NZ201389A

NZ201389A - 3-(haloalkyl or alkylthio)carbonyl-5-(alkyl or alkenyl)(oxy or thio)oxazolidines

Info

Publication number: NZ201389A
Application number: NZ201389A
Authority: NZ
Inventors: E G Teach
Original assignee: Stauffer Chemical Co
Priority date: 1973-10-12
Filing date: 1980-06-17
Publication date: 1984-11-09

Description

New Zealand Paient Spedficaiion for Paient Number £01 389 * #' : A, 201 . n-u>-6o <-?c~2t:on Prsorsty Datc;s;. ■ • ■ _ ^ CO!TJpS3t3 'S'pSCI'i.S Class: g N0V 19g| PubHcat'icsi Pa*.2- • ■ * • P.O. Journal Wo: !Ya Under the provisions of Regulation 23 (I) che .. _ Specification h?s been ante-datel to 1.1 Jw/ve I *&l if K ay ra Divisional Application out of New Zealand Patent Application No. 194070 dated 17 June 1980 Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION -SUBSTITUTED OXAZOLIDINE HERBICIDE ANTIDOTES WE, STAUFFER CHEMICAL COMPANY, a corporation organized and existing under the laws of Delaware, United States of America, of Westport, Connecticut 06880, United States of America, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement (followed by page 1A) 201389 -lpr -SUBSTITUTED OXAZOLIDINE HERBICIDE ANTIDOTES Background of the Invention While many herbicides are immediately toxic to a large number of weed pests, it is known that the effect of many herbicides upon important plant cultivations is either non-selective or not adequately selective. Thus, many herbicides damage not only the weeds to be controlled. but to a greater or lesser extent, the desirable cultivated plants as well. This holds true for many herbicidal compounds which have been commercially successful and are commercially available. These herbicides include types such as triazines, urea derivatives, halogenated acetanilides, carbamates, thiolcarbamates, and the like. Some examples of these compounds are described in U.S. Patent Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786, 3,582,314 and 3,952,056.

The side effect of injury to a cultivated crop "by various herbicides is particularly inconvenient and unfortunate. When used in the recommended amounts to control broadleaf weeds and grasses, serious malformation or stunting of the crop plants sometimes result. This abnormal growth in the crop plants results in loss of crop yield. The search continues for good selective herbicides.

Previous attempts are described to overcome this problem. The treatment of the crop seed with certain "hormonal" antagonistic agents prior to planting is described; see U.S. Patents 3,131,509 and 3,564,768. The protective agents, as well as the herbicide, in these prior processes are largely specific to certain cultivated plant species or in the nature of antagonistic agents. The prior antagonistic agents have not been notably successful. The aforementioned patents _2_ 201389 i '« r specifically exemplify and describe the treatment of seeds employing compounds of a different chemical class, not suggestive of the present invention.

U.S. Patents 3,9 89,503 and 4,124,372 and New Zealand Patent No: 179,99 8 disclose certain substituted oxazolidine compounds. However,,none of these references anticipate or make obvious the particular compounds or the utility of the particular compounds as herbicidal antidotes for thiolcarbamate herbicides; in particular for S-n-propyl N,N-di-n-propyl thiolcarbamate, S-ethyl di-n-propyl thiolcarbamate, S-isopropyl 1-(5-ethyl-2-methyl-piperidine) carbothioate, S-ethyl diisobutyl thiolcarbamate, and S-ethyl cyclohexyl ethyl thiolcarbamate.

Description of the Invention It has been discovered that cultivated crop plants can be protected against injury by thiolcarbamate-type herbicides, and said injury can be decreased when the thiolcarbamate-type herbicides, each alone or in mixtures or combination with other compounds, are applied in a variety of ways.

Further, as an alternative effect, the tolerance of the crop plants to these herbicides can be substantially increased by adding to the soil an antidote compound of the type N-haloacyl oxazolidine substituted in the 5-position according to the following description: With oxy or thio_containing groups, therefore, the present invention also includes a two-part herbicide system comprising a first-part of one or more thiolcarbamate herbicides and a second-part of an effective antidote compound therefore, said antidote compounds corresponding to the following formula J-tr- r CH2XRl 0 2 3 In the above description, the following embodiments are intended for the various substituent groups: For R^, alkyl preferably includes those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain configurations. As exemplary of the alkyl portion within the preferred embodiment are the following: Methyl, e thyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, and n-hexyl; for R^, alkenyl means those members which contain from 3 to 6 carbon atoms and at least one ethylenic or double bond such as in 1-propenyl, - 2-butenyl, 3-butenyl, 1,l-dimethyl-3-butenyl, and the like.

For R2 and R3 as lower alkyl, means those members which contains from 1 to 3 carbon atoms, inclusive; and for R as haloalkyl, means those members which contain from 1 to 5 carbon atoms, inclusive, and the term "halo" includes chloro, bromo and fluoro as mono, di, tri, tetra or hexa substitutions, that is from 1 to 6 halo substituents; and for R as alkylthio includes those members which contain from 1 to 4 carbon atoms, inclusive. Other substituent groups are as indicated in carbon content in the above description.

As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiolcarbamate-type and other herbicides, to patent off! ce '-01589 ' • I render them selective in their action. The observation noted with the presence of the herein described antidote, is a decrease in phytotoxicity with respect to various crops, otherwise observed when various thiolcarbamate herbicides are used for weed control. Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiolcarbamate against weed species present in the crop, with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

Therefore, the terms "antidote", "herbicide antidote" or "antidotal amount", are 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, antagonist or the like, will depend upon the mode of action. The mode of action is varied, but the effect which is desirable, is the result of the method of treating the seed, soil or furrow in which a crop is planted.

The compounds of this invention represented by the above formulae as described above can be prepared by several different procedures depending upon the starting materials.

When X is oxygen and R^ is alkyl or alkenyl, the requisite starting material for the compounds within this invention may be prepared by amination of a 1,2-epoxy-3-alkoxy or alkenoxy propane (I) with aqueous ammonia or ammonium hydroxide to produce a l-amino-3-alkoxy or alkenoxy-2-propanol (II) . Subsequent reaction and cyclization with acetone or other aldehyde ketone (III) yields the N-unsubstituted 2,2-dialkyl 5-alkoxy or alkenoxy methyl oxazolidine product (IV). This sequence of reactions is depicted by the following equations: 2 013 8 9 CH2«^_^CHCH20R1 + NH3/H20 (I) ? h nh2ch2chch2or1 (II) oh I .ff nh2ch2chch2or1 + r2-c-r3 H in h R^R 2 3 ch2OR1 + H2O (II) (III) (IV) wherein R^, R2 and R^ have the same significance as previously defined.

When X is sulfur and R^ is alkyl or alkenyl, the requisite starting material for the compounds within this invention may be prepared by thionation with a mercaptan (VI) of epichlorohydrin (V) to produce the 1-chloro-alkyl or 1-chloro-alkenyl thio-2-propanol (VII), this is followed by reformation of the epoxide (VIII). Amination of the 1,2-epoxy-2-alkylthio or alkenylthio propane (VIII) with ammonia or aqueous ammonia produced a l-amino-3-alkylthio or alkenyl-thio-2-propanol (IX). Subsequent reaction and cyclization with acetone or other aldehyde ketone (III) yields the N-unsubstituted 2,2-dialkyl-5-alkylthio or alkenylthio methyl-oxazolidine product (X), this sequence of reactions is depicted by the following equations: A ch2chch2c1 + rjsh r1sch2-ch-ch2c1 (V) R1SCH2 T -ch- (VI) (VII) /\ CH2C1 + NaOH(pwd) > RjSC^CH-C^ + NaCl RjSC^ (VII) C^J-^H2 + (VIII) oh nh3/h2o- (VIII) OH £ H-C O II r1sch2chch2nh2 + r2cr3 (IX) R1SCH2CH-CH2NH2 (IX) H H H x ^NH ■ch2sRl v-° 2 3 (X) + h20 With reference to the above procedures: (a) The N-acyl-substituted compounds of the invention wherein R is haloalkyl, may be prepared by direct acylation of a 5-substituted oxazolidine compound with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine or an inorganic base, such as sodium hydroxide. the invention wherein R is alkylthio may be prepared by direct alkylthio formulation of a 5-substituted oxazolidine compound with an alkyl chlorothioformate in the presence of an acid chloride acceptor. in the presence of an inert organic solvent, such as benzene. A solvent is normally employed to facilitate the reaction and aid in the work-up of the product. Where good chemical practice dictates a catalyst was used as specified, in some instances a catalyst is not required. The reaction temperatures can vary from -10°C to 90°C. The reaction pressure may be atmospheric, subatmospheric or superatmospheric. However, for convenience of conducting the reactions, the pressure is generally atmospheric. The reaction time will, of course, vary depending upon the reactants and reaction temperature. Generally, the reaction time is from 0.25 to 24 hours. After the reaction is complete, the product is recovered by filtration, extraction and drying. The product can be purified further by trituration with hexane or recrystallization from a suitable solvent. In most instances, the structure was confirmed by analytical techniques, such as infrared spectroscopy, nuclear magnetic resonance or mass spectroscopy. found that it was unnecessary to isolate and purify the compounds before use. The volume of the oxazolidine solution (b) The thiocarbamyl 3-substituted compounds of In the above reactions, the reaction is performed In preparing the oxazolidine intermediates it was 19 N0VI98Z / 2013 was adjusted to give a 25 percent w/v solution s i (4 milliliters - 1 gram) and aliquots were then used for subsequent reactions.

Representative of the above general scheme of reactions, are the following preparations employing specific starting materials and intermediates.

Preparation of Intermediate: l-Chloro-3-ethylthio-2-propanol Sixty five and two tenths (65.2) grams of ethyl mercaptan was added dropwise with stirring to 92.5 grams of epichlorohydrin and 2 grams of zinc chloride in 500 milliliters of dioxane. The mixture was heated to 40°C and the heating removed while the mixture remained at 35-40°C for 3/4 hour. The mixture was then heated at 40°C for 1 1/2 hour and then to reflux at which point the temperature was 105°C.

Yield after stripping was 103 grams, nD 1.4862. The product was confirmed by infrared and nuclear magnetic resonance. Preparation of Intermediate: Ethyl 1,2-epoxyprop-3-yl sulfide One hundred and twenty seven (127.0) grams of 1-chloro-3-ethylthio-2-propanol was added dropwise with vigorous stirring to 82 grams of powdered NaOH in 500 milliliters of diethyl ether. The temperature was kept below 30°C with a water bath and addition took 40 minutes. The product was filtered and the ether stripped off giving 80.8 grams of product, 1.4567. The structure was confirmed by infrared and nuclear magnetic resonance and used in subsequent reactions without purification.

Preparation of Intermediate: 2-Hydroxy-3-aminopropyl ethyl sulfide Eighty seven and eight tenths (87.8) grams of ethyl 1,2-epoxyprop-3-yl sulfide was added dropwise with stirring to 1 liter of aqueous 28% ammonia solution, cooled to O.C overnight in an icebox, and maintained in an ice bath. The epoxide was added over 45 minutes and the reaction mixture was allowed to warm to room temperature and stand in the hood • • 20138 9 overnight. The water and ammonia were stripped off under vacuum and the oily residue distilled to give 59.1 grams of the title compound; b.p. 101-105°C at 1.5-2 millimeters, nQ 1.4910. The structure was confirmed by infrared and nuclear magnetic resonance.

In preparing the oxazolidine intermediates it was found that it was unnecessary to isolate and purify the compounds before use. The volume of the oxazolidine solution was adjusted to give a 25 percent w/v solution (4 milliliters - 1 gram) and aliquots were then used for subsequent reactions. Both the 5-oxymethyl and 5-thiomethyl substituted oxazolidines can be prepared by similar reactions.

Preparation of Intermediate: 1-Amino-3-i sopropoxy-i sopropano1 Sixty-three (63.0) grams of 3-isopropoxy-l,2-epoxy- propane was added dropwise with stirring to 1 liter of 28 percent aqueous ammonia, cooled to 0°C , and kept in an icebox overnight. The solution was allowed to warm to room temperature and stored in a loosely stoppered container for five days in a hood. The water and ammonia was stripped off under vacuum and the oily residue distilled to give 38 grams of the title compound; b.p. 77.5°C at 0.5 millimeters, nD 1.4200. The structure was confirmed by infrared and nuclear magnetic resonance.

Preparation of Intermediate: 2,2-Dimethyl-5-isopropoxymethyl-oxazolidine Twenty six and six tenths (26.6) grams of 1-amino-3-isopropoxy-isopropanol and 12 grams of acetone were added to 150 milliliters of benzene and heated to reflux under a modified Dean-Stark apparatus. When about 4 milliliters of water had been azeotropically removed, an additional 20 milliliters of benzene was distilled off and the mixture allowed to cool to room temperature. The volume was adjusted to 138.4 milliliters with benzene to give a 25 percent w/v solution of the title compound. Aliquots of this solution were used to prepare several of the subject compounds.

The compounds of the present invention and their preparation are more particularly illustated by the following examples. Following the examples of preparation is a table of compounds which are prepared according to the procedures described herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE I Preparation of 2,2-dimethyl-N-trichloroacetyl-5-isopropoxy- methyl-oxazolidine.

To 20.8 milliliters of 25 percent w/v , 2,2-dimethyl- -isopropoxymethyl-oxazolidine solution in 50 milliliters of benzene was added 5.5 grams of trichloroacetyl chloride. To this solution was added dropwise with cooling, 3.1 grams of trimethylamine. After washing with water, drying and removal of the benzene in vacuo, there was obtained 8.1 grams of the title compound, 1.4603. Analytical data supports the structure.

EXAMPLE II Preparation of 2t2-dimethyl-N-dichloroacetyl-5-isopropoxy- methyl-oxazolidine.

In a similar manner as Example I, 27.7 milliliters of 25 percent w/v, 2,2-dimethyl-5-isopropoxymethyl-oxazolidine solution in 50 milliliters of benzene and 4.9 grams of dichloroacetyl chloride was added 4.1 grains of triethylamine.

After the appropriate work up procedure, there was obtained a yield of 8.9 grams, rip 1.4564. Analytical data supports the structure.

EXAMPLE III Preparation of 2,2-dimethyl-3-(p-toluene-sulfonyl-carbamyl) 5-isopropoxymethyl-oxazolidine.

To 20.8 milliliters of 25 percent w/v, 2,2-dimethyl-5-isopropoxymethyl-oxazolidine solution in 50 milliliters of benzene was added 5.9 grams of p-toluene-sulfonyl isocyanate. < 1? NOV 1982 t p Q 1 7 O o -10- ^ Upon completion of the reaction the solvent, benzene, was removed in vacuo. There was obtained 12.8 grams of the title compound, as a glass. Analytical data supports the structure.

EXAMPLE IV Preparation of 2,2-dimethyl-3-(2,3-dibromopropionyl)-5- methoxymethyl-oxazolidine.

To 11.6 milliliters of 25 percent w/v, 2,2-dimethyl- -methoxymethyl-oxazolidine solution in 50 milliliters of benzene with 5.0 grams of 2,3-dibromopropionyl chloride was added dropwise 2.1 grams of triethylamine. After the reaction was complete the mixture was washed with water, separated, dried and the organic solvent removed in vacuo. There was obtained 2.7 grams of the title compound, nD 1.4887. Analytical data supports the structure.

EXAMPLE V Preparation of 2,2-dimethyl-3-dichloroacetyl-5-allyloxymethyl- oxazolidine.

To a reaction mixture of 25 percent w/v, 34.2 milliliters of 2/2-dimethyl-5-allyloxymethyl-oxazolidine solution in 100 milliliters benzene with 4 grams of 50% sodium hydroxide solution, was added dropwise, 7.4 grams of dichloroacetyl chloride. Cooling in an ice bath and vigorous stirring was maintained during the addition of the chloride.

Upon completion of the reaction the mixture was washed with water, dried, separated and the organic solvent removed in vacuo. There was obtained 10.0 grams of the title compound, rip 1.4705. Analytical data supports the structure.

EXAMPLE VI (a-c) (a) Preparation of 2,2-dimethyl-3-chlo^oacetyl-5-ethylthio-methyl-oxazolidine.

To 21 milliliters of 25 percent w/v, 2,2-dimethyl-5-ethylthiomethyl-oxazolidine solution in 25 milliliters of benzene was added dropwise 3.4 grams of chloroacetyl chloride.

While cooling in an ice bath and with vigorous stirring, the further dropwise addition of 3.1 grams of triethylamine was carried out. The reaction mixture was allowed to stir for 19 NOVI982 deceived ^01389 about 1 hour. At the end of this time the mixture was washed with water, separated, dried and the organic solvent removed in vacuo. There was obtained 6.2 grams of the title compound, iip 1.4942. Infrared data supports the structure. (b) Preparation of 2,2-dimethyl-3-ethylthiocarbonyl-5-ethylthiomethyl-oxazolidine.

To 19.3 milliliters of 25 percent w/v, 2,2-dimethyl- -ethylthiomethyl-oxazolidine solution in 25 milliliters of benzene was added 2.9 grams of triethylamine and 3.4 grams of ethyl chlorothiolformate as in the procedure for (a) supra.

Work-up was similar to (a). There was obtained a yield of 7.1 grams of the title compound, 1.4940. Infrared data supports the structure. (c) Preparation of 2,2-dimethyl-3-dichloroacetyl-5-ethylthio-methyl-oxazolidine.

To 52.5 milliliters of 25 percent w/v, 2,2-dimethyl-5-ethylthiomethyl-oxazolidine solution in 100 milliliters of benzene was added 6.5 grams of 50% solution of sodium hydroxide (10% excess) was added 12.1 grams of dichloroacetyl chloride dropwise. The reaction mixture was cooled in an ice bath with vigorous stirring during the dropwise addition. The temperature was maintained at below 10°C during the addition and allowed to stir about 30 minutes at room temperature. The work-up procedure was similar to (a) supra. There was obtained a yield of 15.3 grams of the title compound, 1.4980. '■01 389 TABLE I O II R-C- R2 R3 CI^XRj Compounds Compound Number R XRj R2 R^ Physical — Constant n, a 1 CC13 och(ch3) 2 CH3 CH3 1.4603 2 chci2 och(ch3> 2 CH3 CH3 1.4564 3 CH2C1 och(ch3) 2 ch3 CH3 1.4488 4 CH3CHBrCHBr och(ch3) 2 CH3 CH3 1.4722 p-CH30SO2NH och(ch3) 2 CH3 CH3 (Glass) 6 chci2 OCH3 CH3 CH3 1.4730 7 CH2BrCHBr och3 CH3 CH3 1.4887 8 n-c3h7s OCH3 CH3 CH3 1.4620 9 chci2 OC2H5 CH3 CH3 1.4610 CH2BrCH2 OC2H5 CH3 ch3 1.4620 11 CH2BrCHBr OC2H5 CH3 CH3 1.4998 12 chci2 OCH2CH=CH2 CH3 ch3 1.4705 13 CH2BrCHBr OCH2CH=CH2 CH3 CH3 1.4934 14 CH2BrCH2 OCH2CH=CH2 ch3 CH3 1.4764 ch2cich2 OCH2CH=CH2 CH3 CH3 1.4602 16 ch3chci och2ch^h2 CH3 CH3 1.4562 17 chci2 0-n-C3H7 CH3 CH3 1.4560 18 CH2BrCHBr 0-n-C3H? ch3 CH3 1.4795 19 CH2BrCH2 0-n-C3H7 CH3 CH3 1.4612 ch2cich2 0-n-C3H7 CH3 CH3 1.4470 MiPATerroFFW 19 NOV 1982 wcrrn .'fp.

TABLE I (Cont'd): Compound XR^ R Number R 21 chci2 0-n-C4Hg CH3 22 CH2BrCHBr 0-n-C4H9 CH3 23 CH2BrCH2 0-n-C4H9 CH3 24 ch2cich2 °-n-C4H9 , CH3 ch3chci 0-n-C4Hg CH3 26 ch2ci(ch2) 3 och3 CH3 27 CH2ClCHBr och3 GH3 28 CH2ClCHBr OCH(CH3)2 CH3 29 chci2 0-n-C5Hi;L CH3 CH2BrCHBr O-II-C5H11 CH3 31 CH2BrCH2 O-n-C^H^ CH3 32 ch2ci sc2h5 CH3 33 CH2BrCHBr SC2H5 CH3 34 CH2BrCH2 SC2H5 CH3 ch2cich2 sc2h5 CH3 36 C2H5S sc2h5 CH3 37 CHC12 SC2H5 CH3 38 CH2C1(CH2) 3 och3 CH3 39 CH2C1(CH2) 3 OC2H5 CH3 40 CH2C1(CH2) 3 0-n-C3H7 CH3 41 CH2C1(CH2) 3 OCH(CH3)2 CH3 42 CH2C1(CH2) 3 och2ch=ch2 ch3 43 CH2C1(CH2) 3 0-n-C4H9 ch3 44 n-C5Hj ^CHBrCHBr 0-n-C2H5 ch3 45 n-C5Hi;lCHBrCHBr SC2H5 CH3 46 n-^H^CHBr 0-n-C3H7 CH3 ''-01389 R Physical 3Q Constant n^ CH3 1 .4557 CH3 1 .4788 ch3 1 .4583 CH3 1 .4462 CH3 1 .4420 ch3 1 .4588 CH3 1 .4808 ch3 1 .4692 CH3 1 .4508 ch3 1 .4773 CH3 1 .4568 CE3 1 .4942 ch3 1 .5142 CH3 1 .4973 CH3 1 .4862 ch3 1 .4940 CH3 1 .4980 ch3 1 .4545 CH3 1 .4509 CH3 . 1 .4463 CH3 1 .4476 CH3 1 .4586 ch3 1 .4500 CH3 1 .4682 CH3 1 .4942 CH3 1 .4563 19 NOV 19821 201389 The herbicidal compound employed in the utility of this invention is an active thiolcarbamate herbicide of a general type. That is, it is a member of the class of herbicidally active compounds effective against a wide range of plant species, and may have no discrimination between desirable and undesirable plant species. The method of controlling vegetation comprises applying a herbicidally effective amount of the herein described herbicidal composition to the area or plant -where control is desired.

The herbicidal composition as set forth in this invention include those wherein the antidote is as described above and the preferred active herbicidal compound is selected from the class of thiolcarbamate herbicides and includes the following representative members: S-ethyl dipropyl thiolcarbamate, S-ethyl diisobutyl thiolcarbamate, S-propyl di-n-propyl thiolcarbamate, S-ethyl cyclohexyl ethyl thiolcarbamate, S-ethyl hexahydro-lH-azepine-l-carbothioate, 2,3,3-trichloroallyl N,N-diisopropyl thiolcarbamate, S-isopropyl-1-(5-ethyl-3-methyl-piperidine) carbothioate and S-4-chlorobenzyl diethyl thiolcarbamate.

RECEIVED As an embodiment within the scope of the present invention is a two-part or package herbicide system consisting essentially of a first-part of one or more thiol-carbamate herbicides and a second-part of an antidote compound therefor. It is understood that the antidote compound is used in an effective amount to render the two-part herbicide system selective in decreasing phytotoxic effects to desired or beneficial crops and yet phytotoxic to the undesirable or unwanted vegetation. Thus the soil treated by such a system becomes extremely useful and desirable, allowing previously injured crops to be planted in said treated soil, otherwise injured by the herbicide when used alone. Hence, soil treated with herbicide and antidote as described herein is beneficial, desirable and useful. Likewise, seed treated with the antidote compound is a useful and desirable product.

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

Evaluation Procedure and Method . » Flats to be used for growing the crops and weed species were filled with loamy sand soil. Various methods of application were employed, such as pre-plant incorporation (PPI) of 1) the herbicide 6nd antidote separately, and 2) as a tank mix (PPI-TM) with the herbicide and antidote together. The application was by incorporation, whereinafter the seeds of the crops and weeds were planted in the treated soil; application by an in-furrow (IF) treatment of the seeds and surrounding soil in which the herbicide had been applied previously to the soil; and - f 6 - 20130 t treatment of the crop seeds (ST) with an antidote candidate prior to planting in herbicide treated soil; application to the surface of the'' soil prior to emergence of the growing plants, (1) as separate application (PES) of herbicide antidote and (2) as a tank mix (PES-TM).

Stock solutions of representative thiolcarbamate herbicides and antidote candidates were prepared as follows: Herbicides A. S-ethyl di-n-jpropyl thiolcarbamate -EPTC - EPTAM (k) 6E - 4133 mg. dissolved in 800 ml. water such that 5 ml. applied to the soil from a planting flat is equivalent to 5 lb/A PPI or 3744 mg. dissolved in 600 ml. of water, 5 ml. of which was equivalent to 6 lb/A PPI B. S-isopropyl l-(5-ethyl -2-methyl-piperidine) carbothioate (R-12001) technical, the following is a listing of various stock solutions prepared, also included is the lb/A equivalence per 5 ml. pre-plant incorporated. 120 mg/150 ml acetone; 5 ml = 1 lb/A PPI 176 mg/150 ml acetone; 5 ml = 1.5 lb/A PPI 117 mg/175 ml acetone; 5 ml «= 2 lb/A PPI 975 mg/250 ml acetone;. 5 ml = 5 lb/A PPI 585 mg/125 ml acetone; 5 ml = 6 lb/A PPI C. S-ethyl di-isobutyl thiolcarbamate -SUTAN (R) 6E or S-ethyl cyclohexyl Ethyl thiolcarbamate - RONEET (S) 6E - 390 mg. dissolved in 125 ml. water such that 5 ml. applied to the soil from a planting flat is equivalent to 3 lb/A. For 4 lb/A 1456 mg. was dissolved in 350 ml. water, such that 5 ml. was equivalent to the desired 135 amount.

D. S-ethyl hexahydro-lH-azepine-l-carbothioate ORDRAM(lt) 8E - 164 mg. dissolved in 75 ml. water such that 5 ml. is equivalent to 2 lb/A applied to the soil from a planting 40 flat pre-plant incorporated. t 013 8 9 E. s-propyl di-n-propyl thiolcarbamate -VERNAM'(lt) - '6E (807o), the following is a listing of various stock solutions prepared, also included is the lb/A equivalence for 5 ml. pre-plant incorporated: 122 mg/125 ml ml = 1 lb/A PPI • 183 mg/150 ml H2O ml = 1. lb/A PPI 975 mg/250 ml 1^0 ml = 4 lb/A PPI 2632 mg/450 ml 1^0 ml = 6 lb/A PPI 3412 mg/500 ml 1^0 ml ■= 7 lb/A PPI Antidotes F. For each candidate compound employed in the seed treatment method of application, 250 mg. active ingredient was dissolved in 15 2.5 ml. acetone, with 1% Tween 20(r)(poly- oxyethylene sorbitan monolaurate) such that 0.5 ml. of solution per 10 gm. of seeds is equal to 1/2% w/w.

G. For each candidate compound employed in the 20 "in-furrow" method of application, 95 mg. of active ingredient was dissolved in ml. of acetone with 1% Tween 20(5), such that 1.5 ml. applied to the seed ana soil in the furrow, in one-half of the flat was _ equivalent to 5 lb/A. When 1.0 lb/A is desired 0.3 ml. was used.

H. For each candidate compound employed in the "tank mix" pre-plant incorporation test or separately applied pre-plant incorporated test, 50 mg. of active ingredient was dis solved in 100 ml. of acetone with 1 Tween 20(§), such that when 10 ml. of the stock solution was further dissolved in 90 ml. of acetone, 4 ml. was equivalent to 1/20 lb/A PPI. When 39 mg. of the com-pound was dissolved in 10 ml. of acetone, 5 ml. was equivalent to 5 lb/A PPI, and 1 ml. was equivalent to 1 lb/A PPI. When 16 mg. was dissolved in 20 ml., 10 ml. was 40 equivalent to 2 lb/A PPI and when 16 mg. was dissolved in 40 ml., 5 ml. was equivalent to 0 5 lb/A PPI.

In-furrow application of the antidote employed the above stock solutions. As a preparatory step, a one pint sample of soil was removed from each flat to be retained and used later to cover'the Iseeds after treatment with the stock solutions. The soil was leveled before planting. The herbicide stock solution was applied respectively to separate flats and pre-plant incorporated in the soil from the planting flat at the equivalent rate of 1 lb/A active ingredient or the indicated rate.

Rows 1/4-inch deep were made lengthwise in each treated flat preparatory to seeding. After seeding, the flats were sectioned into two equal portions using a wooden barrier and 1-1/2 milliliters of additive stock solution was atomized directly onto the exposed seed and soil in the open furrow in one-half of the flat. The untreated section of the flat served as an herbicide check and also made it possible to observe any lateral movement of the antidote through the soil. The seeds were covered with the one pint sample of untreated soil which had been removed earlier.

For tank mixes to be applied as a pre-plant incorporated application, the following solutions and procedures were employed. Five milliliters (5 ml.) of herbicide stock solutions were each mixed with five milliliters (5 ml.) of antidote candidate stock solution such that the equivalent of 1 lb/A and 5 lb/A of herbicide and antidote, respectively, were applied and incorporated into the soil of each flat. For pre-plant incorporation, the mixed stock solutions were injected into the soil during incorporation in a 5-gallon rotary mixer. Other stock solutions were employed at indicated rates in the tank mix procedure.

In side-by-side tests with various weed species and crops, it was found that weed control was maintained while at the same time the crop species were protected or injury decreased, when compared to a check or control flat. The control flat contained no candidate antidote compound. The following table includes those results.

For seed treatment, 10 grams of seed in a suitable container was shaken with 0.5 milliliters of antidote stock _ 19- 201389 solution H, or other stock solution as indicated, such that the seed treatment was equivalent to 0.5% w/w, 0.25% w/w, 0.125% w/w or 0.1% w/w. Shaking was continued until the seeds were uniformly covered. The antidote compounds may be applied as liquid slurries and powder or dust treatments. The treated seeds were planted in soil in which herbicide stock solution had been pre-plant incorporated into the soil at a rate equivalent to 1 lb/A active ingredient.

All flats were placed on greenhouse benches where temperatures were maintained between 70-90°F. The soil was watered by sprinkling to assure good plant growth. Injury ratings were taken 2 and 4 weeks after the applications were made. Individual control flats treated with the herbicide alone were included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The results of these tests are tabulated in Table II.

TABLE II.

ANTIDOTE ACTIVITY Application Method: Seed Treatment ~ ST In-Furrow - IF Pre-Plant Incorporation - PPI Pre-Plant Incorporation-Tank Mix - PPI-TM ■ Crop Species: > Barley - BA [Hordeum vulgare (L.)] Corn - CN [Zea maize] Cotton - CT [Gossypium hirsutum] Milo (Grain Sorghum) - MO [Sorghum vulgare] Rice - RC [Dryza sativa] Soybeans - SOY [Glycine max] Wheat - WH [Triticum aestivum] Weed Species: Green Foxtail Johnson Grass Nutsedge Shattercane Watergrass Wild Oats _ 20_ FT [Setaria viridis] JG [Sorghum halepense] NS [Cyperus esulentus] SC [Sorghum bicolor] WG [Echinochloa crusgalli] WO [Avena fatua (L.)] Result Percent Percent injury injury with antidote p iniury of herbicide al resent one TABLE II (Cont'd) Antidote Compound Herbicide Method of Number PPI Application VERNAM VERNAM IF IF PPI Rate (Herb. + Anti.) (lbs/A or % ST.) 1+5 6+5 4+1 EPTAM PPI-TM +5 VERNAM ORDRAM IF IF ST 1+5 6+5 2+0.5% RONEET ST 3+0.5% EPTAM R-12001 PPI-TM PPI-TM ST +0.05 5+5 2+0.5% RONEET PPI-TM 3+1 • % • Crop Result Weed Result CT 40/70 CN 0/70 SOY /50 WG 100/100 FT 90/90 CN 0/80 WG 100/100 FT 100/100 MO 50/95 CN 0/70 j MO /70 WG 1 90/90 SC 70/70 MO /70 WG 80/80 SC 80/80 CN 0/80 WG 100/100 CN 0/80 FT. . 100/100 MO 50/90 WG 95/95 SC1 95/95 MO /80 WG 100/100 FT 100/100 i K) 00 TABLE tt (Cont'd) Antidote Compound Herbicide Method of Number PPI Application Rate (Herb. + Anti,) (lbs/A or % ST,) 3+2 3+5 3 VERNAM IF 6+5 RONEET IF 3+5 I 4 VERNAM IF 1+5 6+5 R-12001 IF 5+5 VERNAM ' IF ' 6+5 IF 4+1 % Injury Crop Result Weed Restrlt MO 0/80 WG 100/100 FT 100/100 MO 0/80 WG 100/100 FT 100/100 CN 10/70 MO 40/75 WG 85/85 ; " SC 95/95 WH 40/70 CT 50/70 RC 30/95 BA 30/50 CN 30/70 CT 0/50 WG 95/95 FT 95/95 SOY 30/55 SOY 20/50 WG 100/100 FT 100/100 N) I '■ J '{j4 TABLE-Iff (Cont'd) Antidote Compound Herbicide Method of Nuiptier, PPI Application RONEET IF 6 VERNAM IF • IF EPTAM PP,I PPI RONEET IF PPI-TM VERNAM EPTAM IF ' IF ' PPI Rate (Herb. + Anti.) (lbs/A or 7. ST:.) 4+5 1+5 6+5 5+0,5 +5 4+5 3+1 3+5 1+5 6+5 5+0.5 / 7. Inlury Crop Result Weed Result MO /60 FT 80/80 J.G. .100/100 MO 50/95 CN 0/90 CN 0/80.

WG 100/100 ?T 100/100 CN 0/80 FT 100/100 MO /60 FT 80/80 SC 100/100 MO /80 WG 100/100 FT 100/100 MO 0/80 WG 100/100 FT 100/100 WH 50/75 CN 0/90 CN 0/80 WG 100/100 FT 100/100 i to ' w I O fAfalE. II (Cont'd) Antidote Compound 'Herbicide Method.of Number PPI Application Rate (Herb. + Anti.) (lbs/A or 7. ST.) PPI 5+5 8 VERNAM IF 1+5 9 VERNAM , IF 1.25+5 IF 1.25+5 , IF ,6+5 RONEET IF 3+1 EPTAM PPI 5+5 ' VERNAM IF 1.25+5 6+5 RONEET IF 3+5 EPTAM ' PPI 5+0.5 Crop Result Weed Result CN 0/80 WG 100/100 FT 100/100 RC /95 MO 1,0/100 BA 40/95 CN " /85 MO 40/90 tyG 95/95 ^C 100/100 CN 0/80 WG io'o'/ioo FT iob/ioo MO 50/100 CN 0/85 MO /90 WG 95/95 SC 100/100 CN 0/80 WG 100/100 FT 100/100 TABLE II (Cont'd) Antidote Compound Herbicide Method of Number PPI Application Rate (Herb. + Anti.) (lbs/A or 7« ST.) 11 VERNAM IF 1.25+5 12 VERNAM IF 1.25+5 IF 1.25+5 IF 6+5 EPTAM PPI 5+0.5 RONEET PPI 3+1 13 VERNAM IF 1.25+5 IF 6+5 EPTAM PPI 5+5 14 VERNAM IF 6+5 IF 6+5 EPTAM ' PPI ' 5+0.5 VERNAM IF EPTAM PPI +5 % Injury' Crop Result Weed Result BA 30/95 MO 30/100 BA 30/90 CN 0/90 CN 0/95 FT 100/100 MO 10/90 WG 100/100 SC 100/100 BA 30/90 CN 0/90 CN 0/80 WG 100/100 FT 100/100 CN 0/90 SOY 20/50 CN 0/80 Wd 100/100 FT 100/100 CN 0/90 CN 0/80 WG 100/100 FT 100/100 • TAIL'S ."it (Cont'd) Antidote Cotm}ound Herbicide Method of Ntinibe'r PPI Application 16 VElfcNAM IF 17 X/ElRNAM IF IF EPTAM PPI RONEET PPI 18 VERNAM IF IF IF ' 'EfcTAM PPI 19 VERNAM IF EPTAM PPI Rate Herb-. + Arttl.) lbs/A or % ST.) 6+5 1.25+5 6+5 +5 3+2 6+5 1.25+5 T.25+5 5+5 6+5 54-0.5 VERNAM EPTAM IF PPI 6+5 5+5 Crop Result CN 50/90 MO CN CN MO CN WH BA CN CN CN CN CN /100 0/90 0/80 WG 1FT /90 WG 'SC 0/90 60/95 60/90 0/80 WG 'FT 0/90 0/80 WG "FT 0/90 0/80 WG 'FT 100/100 100/100 100/100 100/100 100/100 100/100 100/100 'lOO/lOO 100/100 •100/100 TABLB II (Cont'd) Antidote Compound Hferbicide Method of Number PPI Application Rate (Herb. + Anti.) (lbs/A or 7. ST'.) 21 VERNAM IF 6+5 ' EPTAM PPI 5+5 R,ON]EET PPI-TM 3+5 22 VERNAM IF 64-5 EPTAM PPI 5+0.5 VERNAM IF U25+5 23 VERNAM IF 64-5 EPTAM PPI 5+5 24 VERNAM IF 6+5 VERNAM IF 6+5 26 VERNAM . IF 1.25+5 IF 6+5 • • # 7. irt j titY CropResult Weed Result CN' 0/90 CN 0/80 .« WG 100/100 FT 100/100 MO 0/80 WG: 85/100 ETr 100/100' \ CN' 0/90 . ; 'S CN 0/80 WG 106/100 FT 100/100 BA 60/90 CN 0/90' CN 0/80 WG 100/100 F^T 100/100 CN 60/96 CN 60/90 j MO 50/100 CN 0/90, . ^ 03 TARLI-: i; (Cont'd) Antidote Compound, Herbicide Method of Number ftPI Application R,ate (Herb. 4- Ant (lbs/A or 7.

EPTAM PPI 5+5 RONEET PPI-TM 3+5 27 VERNAM IF 1.25+5 IF 1.25+5 IF 1.25+5 IF 6+5 RONEET PPI-TM 3+5 EPTAM PPI '5+5 28 VERNAM IF 1.25+5 IF 6+5 EPTAM PPI .. 5+5 VERNAM PPI-TM 1.25+5 • • • .) T.) 7. Injury Crop Result Weedj Result CN MO MO WH BA CN MO CN BA CN CN WH 0/70 WG FT. 40/80 WG FT 40/100 50/100 20/90 10/90 /80 WG FT 0/70 WG /90 0/90 0/70 /80 FT WG FT WG 100/100 ^oo/xop, 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 95/95 NJ 00 I TABLE il (Cbnt'd) Antidote Comppurtd HStbicide Method of Number PPI Application Rate (Herb. + Anti.) (lbs/A or 7« ST.) 29 VE&NAM IF 6+5 SUTAN PPI-TM 6+1 EPTAM PPI 5+0.5 i RONEET PPI-TM 3+5 VERNAM IF 6+5 31 VERNAM IF 6+5 IF 6+5 32 VERNAM IF 6+5 EPTAM PPI-TM 6+5 33 VERNAM IF • 1.25+5 ' IF 6+5 EPTAM PPI-TM 5+5 CN CT CN MO CN CN SOY CN CN BA CN CN /90 30/50 0/70 /80 70/90 40/90 50/70 /90 10/85 40/85 0/90 0/85 W NS WG FT WG FT WG JG loq/iqp 90/90 100/100 100/100 100/100 100/100 98/98 98/98 WG FT 98/98 98/98 TABLE HI (Corft'd) Antidote Compound Herbicide Method of Nunibgr PPI Application Rate (Herb. + Aritl-.) (lbs/A or 7. ST.) 34 VERNAM IF 6+5 EPTAM PPI-TM 5+0.5 'VERNAM IF 1.25+5 IF' 6+5 E^TAM PPI-TM 5+!> 36 VERNAM PPI-TM ■ l'.'25+5 37 VERNAM IF '6+5 VERNAM IF av25+5 IF 1,-25+5 IF 6+5 EPTAM PPI-TM 5+0.05 RONEET PPI-TM . 3+2 38. VERNAM IF IF 6+5 6+5 % Injury Crop .Result "Weed Result CN ' 0/90 CN 0/85 WG 'JG BA 40/85 CN 30/90 CN 0/85 WG JG WH 50/80 WG SOY 50/65 MO 30/100 BA 40/85 CN ,20/90 CN 0/85 WG JG MO 0/80 WG FT CN 60/95 SOY 50/60 98/98' 98/98 98/98 98/98 50/90 90/98 75/98 100/100 100/100 i (uJ • o i N> GO • • TABLE II (Cont'd) .

Compound Herbicide Number PPI 39 VERNAM 40 VERNAM 41 VERNAM 42 VERNAM 4 3 VERNAM 44 VERNAM 45 VERNAM 46 VERNAM Antidote Method of Application Rate (Herb. + Anti.) (lbs/A or 7. ST.) IF 6+5 IF 6+5 IF 6+5 IF 6+5 IF 6+5 IF 6+5 IF 6+5 IF 1.25+5 IF 6+5 IF 1.25+5 IF 6+5 7- Injury Crop ResultWeedResult CN 20/95 SOY 40/60 CN 50/95 CN 30/95 CN 35/95 'J, SOY 40/60 t CN 75/95 BA 45/75 SOY 20/40 BA 50/75 CN 65/90 © - 32-" 201389 The compounds £nd compositions of this invention were employed in effective herbicidal compositions comprising the antidote and a thiolcarbamate herbicide as described hereinabove. The herbicidal compositions were tested in the above manner.

A preferred herbicidal compositions consists essentially of a thiolcarbamate herbicide and an anti-dotally effective amount of an antidote compound therefor corresponding to the formula described hereinabove, and known as 5-oxy or 5-thiomethyl substituted haloacyl oxazolidines.

The compositions of the present invention for the protection of cultivated crop plants comprise the active herbicidal compound and an antidote therefor selected from the above-described compounds. The compos it ions of herbicide and antidote can be prepared by conventional methods through the thorough mixing and grinding of the active herbicide agents and the antidote with suitable carriers and/or other distribution media, possibly with the addition of dispersion agents or solvents.

The antidote compounds and compositions of the present invention can be used in any convenient form. A solvent or inert carrier is not necessary in view of low volume spray technology which permits the use of neat technical grade materials as sprays.. Thus, the antidote compounds and composition with the thiolcarbamate herbicide can be formulated into emulsifiable liquids, emulsifiable 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 herbicide can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytotoxic quantity of the compound and 53- 2 013 8 9 planted into the soil which has been treated with herbicide, 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 herbicide. The alternative methods of application have been exemplified in the above examples.

The amount of antidote compound present can range between about 0.001 to about 30 parts by weight of antidote compound described herein per each part by weight of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. It is understood that a non-phytotoxic, but effective quantity of antidote compound will be employed in the herbicidal compositions and methods described herein.

After treatment with the antidote and herbicide, there is obtained as a resultant thereof, soil which is novel in composition. Said soil is improved in its capability to grow crops and to offer weed control.

Further, said soil treated with herbicide and antidote has the particular utility for allowing seeds of crops otherwise injured by the herbicide, to be planted and grown. The herbicide has its utility in controlling undesirable vegetation; the antidote compound decreases the Injury from the herbicide upon the crop species, and the soil treated with herbicide and antidote compound provides an improved media to grow the crop in the presence of an otherwise injurious herbicide.

In the utility of the present antidote compounds and improved herbicide system, the thiolcarbamate can be applied to the soil. Application of the herbicide to the soil can take place by pre-plant incorporation. In conjunction with the prior application of the herbicide employing the present invention crop seeds are planted. Seed planting is followed by application of the antidote as a pre-emergence surface application. 34" 20138 9 This sequence of application of herbicide, seed planting and antidote is unusual.and fully effective in decreasing injury to the plant crop, otherwise Injured by the thiolcarbamate herbicide. -0 J 389

Claims

WHAT WE CLAIM IS:

1.I. compounds according to the formula o . ch_xr II % '2 1 R-C- £> R2 R3 wherein X is oxygen or sulfur, R^ is selected from the group consisting of alkyl and alkenyl; R is selected from the group^ consisting of p-toluene-sulphonamido, haloalkyl and alkylthio; and FL, and independently selected from the group consisting of hydrogen and lower alkyl, provided that R^ + R2 is less than or equal to 6 carbon atoms and further provided that when XR^ is ethylthio, then R is other than haloalkyl having 3 or 4 carbons and provided that when XR^ is methoxy, R is other than 2,3-dibromopropyl.

2. A herbicidal composition consisting essentially of a thiolcarbamate herbicide and a non-phytotoxic antidotally effective amount of an antidote compound therefor corresponding to the formula o ^ — ch2xr1 " ^ I R-C-I O R2 R3 wherein X is oxygen or sulfur, R^ is selected from the group consisting of alkyl and alkenyl; R is selected from the group consisting of haloalkyl and alkylthio; and R2 and R^ are independently selected from the group consisting of hydrogen and lower alkyl, provided that R^ + R2 is less than or equal to 6 carbon atoms and further provided that when XR^ is ethylthio, then R is other than haloalkyl having 3 or 4 carbons and provided that when XR^^ is methoxy, R is other than 2,3-dibromopropyl. i —i mx patent office 19 NOV 1982 i «ECEV!sD -36- 201389

3. The method of decreasing injury to crops, said injury due to a thiolcarbamate herbicide, comprising application to the soil in which said crop is to be planted and grown, a non-phytotoxic antidotally effective amount of an antidote compound corresponding to the formula ch2XR1 wherein X is oxygen or sulfur, is selected from the group consisting of alkyl and alkenyl; R is selected from the group consisting of haloalkyl and alkylthio; and R2 and R^ are independently selected from the group consisting of hydrogen and lower alkyl, provided that R^ + R2 is less than or equal to 6 carbon atoms and further provided that when XR^ is ethylthio, then R is other than haloalkyl having 3 or 4 carbons and provided that when XR^ is methoxy, R is other than 2,3-dibromopropyl.

4. A method of decreasing injury to crops, said injury due to a thiolcarbamate herbicide, comprising applying into the seed furrow to the seed and adjacent soil in the open furrow prior to covering to achieve a planted state, a non-phytotoxic antidotally effective amount of a compound corresponding to the formula wherein X is oxygen or sulfur, R^ is selected from the group consisting of alkyl and alkenyl; R is selected from the group consisting of haloalkyl and alkylthio; and R2 and R3 are independently selected from the group consisting of hydrogen and lower alkyl, provided that R1 + R2 is less than or equal to 6 carbon atoms and further provided that when XR^^ is ethylthio then R is other than haloalkyl having 3 or 4 carbons and provided that when XR1 is methoxy, R is other than 2,3-dibromopropyl. 201389 -37-

5. A process for preparing compounds according to the formula o / _CH2xr^ R-C-N R 0 2 R3 wherein X is oxygen or sulfur, R^ is selected from the group consisting of alkyl and alkenyl; R is selected from the group consisting of haloalkyl and alkylthio; and R2 and R^ are independently selected from the group consisting of hydrogen and lower alkyl, provided that R^ and R£ is less than or equal to 6 carbon atoms and further provided that when XR^ is ethylthio, then R is other than haloalkyl having 3 or 4 carbons and provided that when XR^ is methoxy, R is other than 2,3-dibromopropyl; said process comprising, in a single step, reacting a 5-substituted oxazolidine compound having the formula H N % 0 A- H CH„XR (IVa) R2 R3 wherein X is oxygen or sulfur, R^ is alkyl or alkenyl, and R2 and R^ are as defined above in an organic solvent with an appropriate acid chloride in the presence of hydrogen chloride acceptor, or an alkyl chlorothioformate in the presence of an acid chloride acceptor, to form the corresponding N-acyl-substituted compound wherein R is haloalkyl, &z.PATBrromcf 19 NOV 1982 '-01 339 -38- or the thiocarbamyl 3-substituted compound wherein R is alkylthio.

6. A process according to Claim 5 wherein in the compound of formula IVa X is oxygen and R^ is alkyl or alkenyl and such compound is prepared by amination of a 1,2-epoxy-3-(alkoxy or alkenoxy)-propane to produce a l-amino-3-(alkoxy or alkenoxy)-2-propanol which is subsequently reacted with an aldehyde or ketone of the formula 0 1 r2 - c - R3 in which R2 and R3 are hydrogen or lower alkyl to form an appropriate compound of formula IVa.

7. A process according to Claim 5 wherein in the compound of formula IVa X is sulfur and R^ is alkyl or alkenyl, such compound is prepared by thionation with a mercaptan of formula R^ SH, where R^ is alkyl or alkenyl, of epichlorohydrin to produce a l-chloro-3-[ (alkyl or alken^)-thio]-2-propanol, reforming such compound into an epoxide ,/amination of the l,2-epoxy-2-[(alkyl or alkenyl) thio]-propane to produce a 1-amino- 3-[(alkyl or alkenyl)] thio-2-propanol which is then reacted with an aldehyde or ketone of the formula O II R2 - C - *3 in which R^ and R^ are hydrogen or lower alkyl, to form an appropriate compound of formula IVa. &Z. PATEI^ST QFFICg 19 NOV mi b RECEIVED v V 39 2 0 1 3

8. The compound as claimed in Claim 1 in which R is CCl^ f XR^ is OCH (CH^) 2' R2 CH3 anc* R3 CH3 *

9. The compound as claimed in Claim 1 in which R is CHCl2f XR^ is OCH(CH3)2, R2 CH3 an<^ R3 CH3 *

10. The compound as claimed in Claim 1 in which R is CHC12, XR^ is OCH^, R2 is CH^ and R^ is CH^•

11. The compound as claimed in Claim 1 in which R is CH2BrCHBr, XR^ is OCH^, R2 is CH^ and R^ is CH^•

12. The compound as claimed in Claim 1 in which R is CHC12/ XRx is OC2H5, R2 is CH3 and R3 is CH3.

13. The compound as claimed in Claim 1 in which R is CH2BrCH2, XR^ is R2 is CH3 and R3 is CH3.

14. The compound as claimed in Claim 1 in which R is CHBrCHBr, XR1 is OC2H5, R2 is CH3 and R3 is CH3»

15. The compound as claimed in Claim 1 in which R is CHC12, XR1 is OCH2CH=CH2, R2 is CH3 and R3 is CH-j.

16. The compound as claimed in Claim 1 in which R is CH2BrCHBr, XRX is OCH2CH=CH2, R2 is CH3 and R3 is ch3.

17. The compound as claimed in Claim 1 in which R is CH2BrCH2, XR^^ is OCH2CH=CH2, R2 is CH3 and R3 is CH-j.

18. The compound as claimed in Claim 1 in which R is CH2C1CH2, XRx is OCH2CH=CH2, R2 is/CH3 and R3 is CH3.

19. The compound as claimed in Claim 1 in which R is CHC12, XR^ is O-n-C-jH^, R2 is CH3 and R3 is CH3.

20. The compound as claimed in Claim 1 in which R is CHBrCHBr, XR^ is 0-n-C3H^ and R2 is CH3 and R3 is CH3

21. The compound as claimed in Claim 1 in which R is CH2BrCH2, XR^ is 0-n-C3H^, R2 is CH3 and R3 is CH3. -40- 20 1

22. The compound as,claimed in Claim 1 in which R is CH^CICI^/ XR^ is O-n-C^H^, R2 is CH^ and R^ is CH^ •

23. The compound as claimed in Claim 1 in which R is CHC12, XR^ is O-n-C^Hg, R2 is CH^ and R^ is CH^.

24. The compound as claimed in Claim 1 in which R is CH0BrCHBr, XR, is 0-n-C.,Ho, R0 is CH-, and R-, is CH0. 2 1 — 49 2 3 3 3

25. The compound as claimed in Claim 1 in which R is CH2BrCH2# XR1 is O-n-C^Hg, R2 is CH3 and R^ is CH3.

26. The compound as claimed in Claim 1 in which r is ch2ci(ch2)3, xrx is och3, r2 is ch3 and r3 is ch3.

27. The compound as claimed in Claim 1 in which R is CH2ClCHBr, XR^ is OCH3, R2 is CH3 and R3 is CH3.

28. The compound as claimed in Claim 1 in which R is CH2ClCHBr, XR1 is OCH(CH3)2, R2 is CH3 and R3 is CH3.

29. The compound as claimed in Claim 1 in which R is CHC12, XR^ is O-n-CgH^, R2 is CH3 and R3 is CH3«

30. The compound as claimed in claim 1 in which R is CH2BrCH2/ XR^ is O-n-C^H^^, R2 is CH3 and R3 is CH3.

31. The compound as claimed in Claim 1 in which R is CH2C1, XR^ is SC2Hj.f R2 is CH3 and R3 is CH3.

32. The compound as claimed in Claim 1 in which R is CJ^BrCHBr, XR^ is SC2H,-, R2 is CH3 and R3 is CH3.

33. The compound as claimed in Claim 1 in which R is CH2BrCH2, XR^ is SC^,-, R2 is CH3 and R3 is CH3«

34. The compound as claimed in Claim 1 in which R is CH2C1CH2, XR^ is SC2H,-/ R2 is CH3 and R3 is CH3.

35. The compound as claimed in Claim 1 in which R is CHC12, XR^ is SC2H^/ R2 is CH3 and R3 is CH3. 20138 9

36. A herbicidal composition as claimed in Claim 2 wherein the antidote compound is a compound as claimed in any one of Claims 8 to 35.

37. A method of decreasing injury to crops as claimed in Claim 3 in which the antidote compound is a compound as claimed in any one of Claims 8 to 35.

38. A method of decreasing injury to crops as claimed in Claim 4 in which the antidote compound is a compound as claimed in any one of Claims 8 to 35.

39. Compounds of the formula given in Claim 1 as herein particularly described.

40. A herbicidal composition consisting essentially of a thiolcarbamate herbicide and a non-phytotoxic antidotally effective amount of a compound of the formula given in Claim 1, as herein particularly described.

41. A method of decreasing injury to crops, said injury due to a thiolcarbamate herbicide substantially as herein described with reference to Table II herein. STAUFFER CHEMICAL COMPANY heir Attorneys vln, SON & CAREY | 26 JUL 1982