1=CHCH2 CHC1=CHCH2 1.5270 14 CH2CHCH2 CH2 =CHCH2 1.4850 16 CC12=CC1CH CC12=CC1CH2 1.5810 17 phenyl CH2CH=CC12 1.5905 18 C1CH2CH2CH CH2C H2 CH2 C 1 1.4528 19 HOCH2CH2 n-C8H17 1.4710 20 H N-CH CH CH CH NH0 b.p. 64-67 .3- .4tnm 0 0 II II 21 C2H5SCNHCH2CH2 CH2CH2NHCSC2H5 130-132 n liquid 0 0 11 26 C12CHCNHCH2CH2 CH2CH2NHCCHC12 111-115 The compounds of this invention were employed in effective herbicidal antidote compositions comprising thiocarbamates or substituted acetanilides in combination with antidote compound described hereinabove. They were tested in the following manner.

Corn Seed Treatment Test 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 using a predetermined amount of a stock solution containing 936 mg. of 75.57. active ingredient to 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 contained 7 mg. of herbicide which equals one pound per acre when applied to the soil in the 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 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 inch deep were made for planting seeds. Alternating rows of treated and untreated crop seeds were sown. In each test, six DeKalb XL 374 field corn seeds were planted in each row. Rows were approximately 1-1/2 inches apart in the flat. Seeds were treated by placing 50 mg. of the antidote compound with 10 grams of corn seed in a suitable container and shaking them until the seeds were uniformly covered with the compound. Antidote compounds were also applied as liquid slurries and powders or dusts. In some cases, acetone was used to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.

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

In each test, the herbicide was applied alone, in combination with the seed protectant, and the seed protectant was applied alone to check for phytotoxicity . The untreated adjacent row was employed to observe any beneficial laterial movement of the antidote compound through the soil. The degree of the effect was noted by comparison with the control. The results of these tests are tabulated in Table II.

TABLE II Per Cent Injury to Corn from EPTC* Seed Treatment Test Per Cent Injury, weeks Treated Untreated COMPOUND EPTC Seed Seed NUMBER lb/A (0.5% w/w) (2 wks) Ad acent Row (3 wks 1 50 50 2 40 65 3 50 80 4 65 70 5 80 70 EPTC Untreated Seed 90 - S-ethyl dipropylthiocarbamate Procedure: ^lticrop Antidote Screen Flats were filled with Felton loamy sand soil. A variety of grass and broadleaf crops were used in these tests.

EPTAM® (EPTC) was incorporated at 1/2, 3 or 5 lb/A, while a constant rate of 5 lb/A of the additive was used. LASSO® fi (EPTC) or ORDRA ^ (S-ethyl hexahydro-l-H-azepine-l-carbothioate) and the candidate herbicide antidote were applied separately by pipetting measured amounts of the appropriate stock solutions into the soil during incorporation in a 5 gallon rotary cement mixer. Stock solutions were prepared as follows: A. 1/2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) is diluted with 500 ml. of deionized water so that 2 ml. equals 1/2 lb/A flat.

B. 5 lb/A: 6700 mg. of EPTC 6E (75.5% a.i.) is dilute with 500 ml. of deionized water so that 2 ml. equals 5 lb/A flat.

C. 2 lb/A: 427 mg. LASSO 4E is diluted with 100 ml. of deionized water so that 1 ml. equals 2.05 mg. (a.i.) and 4 ml. equals 8.2 mg. equivalent to 2 lb/A flat.

D. 6 lb/A: 4312 mg. of ORDRAM 6E (71.3% a.i.) was diluted with 500 ml. of deionized water so that 4 ml. of the stock solution equaled 6 lb/A when applied to a flat.

Antidote stock solutions are prepared by diluting 102 mg. of technical material with 10 ml. of acetone 1° Tween 20 (polyoxyethylene sorbitan monolaurate) so that 2 ml. equals 5 lb/A flat.

After the soil is treated with both herbicide and additive, the soil is transferred from the mixer back into the flat where it is then prepared for seeding. · The initial step in preparation is to remove a one pint sample of soil from- each r_ flat to be retained and used to cover the seeds after planting^ The soil is then leveled and rows one-quarter inch deep are made in each flat. Flats treated with the herbicide and additive are seeded with corn (Zea maize) , sugarbeets (Beta vulgare) , sunflowe (Helianthus annus) , cotton (Gossypium hirsutum) , soybeans (Glyci max) and oilseed rape (Brassica napus) . Flats treated with 1/2 lb/A of EPTAM are seeded with red oats (Avena byxantina) , milo (Sorghum vulgare) , wheat (Triticum aestivum) , giant foxtail (Seteria feberii) , rice (Oryza sativa) and barley (Hordeum vulgar Flats treated with 2 lb/A of LASSO are seeded with corn (Zea maize) , wheat (Triticum aestivum), rice (Oryza sativa) , milo (Sorghum vulgare) , and barley (Hordeum vulgare) . Seeds are then covered with the pint soil sample removed prior to seeding.

The flats are then placed on greenhouse benches where temperatures are maintained between 70-90°F. The soil is watered by sprinkling to assure good plant growth.

Injury ratings are taken at 2, 3 or 4 weeks after the treatments are applied. Soil treated with the herbicides alone at 1/2, 2, 3, 5 or 6 lb/A is included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The per cent protection is determined by a comparison with flats not treated with the candidate antidote, but with the herbicide alone. Results are given in Table III.

TABLE III MULTICROP SCREEN RESULTS PER CENT PROTECTION Rate of % Pro- COMPOUND Rate of Antidote tec tio NUMBER Herbicide lb/A lb/A Crop (4 wks 6 EPTCa 3.0 5.0 corn 100 EPTC 3.0 5.0 soybeans 40 7 EPTC 3.0 5.0 corn 75 8 EPTC 0.5 5.0 sorghum 100 EPTC 0.5 5.0 rice 30 EPTC 3.0 5.0 corn 100 ORDRAM° 6.0 5.0 rice 72 LASSOc 2.0 5.0 wheat 38 LASSO 2.0 5.0 sorghum 100 9 EPTC 0.5 5.0 sorghum 50 EPTC 0.5 5.0 rice 44 10 EPTC 3.0 5.0 mustard 100 11 EPTC 0.5 5.0 sorghum 50 EPTC 0.5 5.0 rice 38 EPTC 3.0 5.0 corn 67 12 EPTC 3.0 5.0 corn 100 13 EPTC 5.0 5.0 sunflower 67 (3 14 EPTC 0.5 5.0 rice 100 (3 ORDRAM 6.0 5.0 rice 30 15 EPTC 0.5 5.0 rice 100 (3 16 EPTC 0.5 1.0 rice 11 17 EPTC 0.5 5.0 sorghum 67 EPTC 3.0 5.0 corn 83 18 EPTC 0.5 5.0 barley 45 19 EPTC 5.0 5.0 sunflower 67 20 EPTC 5.0 5.0 rape 87 21 EPTC 0.5 5.0 rice 86 22 EPTC 0.5 5.0 rice 100 EPTC 5.0 5.0 sunflower 75 TABLE III (continued) Rate of % pro- COMPOUND Rate of Antidote tec o IMBER Herbicide lb/A lb/A Crop (4 w¾s 23 EPTC 0.5 5.0 rice 100 EPTC 5.0 5.0 sunflower 75 24 EPTC 0.5 5.0 rice 62 25 EPTC 5.0 5.0 corn 15 26 EPTC 5.0 5.0 corn 45 = S-ethyl dipropylthiocarbamate ^ = S-ethyl hexahydro-lH-azepine-l-carbothioate = 2-chloro-21 ,61 -diethyl-N- (methoxymethyl)acetamide The antidote compounds and compositions of the present invention can be used in any convenient form. Thus, the antidote compounds can be formulated into emulsifiable liquids, emulsifi-able concentrates, liquid, wettable powder, powders, granular or any other convenient form. In its preferred form, a non-phytotoxic quantity of an herbicidal antidote compound is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytotox quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The addition of the antidote compound does not affect the herbicidal activity of the herbicides .

The amount of antidote compound present can range between about 0.01 to about 15 parts by weight of antidote compound described herein per each part by weight of herbicide.

The exact amount of antidote compound will usually be de ermine on economic ratios for the most effective amount usable. It is understood that a non-phytotoxic quantity of antidote compound will be employed in the herbicidal compositions described herein.

The herbicides indicated in the tables and elsewhere 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 or recommended amount.

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 the present invention are 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 utility 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. The compositions as set forth in this invention include those wherein the preferred active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiocarbamate , S-propyl dipropyl thiocarbamate , S-2,3,3-tri-chloroallyl-diisopropyl thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, 2-chloro-21 ,61 -diethyl-N- (methoxymeth l) acetanilid 5-ethyl hexahydro-lH-azepine-l-carbothioate, 2-chloro-N-isopropyl acetanilide, N,N-diallyl-2-chloroacetamide , S-4-chlorobenzyl diethyl thiocarbamate, 2-chloro-4-ethylamino-6-isop opylamino-s-triazine, 2-chloro-4,6-bis(ethylamino)-s-triazine, 2(4-chloro- 6-ethylamine-s-triazine-2-yl-amino) -2-methylpropionitrile, 2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine , 2 ,4-di-chlorophenoxyacetic acid, its esters and salts, and 3-(3,4-di-chlorophenyl)-l, 1-dimethylurea and combinations thereof.

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, emer ging seedlings, and established vegetation, including the roots and above-ground portions. 45583/2

Claims (36)

1. An herbicide composition comprising a mixture of an herbicide of the thiocarbamate type or substituted acetanilide type and an antidote compound corresponding to the formula wherein R-^ is selected from the group consisting of di-p-chloro- phenylme hyl, phthalimidome thyl , pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl , aminoalkyl, hydroxyethyl, carboxymet yl N-alkylcar amoyIce hyl, mono -chlorobenzamidoethyl , die hloro-benzamidoethy1 , mono -bromobenzamidoe hyl, ^-S -ethylthiocarboxyl-aminoethyl and dichloroacetamidoethyl ; and is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, -hydroxytrichloroethyl, alkenyl, chloroalkenyl, arninoalkyl, cyanoalkyl , c anochloroalkyl , mono-chlorobenzylaminodethyl , diehlorobenzamidoethyl , mono-bromobenzamidoe hyl , -ethy1-thiocarboxylaminoethyl and dichloroaceta idoethyl.

2. The herbicidal composition as set forth in Claim 1 wherein said antidote compound is present in an amount ranging between about 0,01 to about 15 parts by weight for each part by weight of herbicide.

3. The composition according to Claim 1 in which R^ is chloroalkenyl and R2 is chloroalkenyl.

4. The composition according to Claim 1 in which is 3 , 3 -dichloroallyl and R2 is 3 , 3 -die hloroallyl .

5. The composition according to Claim 1 in which ^butentyl-2 and R2 is 3-chlorobutenyl-2.

6. The composition according to Claim 1 in which R^ oallyl and R2 is 3-chloroallyl .

7. The composition according to Claim 1 in which R^ richloroallyl and R2 is 2 , 3 , 3-trichloroallyl .

8. The composition according to Claim 1 in which R^ hloroallyl and R2 is 2 ,3 -dichloroallyl .

9. The composition according to Claim 1 in which R^ lorophenylmethyl and R2 is p-chlorophenyl.

10. The composition according to Claim 1 in which R-^ midomethyl and R2 is alkyl.

11. The composition according to Claim 10 in which R yl.

12. The composition according to Claim 10 in which R

13. The composition according to Claim 10 in which R l.

14. The composition according to Claim 1 in which R^ and R2 is alkenyl.

15. The composition according to Claim 14 in which R nd R2 is allyl.

16. The composition according to Claim 1 in which R^ lorobenzamidoethyl and R2 is raono-chlorobenzamidoethyl .

17. The composition according to Claim 1 in which is dichlorobenzamidoe hyl and R2 is dichlorobenzamidoe thyl .

18. The composition according to Claim 1 in which R^ is mono-bromobenzamidoethyl and R2 is mono-bromobenzamidoethyl.

19. The composition according to Claim 1 in which R^ is dichloroacetamidoethyl and R2 is dichloroacetamidoethyl .

20. The composition according to Claim 1 in which R^ is haloalkyl and R2 is haloalkyl.

21. The composition according to Claim 20 in which R^ is 3-chloropropyl and R2 is 3-chloropropyl.

22. The composition according to Claim 1 in which R^ ' is -S-eth lthiocarboxylaminoe hyl and R2 is ^-S -e hylthio-carboxylaminoethyl .

23. The composition according to Claim 1 in which R^ is pentachlorophenyl and 2 is mono-chloroethyl .

24. The composition according to Claim 1 in which R^ is carboxymethylene and R2 is cyanomethylene .

25. The composition according to Claim 1 in which R^ is hydroxyethyl and R2 is ethyl.

26. The composition according to Claim 1 in which R-^ is chloroalkenyl and R2 is alkyl.

27. The composition according to Claim 26 in which R^ is 2 ,3,3-trichlorobutenyl-2 and R2 is ethyl.

28. The method of protecting rice crop from injury due to a thiocarbamate herbicide, comprising applying to the habitat prior to planting from about 0.01 to about 15 parts by weight for each part by weight of the thiocarbamate herbicide an antidote compound corresponding to the formula R1"S"R2 wherein is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxymethyl N-alkylcarbamoylmethyl, mono-chlorobenzamidoe hy1, dichlorobenz-amidoethyl, mono-bromobenzamidoethy1, ^-S-ethylthiocarboxylamino ethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, (^-hydroxy-trichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanochloro-alkyl, mono-chlorobenzylamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, ^-S-ethylthiocarboxylaminoethyl and dichlor acetamidoethyl .

29. The method of Claim 28 in which the thiocarbamate herbicide is S-ethyl hexahydro-lH-azepine-l-carbothioate and the antidote in which R^ is chloroalkenyl and R2 is chloroalkenyl.

30. The method of Claim 29 in which R-^ is 3,3-dichloro allyl and R2 is 3,3-dichloroallyl .

31. The method of Claim 28 in which the thiocarbamate is S-ethyl hexahydro-lH-azepine-l-carbothioate and the antidote in which R^ is alkenyl and R2 is alkenyl.

32. The method of Claim 31 in which R^ is allyl and R2 is allyl.

33. The method of protecting a crop from injury due to a substituted acetanilide herbicide, comprising pre-plant incorporation in the soil in which said crop is to be planted, a non-phytotoxic antidotally effective amount of a compound corresponding to the formula R-j^—S— wherein R-^ is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxymethyl N-alkylcarbamoylraethyl, mono-chlorobenzamidoethyl, dichloro-benzamidoethyl, mono-bromobenzamidoethyl, ^-S-ethylthiocarboxyl-aminoethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, O^-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanoalkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl,^7 -S-ethylthio-carboxylaminoethyl and dichloroacetamidoethyl.

34. In the method according to Claim 33 in which said substituted acetanilide herbicide is 2-chloro-2 ' ,61 -diethyl-N-(me hoxymeth l) acetanilide .

35. The method of protecting corn crop from injury ditfe to a thiocarbamate herbicide, comprising applying to the corn seed prior to planting a non-phyto toxic antidotally effective amount of a compound corresponding to the formula wherein is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, ca boxymethyl N-alkylcarbamoylmethyl, mono-chlorobenzamidoethyl, dichlorobenz-amidoethyl, mono-bromobenzamidoethyl, ^ -S-ethylthiocarboxyl-aminoethyl and dichloroacetamidoethyl; and is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, d-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanoalkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichlo benzamidoethyl, mono-bromobenzamidoethyl, aminoethyl and dichloroacetamidoethyl.

36. In the method according to Claim 35 in which said thiocarbamate is S-ethyl dipropyl thiocarbamate.