CA1040450A

CA1040450A - Sulfide herbicide antidote compositions and methods of use

Info

Publication number: CA1040450A
Application number: CA208,002A
Authority: CA
Inventors: Don R. Baker; Duane R. Arneklev
Original assignee: Stauffer Chemical Co
Current assignee: Stauffer Chemical Co
Priority date: 1973-09-04
Filing date: 1974-08-28
Publication date: 1978-10-17
Also published as: NL176738C; MY7700329A; DK310476A; NL176738B; NL7411682A; FR2242028A1; HU173775B; HU175830B; JPS562523B2; MX6146E; GB1459112A; DE2441741C2; IT1050240B; JPS5049433A; PH11676A; CH598751A5; GB1459111A; AU7293374A; AR214035A1; DK142932B

Abstract

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 R1 is elected from the group consisting of di-p-chlorophenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloro-alkenyl, aminoalkyl, hydroxyethyl, carboxymethyl, N-alkylcarbamoylmethyl, mono-chlorobenzamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthiocarboxylaminoethyl and dichloro-acetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, .alpha.-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanoalkyl, cyanochloroalkyl, mono-chlorobenzyamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthiocarboxyl-aminoethyl and dichloroacetamidoethyl.

Description

~040~50 Back~round of the Invention Among the many herbicidal compound~ co~mercially 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 in~uries to the crop plant. When used in the recommended amounts in the soil to control many broadleaf weeds and grasses, serious malformation and stunting of the crop plants result. This abnor-mal growth in the crop plants results in loss of crop yield.
Previous attempts to overcome this problem involves the treat-ment 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 not suggestive of the present invention.

. '' . ~

~ . 104Q450 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 com-pounds 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:

wherein Rl is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, chloroalkenyl, aminoalkylj hydroxyethyl, carboxymethyl, N-alkyl-carbamoylmethyl, haloalkyl, mono-chlorobenzamidoethyl, dichloro-benzamidoethyl, mono-bromobenzamidoethyl, ~-S-ethylthiocarboxyl-aminoethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, ~-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyano-alkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichloro-benzamidoethyl, mono-bromobenzamidoethyl, ~-S-ethylthiocarboxyl-aminoethyl and dichloroacetamidoethyl.
In the above description, the following embodiments are intended for the various substituent groups: For Rl, alkenyl perferably 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; the term amino-. .. .
'~. alkyl includes those members having at least one amino group .~.

,., (NH2-) and an alkyl moiety having from 1 to 6 carbon atoms, inclusive. For R2~ 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 (NH2-) and an alkyl moiety having from 1 to 6 carbon atoms, inclusive; cyanoalkyl includes those members having at least one cyano group (-C~) and an alkyl moiety having from 1 to 4 carbon atoms; cyano-chloroalkyl 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 o 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 con-tinued herbicidal effect of the thiocarbamate or other herbicide ; with the accomp~nying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

.

; Therefore, the terms herbicide, antidote or anti~otal amount, is meant to describe that effect which tends to counter-act the nonmal injurious herbicidal response that the herbicide might othe~ise 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 purpose.

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 sul-fide nona-hydrate which had been coarsely ground was added. The addition is at reduced temperature, approximately 15C. 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 lil~e. Sodium hydroxide ~, solution is added and the reaction mixture heated. An active organo halide is added and the mixture refluxed. Wor~-up is by normal procedures of extraction, solvent removal, distillation or crystallization, .
, _5_ 104~450 The compounds and the present invention and their pre-paration 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 num~ers 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-1 (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 15C. The mixture was stirred at 25-30C. for 3 hours and at 50C. for 2 hours. It was allowed to stand over-night 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 re-moved in vacuo. The residual solvent was removed at about 0.5 mm.
There was obtained a red brown liquid, yield: 853 g. (90%).
Structure was confirmed by NMR spectroscopy. The product distilled at b.p. 75-77/35mm.

"

~0404S0 EXAMPLE II

Pre~aration of bis~ m-chlorobenzamidoethyl)sulfide.
To a solution of bis-( ~ -aminoethyl)sulfide (2.5 8 , 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 10-20C. 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. 150-152C. Its structure was confirmed by IR spectroscopy. Yield: 7.0 g. (8870).

, . .
,;, .
, ' ' ' ~ TABLE I

Rl-S-R2 m.p. C.
COMPOUND Rl R2 o r NDO

1 (Cl-phenyl)2CH p-Cl-phenyl 1.6460 2 ~ \~ CH CH(CH3)2 57-62 : O
o ; 3 CH2C-NHCH2cH~cH3)2 p-Cl-phenyl 107-112 O
Il

4 ~ " " N-CH2 CH2CH3 64-72 O

~ / N CH2 CH2CH2CH3 1.5561 O

Cl ~ CH2CH2C1 133-134 C
OIH
7 p-Cl-phenyl CHCC13 73-76 8 CC12=CHCH2 CC12-CHCH2 75-77/35mm.
9 phenyl CC12CH2C - N 1.6073 CC12=CClCH2 CH2CH3 1.5325 11 CH3CCl=CHCH2 CH3CCl=CHCH2 1.5387 ~`, O
12 CH2C-OH CH2C N 1.5217 ~:

- ~ ;

TABLE I (continued) 104~450 m.p. c.
COMPOUND Rl R2 or N30 13 CHCl-CHCH2 CHCl=CHCH2 1.5270 14 CH2CHCH2 CH2=CHCH2 1.4850 HOCH2CH2 CH3CH2 1.4816 16 CC12=CClCH2 CC12=CClCH2 1.5810 17 phenyl CH2CH=CC12 1.5905 18 ClCH2CH2CH2 CH2CH2CH2C1 1.4528 19 HOCH2CH2 n C8H17 1.4710 ; 20 . H2N-CH2CH2 CH2CH2NH2 b p 64^6~C.
O
21 C2H5SCNHcH2cH2 CH2CH2NHCSC2H5 130-132 22 ~ C~-NHCH2CH2 CH2CH2NHC ~ 148-lSl 23 ~ CNHCH2CH2 CH2CH2NHC ~ 150-152 ' C
24 ~ C-NHCH2CH2 CH2CH2NHC ~ 170-172 Br Br Cl-CH=CCl-CH2 CH2CCl=CHCl red/bro~n O O
26 C12CHC~HCH2CH2 CH2CH2NHCCHC12 111-115 The compounds of this invention were employed in effec-~; tive herbicidal antidote compositions comprising thiocarbamates or substituted acetanilides in combination with antidote compo~nds described hereinabove. They were tested in the following manne~.

_g_ 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 pre-determined amount of a stock solution containing 936 mg. of 75.5% 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 herb cide 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 approximatley 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 com-pounds 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.

~040450 After the flats were seeded, they were covered with the one pint of soil which had been removed 3ust prior to p~anting.
Flats were placed on gxeenhouse benches where temperatures ranged from 70-90F. 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 com-bination with the seed protectant, and the seed protectant was applied alone to check for phytotoxicity. The untreated adiacent 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 IniurY to Corn from EPTC*
Seed Treatment Test Per Cent IniurY weeks Treated Untreated COMPOUND EPTCSeed Seed fl _NU~IBER lb/A(0.5% w/w) (2 wks) Adjacent Row (3 wks) ; 5 6 80 70 EPTC
Untreated Seed -_ go __ -* = S-ethyl dipropylthiocarbamate .

:, Procedure: Multicrop Antidote Screen Flats were filled with Felton loamy sand soil. A
variety of grass and broadleaf crops were used in these tests.
EPTA ~ (EPTC) was incorporated at 1/2, 3 or 5 lb/A, while a constant rate of 5 lb/A of the additive was used. LASS ~
(EPTC) or ORD ~ (S-ethyl hexahydro-1-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 diluted 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 ,t 1()4~)450 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), sun-flower (Helianthus annus), cotton (Goss~ypium hirsu'tum), soybeans ; (Glycine 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 vulgare). 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 vul~are). 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 70-90F. 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 V 2, 2, 3, 5 or 6 lb/A is included to provide a basis for 20 determining the amount of injury reduction provided by the herbi-cide 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 tecti~
NUMBER Herbicide lb/A lb/A Crop (4 ~ks~

6 EPTCa 3.0 5.0 corn lOQ
EPTC 3.0 5.0 soybeans 40

7 EPTC 3.0 5.0 corn 75

8 EPTC O.5 5.0 sorghum 10 EPTC 0.5 5.0 rice 30 EPTC 3.0 5.0 corn 10~
ORDRAMb 6.0 5.O rice 72 LASSOC 2 0 S O wheat 38 LASSO 2 0 5 0 sorghum 100

9 EPTC 0.5 5.0 sorghum 50 : EPTC 0.5 5.0 rice 44 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 10~
13 EPTC 5.0 5.0 sunflower67 (3) 14 EPTC 0.5 5.0 rice 100 (3) ORDRAM 6.0 5.0 rice 30 EPTC 0.5 5.0 rice 100 (3) 16 EPTC 0.5 1.0 rice 11 17 EPTC 0.5 5.0 80 rghum 67 EPTC 3.0 5.0 corn 83 18 EPTC 0.5 5.0 barley 45 19 EPTC 5.0 5.0 sunflower 67 EPTC 5.0 5.0 rape 87 21 EPTC 0.5 5.0 rice 86 22 EPTC O 5 5 0 rice 100 EPTC 5 0 5 0 sunflower 75 TA~LE III (continued) 1~409~50 Rate of % Pro-CO~OUND Rate of Antidote tection NU~E~ Herbicide lb/h lb/A CroP (4 wks) 23 EPTC 0.5 5.0 rice lOO
EPTC 5.0 5.0 sunflower 75 24 EPTC 0.5 5.0 rice 62 EPTC 5.0 5.0 corn 15 26 EPTC 5.0 5.0 corn 45 a = S-ethyl dipropylthiocarbamate b = S-ethyl hexahydro-lH-azepine-l-carbothioate c = 2-chloro-2',6'-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 fo m, In its preferred form, a non-phytotoxic quantity of an herbicidal antidote compound is admi~ed 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 there-after the antidote compound can be incorporated into the soil.
Moreover, the crop seed itself can be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and sub-sequently treated with the herbicide. The addition of the anti-dote 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 com-pound described herein per each part by weight of herbicide.

, The exact amount of antidote compound will usually be deter~ined on economic ratios for the most effective amount usable. It Ls 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 ia-stance is commercially acceptable within the desired or reco~-mended amount.

It is clear that the classes of herbicidal agents d~s-cribed and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbL-cidal activity varies among specific compounds and among combi-nations 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 combinati~n may be applied. Thus, selection of a specific herbicidal com-pound 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 specifLc compound or combination may be achieved. The beneficial plznt species which can be protected by this method is not intended to be limited by the specific crops employed in the examples.

; 25 The herbicidal compounds employed in the utility o~
this invention are active herbicides of a general type. That is, ` the members of the classes are herbicidally effective against a .
~' . .

104~450 wide range of plant species with no discrimination between desir-able and undesirable species. The method of controlling vege-tation 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-2',6'-diethyl-N-(methoxymethyl)~cetanilide, S-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-isopropyl2mino-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,l-dimethylurea and combinations thereof.

An herbicide as used herein means a compound which 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, dwarf-ing and the like. By "plants", it is meant germinant seeds, emer-ging seedlings, and established vegetation, including the roots ; and above-ground portions.

Claims

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

1. An herbicide composition comprising a mixture of a thiocarbamate or a substituted acetanilide herbicide and an antidote compound corresponding to the formula wherein R1 is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxy-methyl, N-alkylcarbamoylmethyl, mono-chlorobenzamidoethyl, di-chlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthio-carboxylaminoethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, .alpha.-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanoalkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethyl-thiocarboxylaminoethyl and dichloroacetamido ethyl, said antidote compound being present in an amount ranging between about 0.01 to about 15 parts by weight for each part by weight of herbicide.

2. The composition according to Claim 1 in which R1 is chloroalkenyl and R2 is chloroalkenyl.

3. The composition according to Claim 1 in which R1 is 3,3-dichloroallyl and R2 is 3,3-dichloroallyl.

4. The composition according to Claim 1 in which R1 is 3-chlorobutenyl-2 and R2 is 3-chlorobutenyl-2.

5. The composition according to Claim 1 in which R1 is 3-chloroallyl and R2 is 3-chloroallyl.

6. The composition according to Claim 1 in which R1 is 2,3,3-trichloroallyl and R2 is 2,3,3-trichloroallyl.

7. The composition according to Claim 1 in which R1 is 3,3-dichloroallyl and R2 is 2,3-dichloroallyl.

8. The composition according to Claim 1 in which R1 is di-p-chlorophenylmethyl and R2 is p-chlorophenyl.

9. The composition according to Claim 1 in which R1 is phthalimidomethyl and R2 is alkyl.

10. The composition according to Claim 9 in which R2 is isopropyl.

11. The composition according to Claim 9 in which R2 is ethyl.

12. The composition according to Claim 9 in which R2 is n-propyl.

13. The composition according to Claim 1 in which R1 is alkenyl and R2 is alkenyl.

14. The composition according to Claim 13 in which R1 is allyl and R2 is allyl.

15. The composition according to Claim 1 in which R1 is mono-chlorobenzamidoethyl and R2 is mono-chlorobenzamidoethyl.

16. The composition according to Claim 1 in which R1 is dichlorobenzamidoethyl and R2 is dichlorobenzamidoethyl.

17. The composition according to Claim 1 in which R1 is mono-bromobenzamidoethyl and R2 is mono-bromobenzamidoethyl.

18. The composition according to Claim 1 in which R1 is dichloroacetamidoethyl and R2 is dichloroacetamidoethyl.

19. The composition according to Claim 1 in which R1 is haloalkyl and R2 is haloalkyl.

20. The composition according to Claim 19 in which R1 is 3-chloropropyl and R2 is 3-chloropropyl.

21. The composition according to Claim 1 in which R1 is .beta.-S-ethylthiocarboxylaminoethyl and R2 is .beta.-S-ethylthio-carboxylaminoethyl.

22. The composition according to Claim 1 in which R1 is pentachlorophenyl and R2 is mono-chloroethyl.

23. The composition according to Claim 1 in which R1 is carboxymethylene and R2 is cyanomethylene.

24. The composition according to Claim 1 in which R1 is hydroxyethyl and R2 is ethyl.

25. The composition according to Claim 1 in which R1 is chloroalkenyl and R2 is alkyl.

26. The composition according to Claim 25 in which R1 is 2,3,3-trichlorobutenyl-2 and R2 is ethyl.

27. 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 wherein R1 is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxymethyl, N-alkylcarbamoylmethyl, mono-chlorobenzamidoethyl, dichlorobenz-amidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthiocarboxylamino-ethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, .alpha.-hydroxy-trichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanochloro-alkyl, mono-chlorobenzylamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthiocarboxylaminoethyl and dichloroacetamidoethyl.

28. The method of Claim 27 in which the thiocarbamate herbicide is S-ethyl hexahydro-1H-azepine-1-carbothioate and the antidote in which R1 is chloroalkenyl and R2 is chloroalkenyl.

29. The method of Claim 28 in which R1 is 3,3-dichloroallyl and R2 is 3,3-dichloroallyl.

30. The method of Claim 27 in which the thiocarbamate is S-ethyl hexahydro-1H-azepine-1-carbothioate and the antidote in which R1 is alkenyl and R2 is alkenyl.

31. The method of Claim 30 in which R1 is allyl and R2 is allyl.

32. 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 corres-ponding to the formula wherein R1 is selected from the group consisting of di-p-chloro-phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxy-methyl, N-alkylcarbamoylmethyl, mono-chlorobenzamidoethyl, di-chlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthio-carboxylaminoethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, .alpha.-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanoalkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthio-carboxylaminoethyl and dichloroacetamidoethyl.

33. In the method according to Claim 32 in which said substituted acetanilide herbicide is 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide.

34. The method of protecting corn crop from injury due to a thiocarbamate herbicide, comprising applying to the corn seed prior to planting a non-phytotoxic antidotally effective amount of a compound corresponding to the formula wherein R1 is selected from the group consisting of di-p-chlorophenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl, haloalkyl, chloroalkenyl, aminoalkyl, hydroxyethyl, carboxy-methyl, N-alkylcarbamoylmethyl, mono-chlorobenzamidoethyl, di-chlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethylthio-carboxylaminoethyl and dichloroacetamidoethyl; and R2 is selected from the group consisting of p-chlorophenyl, alkyl, haloalkyl, .alpha.-hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyanoalkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichlorobenzamidoethyl, mono-bromobenzamidoethyl, .beta.-S-ethyl-thiocarboxylaminoethyl and dichloroacetamidoethyl.

35. In the method according to Claim 34 in which said thiocarbamate is S-ethyl dipropyl thiocarbamate.