5-SUBSTITUTED OXAZOLIDINES HAVING HERBICIDE ANTIDOTE ACTIVITY, PRODUCTION THEREOF, HERBICIDAL COMPOSITIONS CONTAINING THEM, USE THEREOF IN PREVENTING INJURY TO CROPS AND CROP SEEDS COATED THEREWITH

Abstract: N-haloacyl oxazolidines substituted in the 5-position with oxy or thio containing groups of the formula A-Compounds: wherein XR₁ is phenoxy, R is selected from the group consisting of haloalkyl, where halo is chloro or bromo, and p-methyl phenylsulfonylamido; and R₂ and R₃ are independently selected from lower alkyl; B-Compounds: wherein X is selected from the group consisting of oxygen and sulfur; R₁ is selected from the group consisting of alkyl and alkenyl; R is selected from the group consisting of haloalkyl, alkylthio and p-tolylsulfonamido; R₂ and R₃ are independently selected from the group consisting of hydrogen and lower alkyl, each having 1 to 3 carbon atoms, inclusive; provided that the carbon content of R₁ + R₂ is less than or equal to 6 carbon atoms and further provided that when XR₁ is alkylthio, then R is other than haloalkyl having 3 to 4 carbon atoms inclusive, and provided that when XR₁ is methoxy, R is other than 2,3-dibromopropyl; and in addition a compound selected from the group of compounds consisting of 2,2-dimethyl-3(3-bromopropionyl)5-pentoxymethyl oxazolidine; 2,2-dimethyl-3(5-chlorovaleryl)5-isopropoxymethyl oxazolidine; 2,2-dimethyl-3(5-chlorovaleryl)-5-allyloxymethyl oxazolidine; C-Compounds: wherein X is oxygen or sulfur and R₁ is alkyl; R is selected from the group consisting of haloalkyl, and alkoxy carboalkyl; R₂ is selected from the group consisting of phenyl, p-chlorophenyl and p-bromophenyl; and R₃ is selected from the group consisting of hydrogen and methyl. These new compounds have utility as active herbicidal antidotes to protect against and decrease crop injury when used with thiolcarbamate herbicides, and may be when applied in various ways to achieve this. These ways include soil treatment, seed treatment and in-furrow treatment. Improved herbicidal compositions comprising a first-part of one or more thiolcarbamate herbicides and a second part of an effective antidote compound therefor as defined above are disclosed.

Description: Title "5-Substituted oxazolidines having herbicide antidote activity, production thereof, herbicidal compositions containing them, use thereof in preventing injury to crops and crop seeds coated therewith". 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. Patents 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 have been described to overcome this problem. The treatment of the crop seed with certain "hormonal" antagonistic agents prior to planting has been 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 specifically exemplify and describe the treatment of seeds employing compounds of a different chemical class, not suggestive of the present invention. U.S. Patents 3,989,503, 4,072,688 and 4,124,372 disclose certain substituted oxazolidine compounds. The compounds of the present invention are distinguished from the disclosure of the prior art both from the point of view of structure and utility as herbicidal antidotes for thiolcarbamate herbicides; in particular for S-n-propyl N,N-di-n-propyl thiolcarbamate, S-ethyl di-n-propyl thiocarbamate, S-isopropyl 1- (5-ethyl-2-methyl-piperidine) carbothioate, S-ethyl diisobutyl thiolcarbamate,- and S-ethyl cyclohexyl ethyl thiolcarbamate. It has been discovered that cultivated crop plants can be substantially protected against injury by thiolcarbamate-type herbicides, and said injury can be decreased by the use as antidotes of the herein defined compounds in a variety of ways as more fully described below. The invention provides in one aspect thereof Nhaloacyl oxazolidines of the following formula EMI2.1 in which (A) the group XR1 is phenoxy, and R is selected from the group consisting of haloalkyl containing from 1 to 5 carbon atoms, inclusive, where halo is chloro or bromo, and p-methyl phenylsulfonylamido; and R2 and R3 are independently selected from lower alkyl containing from 1 to 3 carbon atoms, inclusive, where R2 and R3 are lower alkyl this preferably includes those members which contain from 1 to 3 carbon atoms, inclusive, in particular the following: Methyl, ethyl, n-propyl and isopropyl. Where R is haloalkyl, this preferably includes those members which contain from 1 to 5 carbon atoms, inclusive, and the term "halo" includes chloro and bromo as mono, di, tri, tetra or hexa substitutions, that is from 1 to 6 halo substituents. (B) the group X is oxygen or sulphur, R1 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 XR1 is thioethyl, 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 or the N-haloacyl oxazolidine is one of the following specific compounds 2,2-dimethyl3(3-bromopropionyl)5-pentoxymethyl oxazolidine; 2, 2-dimethyl3(5-chlorovaleryl)5-isopropoxymethyl oxazolidine; 2,2 dimethyl-3 (5-chlorovaleryl) 5-allyloxymethyl oxazolidine. In the above description, the following embodiments are intended for the various substituent groups: when R1 is alkyl this preferably includes those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain configurations in particular the following: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, and n-hexyl; when R1 is alkenyl this preferably includes those members which contain from 3 to 6 carbon atoms and at least one ethylenic or double bond such as in l-propenyl, 2-butenyl, 3-butenyl, 1, l-dimethyl-3-butenyl, and the like. When R2 and R3 are lower alkyl this preferably includes those members which contains from 1 to 3 carbon atoms, inclusive; and when R is haloalkyl this preferably includes 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 when R is alkylthio this preferably 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. (C) the group X is oxygen or sulphur and R1 is alkyl; R is selected from the group consisting of haloalkyl, and alkoxycarboalkyl; R2 is selected from the group consisting of phenyl, p-chloro-phenyl and p-bromophenyl; and R3 is selected from the group consisting of hydrogen and methyl. When R1 is alkyl this preferably includes those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain Fonfigurations, in particular the following: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, and tert.-butyl. When R is haloalkyl this preferably includes those members which contain from 1 to 4 carbon atoms, inclusive, and the term "halo" includes chloro and bromo as mono, di, tri, tetra or hexa substitutions, that is from 1 to 6 halo substituents; and when R is alkoxycarboalkyl this preferably includes those members having 3 to 6 carbon atoms, inclusive, such as methoxy propanoyl, methoxy ethanoyl (acetyl), ethoxy propanoyl, ethoxy ethanoyl and the like. Other substituent groups are as indicated in carbon content in the above description. The compounds according to the invention may be formulated in a composition with a thiolcarbamate herbicide and according to a further aspect of the invention there is provided a herbicidal composition which contains a thiolcarbamate herbicide and an antidotally effective amount of an oxazolidine according to the invention. It seems that the compounds of this invention may interfere with the normal herbicidal action of the thiolcarbamate-type and other herbicides, to render them selective in their action. Associated with the presence of the antidote of the invention, is a decrease in phytotoxicity with respect to various crops, otherwise observed when various thiolcarbamate herbicides are used for weed control. 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 wherein the definitions are classified under the heading A, B, and C, can in general be prepared from an intermediate of the formula XI which has the formula EMI5.1 in which X, R1, R2 and R3 have the meanings given above as described below. The general formula covers not only compounds in which X is 0 but also where X is S. These are represented by formulae VI and X below the production of which will now be described. A. When X is oxygen and R1 is phenyl, the requisite starting material (IV) for the compounds within'this invention may be prepared by amination of a 1,2-epoxy3-phenoxy propane (I), with aqueous ammonia or ammonium hydroxide to produce a l-amino-3-phenoxy-2-propanol (it). Subsequent reaction and cyclization with acetone or other ketone (III), yields the N-unsubstituted 2,2-dialkyl 5-phenoxymethyl oxazolidine product (IV). This sequence of reactions is depicted by the following equations: EMI6.1 wherein R1, R2 and R3 have the same significance as previously defined. B. When X is oxygen and R1 is alkyl or alkenyl, the requisite starting material (IV) for the compounds within this invention may be prepared by amination of a l,2-epoxy-3-alkoxy or alkenoxy propane (I) with aqueous ammonia or ammonium hydroxide to produce a l-amino-3alkoxy 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: EMI7.1 wherein R1, R2 and R3 have the same significance as previously defined. When X is sulphur and R1 is alkyl or alkenyl, the requisite starting material (X) for the compounds within this invention may be prepared by thionation with ,a mercaptan (VI) of epichlorohydrin (V) to produce the l-chloro alkyl or l-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 keto (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: EMI7.2 EMI8.1 C. When X is oxygen and R1 is alkyl, the requisite starting material (IV) for the compounds within this invention may be prepared by amination of 1,2-epoxy-3alkoxy or alkenoxy propane (I) with aqueous ammonia or ammonium hydroxide to produce a l-amino-3-alkoxy isopropanol (II). Subsequent reaction and cyclization with benzaldehyde or a substituted benzaldehyde, phenyl or substituted phenyl ketone (III), yields the N-substituted 2,2-dialkyl 5-alkoxy oxazolidine product (IV). This sequence of reactions is depicted in the following equations: EMI8.2 wherein R1, R2 and R3 have the same significance as previously defined. When X is sulphur and R1 is alkyl, the requisite starting material (X) for the compounds within this invention may be prepared by thionation with a mercaptan (VI) of epichlorohydrin (V) to produce the l-chloro alkyl thio-2-propanol (VII), this is followed by reformation of the epoxide (VIII). Amination of the 1,2epoxy-3-alkylthio propane (VIII) with ammonia or aqueous ammonia produce a l-amino-3-alkylthio 2-propanol (IX). Subsequent reaction and cyclization benzaldehyde or a substituted benzaldehyde, phenyl or substituted phenyl ketone (III) yields the N-unsubstituted 2,2dialkyl methyl oxazolidine product (X), this sequence of reactions is depicted by the following equations: EMI9.1 The intermediates of formulae (IV) and CX) may then be converted to the end products as follows: (a) The N-acyl-substituted compounds of the invention wherein R is haloalkyl or alkoxy carbo alkyl may be prepared by direct acylation of a 5-substituted oxazolidine compound for example with an appropriate acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine or an inorganic base, such as sodium hydroxide. (b) The thiocarbamyl 3-substituted compounds of the invention wherein R is alkylthio may be prepared by direct alkylthio formulation of a 5substituted oxazolidine compound with an alkylhalothioformate e.g. an alkylchlorothioformate suitably in the presence of an acid chloride acceptor. (c) The p-toluene sulphonylcarbamyl 3-substituted compounds of the invention wherein R is p-toluene sulphonyl may be prepared by direct carbamylation of a 5-substituted oxazolidine compound with p-toluene sulphonyl isocyanate. In the above reactions, the reaction is preferably performed 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 -100C to 900C. 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 recyrstallization from a suitable solvent. In most instances, the structure was confirmed by analytical techniques, such as infrared spectroscopy, nuclear magnetic resonance or mass spectroscopy. There is therefore provided according to the invention a process for the preparation of compounds according to the invention which comprises treating an intermediate of the formula EMI11.1 in which X, R1, R2 and R3 have the meanings given above and R has the meaning given above by one of the following procedures namely: 1. For the production of compounds in which R is haloalkyl or alkoxycarboalkyl, direct acylation of the compound of formula XI; 2. For the production of compounds in which R is alkylthio, direct alkylformulation of a compound of formula XI; 3. For the production of compounds in which R is p-toluene sulphonyl direct carbamylation of the compound of formula XI. 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 millilitres - 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 A-Compounds Preparation of Intermediate: l-Amino-3-phenoxy isopropanol One hundred (100.0) grams of 3-phenoxy-1,2-epoxy propane was added dropwise with stirring to 1 litre of aqueous 28% ammonia cooled to 0 C overnight in the icebox. During addition over 2 hours, a fine precipitate formed and on standing overnight, this formed a layer at the surface of the mixture. The precipitate was taken up in methylene chloride, dried over MgSO4 and stripped. Yield was 58 grams of material mp 69-750C. A small portion which crystallized from the methylene chloride had mp 79-820C. The structure was confirmed by infrared and nuclear magentic resonance. Preparation of Intermediate : 1,2-Dimethyl-S-phenoxymethyl oxazolidine Thirty (30.0) grams of l-amino-3-phenoxyisopropanol and 15 grams of acetone were combined in 150 millilitres of benzene and ref fluxed under a modified Dean-Stark apparatus. When about 4 millilitres of water had been removed azeotropically, the mixture was cooled and the volume adjusted to 165.2 millilitres, giving a 25 percent w/v solution (4 millilitres = 1 gram). A small sample was stripped to give the title compound n3 1.5150. The structure was confirmed by infrared and nuclear magnetic resonance. Aliquots of this mixture were used in subsequent reactions. The compounds of 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 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 12-dimethyl-N-trichloroacetyl-5-phenoxy- methyl oxazolidine. To 24.8 milliliters of 25 percent w/v, 2,2dimethyl-5-phenoxymethyl oxazolidine in 50 milliliters of benzene was added 5.5 grams of trichioroacetyl chloride. To this solution was added dropwise with cooling 3.1 grams of trimethylamine. After work-up with water, drying and removal of the benzene in vacuo, there was obtained 8.1 grams of the title compound, nD3O 1.5272. Analytical data supports the structure. EXAMPLE II Preparation of 2s2-dimethyl N-2,3-dibromopropionyl-5- phenoxymethyl oxazolidine. In a similar manner as Example I, to 20.7 milliliters of 25 percent w/v, 2,2-dimethyl-5-phenoxymethyl oxazolidine in 50 milliliters of benzene and 6.6 grams of 2,3-dibromopropional chloride was added 2.6 grams of triethylamine. After the appropriate work-up procedure, there was obtained a yields 4.3 grams, nod30 1.5423. Analytical data supports the structure. EXAMPLE III Preparation of 3 2-dimethvl-3- (p-toluene-sulfonyl carbamyl) 5-phenoxymethyl oxazolidine. 'To 20.7 milliliters of 2,2-dimethyl-5-phenoxymethyl oxazolidine, 25 percent w/v in 50 milliliters of benzene was added 419 grams of p-toluene sulfonyl isocyanate. 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. Preparation of B-Compounds 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 400C and the heating removed while the mixture remained at 35-40"C for 3/4 hour. The mixture was then heated at 400C for 1 1/2 hour and then to reflux at which point the temperature was 1050C. Yield after stripping was 103 grams, nod30 1.4862. The product was confirmed by infrared and nuclear magnetic resonance. Preparation of Intermediate: 3-Ethyl-1,2-epoxypropyl sulfide One hundred and twenty seven (127.0) grams of l-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 300C with a water bath and addition took 40 minutes. The product was filtered and the ether stripped off giving 80.8 30 grams of product, nod 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 3-ethyl-1,2-epoxypropyl sulfide was added dropwise with stirring to 1 liter of aqueous 28% ammonia solution, cooled to OOC 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 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. 101-1050C at 1.5-2 millimeters, nD3O 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: l-Amino-3-isopropoxy isopropanol Sixty-three (63.0) grams of 3-isopropoxy-1,2-epoxy propane was added dropwise with stirring to 1 liter of 28 percent aqueous ammonia, cooled to OOC, 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. 77.50C at 0.5 millimeters, 30 nD 1.4200. The structure was confinmed by infrared and nuclear magnetic resonance. Preparation of Intermediate: 2,2-Dimethyl-5-isopropoxymethyl oxazolidine Twenty six and six tenths (26.6) grams of l-amino3-isopropoxy isopropanol and 12 grams of acetone were added to 150 millilieters of benzene and heated to reflux under a modified Dean-Stark apparatus. When about 4 milliliters of water had been azectropically 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 illustrated by the following examples. Following the examples of preparation is a table of compounds which áre 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-dimethyl5-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, nod30 1.4603. Analytical data supports the structure. EXAMPLE II Preparation of 2,2-dimethyl N-dichloroacetyl-5-isopropoxymethyl oxazolidine. In a similar manner as Example 1, 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 grams of triethylamine. After the appropriate work up procedure, there was obtained a yield of 8.9 grams, nD30 1.4564. Analytical data supports the structure. EXAMPLE III Preparation of 2,2-dimethyl-3- (p-tcluene-sulfonyl carbamyl) 5-isopropoxymethyl oxazolidine. To 20.8 milliliters of 25 percent w/v, 2,2-dimethyl5-isopropoxymethyl oxazolidine solution in 50 milliliters of benzene was added 5.9 grams of p-toluene sulfonyl isocyanate. 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. ExMfFLE IV Preparation of 2,2-dimethyl-3- (2,3-dibromopropionyl)-5 methoxymethyl oxazolidine. To 11.6 milliliters of 25 percent w/v, 2,2-dimethyl5-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, nD30 1.4887. Analytical data supports the structure. EXAMPLE V Preparation of 2 2-dimethy1-3-dichloroacetyl-5-a1lyloxymethyl 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, nD30 1.4705. Analytical data supports the structure. EXAMPLE VI (a-c) (a) Preparation of 2,2-dimethyl-3-chloroacetyl-5-ethylthiomethyl oxazolidine. To 21 milliliters of 25 percent w/v, 2,2-dimethyl5-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 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, fly30 1.4942. Infrared data supports the structure. (b) Preparation of 2,2'-dimethyl-3-ethylthiocarbamyl-5- ethylthiomethyl oxazolidine. To 19.3'milliliters of 25 percent w/v, 2,2-dimethyl5-ethylthiomethyl oxazolidine solution in 25 milliliters of benzene was added 2.9 grams of triethylamine and 3.4 grams of ethylchlorothiolformate 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, nod30 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-dimethyl5-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 100C 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, nD30 1.4980. Preparation of C-Compounds 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 400C and the heating removed while the mixture remained at 35-400C for 3/4 hours. The mixture was then heated at 400C for 1 1/2 hours and then to reflux at which point the temperature was 1050C. Yield after stripping was 103 grams, nD30 1.4862. The product was not further purified. The structure was confirmed by infrared and nuclear magnetic resonance spectroscopy. Preparation of Intermediate: 3-Ethyl-l , 2-epoxypropyl sulfide One hundred and twenty seven (127.0) grams of l-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 300C with a water bath and addition took 40 minutes. The product was filtered and the ether stripped off giving 80.8 grams of product, nD3O 1.4567. The structure was confirmed by infrared and nuclear magnetic resonance spectroscopy 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 3-ethyl-1,2-epoxypropyl sulfide was added dropwise with stirring to 1 liter of aqueous 28 percent ammonia solution, cooled to OOC 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 overnight. The water and ammonia were stripped off under vacuum and the only residue distilled to give 59.1 grams of the title compound, b.p. 101-105 C at 1.4-2 milli 30 meters, nD 1.4910. The structure was confirmed by infrared and nuclear magnetic resonance spectroscopy. In preparing the oxazolidine intermediate it was found that is was unnecessary to isolate and purify the compounds before use. The volume of the oxazolidine solution was adjusted to give a 25% 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: l-Amino-3-isopropoxy isopropanol Sixty three (63.0) grams of 3-isopropoxy-1,2-epoxypropane was added dropwise with stirring to 1 liter of 28 percent aqueous ammonia, cooled to OOC 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 only residue distilled to give 38 grams of the title compound, b.p. 77.50C at 0.5 millimeters, nD30 1.4200. The structure was confirmed by infrared and nuclear-magnetic resonance spectroscopy. Preparation of Intermediate: 2-p-Chlorophenyl-5-methoxymethyl oxazolidine Twelve and six tenths (12.6) grams of l-amino-3methoxy-2-propanol and 16.9 grams of p-chlorobenzaldehyde were combined in 150 milliliters of benzene and heated to reflux under a modified Dean-Stark apparatus until about 2.5 milliliters of water were azeotropically removed. An additional 50 milliliters of benzene was distilled over and the mixture was cooled to room temperature and the volume was adjusted to 109.2 milliliters, so that 4 milliliters = gram of intermediate. Aliquots of this solution were used in subsequent reactions. Preparation of Intermediate: 2-Phenyl-5-ethylthiomethyl oxazolidine Thirteen and five tenths (13.5) grams of 2-hydroxy3-aminopropyl ethyl sulfide and 10.6 grams of benzaldehyde were combined in lOO milliliters of benzene and refluxed under a modified Dean-Stark apparatus until about 2 milliliters of water had beenazeotropically removed. The mixture was cooled to room temperature and the volume adjusted to 89.2 milliliters (4 milliliters = 1 gram). Aliquots of this mixture were used in subsequent reactions. The compounds of 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 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-p-chlorophenyl-2(2,3-dibromopropionyl)5- methoxymethyl oxazolidine. To 20.8 milliliters of 25 percent w/v, p-chlorophenyl-5-methoxymethyl oxazolidine solution in 50 milliliters of benzene was added 5 grams of 2,3-dibromopropionyl chloride. To this solution was added 1.6 grams of 50% sodium hydroxide. After washing with water, drying and removal of the benzene in vacuo, there was obtained 4.8 grams of the title compound, 30 nD30 1.5478. Analytical data supports the structure. EXAMPLE II Preparation of 2-p-chlorophenyl-3(2,3-dibromopropionylt propoxymethyl. In a similar manner as Example I, 17.9 milliliters of 25 percent w/v, 2-g-chlorophenyl oxazolidine solution in 50 milliliters of benzene and 4.4 grams of 2,3-dibromopropionyl chloride was added 1.4 grams of 50% sodium hydroxide. After the appropriate work-up procedure, there was obtained a yield of 6.4 grams of the title compound, 30 1.5310. Analytical data supports the structure. nD EXAMPLE III Preparation of 2-D-chlorophenyl-3(3-carbomethoxypropionyl) 5-propoxymethyl oxazolidine. To 25.6 milliliters of 25 percent w/v, 2-2- chlorophenyl-5-propoxymethyl oxazolidine solution in 50 milliliters of bensene was added 3.8 grams of 3-carbomethoxypropionyl chloride. To this reaction mixture was added 2 grams of 50% sodium hydroxide. Upon completion of the reaction solvent, benzene, was removed in vacuo. There was obtained 6.0 grams of the title compound, n, 1.4975. Analytical data supports the structure. - EXAMPLE IV Preparation of 2-phenyl-2 (3-carbomethoxypropionyl)5-methoxymethyl oxazolidine. To 19.3 milliliters of 25 percent w/v, 2-phenyl-5methoxymethyl oxazolidine solution in 50 milliliters of benzene with 3.8 grams of 3-carbomethoxypropionyl chloride was added 2.0 grams of 50% sodium hydroxide. After the reaction was complete the mixture was washed with water, separated, dried and the organic solvent removed in vacuo. There was obtained 6.8 grams of the title compound, nD30 1.4913. Analytical data supports the structure. EXAMPLE V Preparation of 2-phenyl-3-chloroacetyl-5-ethylthiomethyl oxazolidine. To a reaction mixture of 10.1 milliliters of 25 percent w/v, 2-phenyl-5-ethylthiomethyl oxazolidine solution in 25 millilitesrs benzene, 2.5 grams of triethylamine were added dropwise. Cooling in an ice bath and vigorous stirring was maintained during the addition of the chloride and triethylamine, then allowed to stir one hour at room temperature. Upon completion of the reaction, the mixture was washed with water, dried, and the solvent removed in vacuo. There was obtained a yield of 6.0 grams of the title compound, nod 1.5410. TABLE I EMI23.1 A-Compounds Compound XR1 R2 R3 Physical 30 Number R XR1 R2 R3 Constant 1 C13C- phenoxy CH3 CH3 1.5272 2 Cl2CH- phenoxy CH3 CH3 1.5203 3 C1CH2- phenoxy CH3 CH3 1.5198 4 CH3CHB$CHBr- phenoxy CH3 CH3 1.5423 5 p-CH3#SO2NH- phenoxy CH3 CH3 (Glass) B-Compounds 6 CCl3 OCH(CH3)2 CH3 CH3 1.4603 7 CHCl2 OCH(CH3)2 CH3 CH3 1.4564 8 CH2C1 OCH(CH3)2 CH3 CH3 1.4488 9 CH3CHBrCHBr OCH(CH3)2 CH3 CH3 1.4722 10 CH3#SO2NH OCH(CH3)2 CH3 CH3(Glass) 11 CHCl2 OCH3 CH3 CH3 1.4730 12 CH2BrCHBr OCR3 CH3 CH3 1.4887 13 C3H7S OCH3 CH3 CH3 1.4620 14 CHCl2 OC2H5 CH3 CH31.4610 15 CH2BrCH2 OC2H5 CH3 CH3 1.4620 16 CH2BrCHBr OC2H5 CH3 CH3 1.4998 TABLE I (Cont'd) Compound Physical 30 Number R XR1 R2 R3 Constant 17 CHCl2 OCH2CH=CH2 CH3 CH31.4705 18 CH2BrCHBr OCH2CH=CH2 CH3 CH3 1.4934 19 CH2BrCH2 OCH2CH=CH2 CH3 CH3 1.4764 20 CH2C1CH2 OCH2CH=CH2 OH3 CH3 1.4602 21 CH3CHC1 OCH2CH=CH2 CH3 CH3 1.4562 22 CHCl2 OC3H7 CH3 CH3 1.4560 23 CH2BrCHBr OC3H7 CH3 CH3 1.4795 24 CR2BrCH2 OC3H7 CH3 CH3 1.4612 25 CH2C1CH2 OC3H7 CH3 CH3 1.4470 26 CHC12 OC4H9 CH3 CH3 1.4557 27 CH2BrCHBr OC4Hg CH3 CH3 1.4788 28 CH2BrCH2 OC4Hg CH3 CH3 1.4583 29 CH2C1CH2 OC4Hg CH3 CH3 1.4462 30 CH3CHCl OC4H9 CH3 CH31.4420 31 CH2Cl(CH2)3 OCR3 CH3 CH3 1.4588 32 CH2ClCHBr 0CH3 CH3 CH3 1.4808 33 CH2C1CB r OCH(CH3)2 CH3 CH3 1.4692 34 CHCl2 OC5Hll CH3 CH3 1.4508 35 CH2BrCHBr OC5H11 CH3 CH31.4773 36 CH2BrCH2 OC5H11 CH3 CH3 1.4568 TABLE I (Cont'd) Compound XR1 R2 R3 Physical 30 Number R XR1 R2 R3 Constant nD 37 CH2Cl SC2H5 CH3 CH3 1.4942 38 CH2BrCHBr SC2H5 CH3 CH3 1.5142 39 CH2BrCH2 SC2H5 CH3 CH3 1.4973 40 CH2C1CH2 SC2H5 CH3 CH3 1.4862 41 C2H5S SC2H5 CH3 CH3 1.4940 42 CHCl2 SC2H5 CH3 CH3 1.4980 43 CH2Cl(CH2)3 OCR3 CH3 CH3 1.4545 44 CH2C1(CH2)3 OC2H5 CH3 CH3 1.4509 45 CH2Cl(CH2)3 OC3H7 CH3 CH3 1.4463 46 CH2Cl(CH2)3 OCH(CH3)z CH3 CH3 1.4476 47 CH2C1(CH2)3 OCH2CH=CH2 CH3 CH3 1.4586 48 CH2Cl(CH2)3 OC4Hg CH3 CH3 1.4500 49 C5H11CHBrCHBr OC2H5 CH3 CH3 1.4682 50 C5HllCHBrCB r SC2H5 CH3 CH3 1.4942 51 C3H7CHBr OC3H7 CH3 CH3 1.4563 C-Compounds 52 CHCl2 OCR3 p-Cl phenyl H 1.5530 53 CH2BrCHBr OCH3 p-Cl phenyl H 1.5478 54 CH2BrCH2 OCR3 p-Cl phenyl H 1.5341 55 CH2C1CH2 OCH3 p-Cl phenyl H 1.5248 TABLE I (Cont'd) Compound Physical Number R XR1 R2 R3 Constant nD 56 CH3OC(O)CH2CH2 OCR3 p-Cl phenyl H 1.5094 57 CHCl2 OC3H7 p-Cl phenyl H 1.5171 58 CH2BrCHBr OC3H7 p-Cl phenyl H 1.5310 59 CH2BrCH2 OC3H7 p-Cl phenyl H 1.5195 60 CH2ClCH2 OC3H7 p-Cl phenyl H .1.5088 61 CH3OC(O)CH2CH2 OC3H7 p-Cl phenyl H 1.4975 62 CHCl2 OCR3 phenyl H 1.5230 63 CH2C1CH2 OCR3 phenyl H 1.5130 64 CH3OC(O)CH2CH2 OCH3 phenyl H 1.4913 65 CH3CHC1 OCR3 phenyl H 1.5075 66 CHCl2 OC3H7 phenyl H 1.5065 67 CH2BrCH2 OC3H7 phenyl H 1.5090 68 CH2C1CH2 OC3H7 phenyl H 1.5010 69 CH3OC(O)CH2CH2 OC3H7 phenyl H 1.4868 70 CH3CHCl OC3H7 phenyl H 1.4979 71 CHC12 OCH3 p-Br phenyl H 1.5363 72 CH2BrCHBr OC3H7 p-Br phenyl H 1.5390 73 CH3OC(O)CH2CH2 OC3H7 p-Br phenyl H 1.5032 74 CHC12 OC5H11 phenyl H 1.4960 75 CH2BrCHBr OC5H11 phenyl H 1.5123 TABLE I (Cont'd) Compound Physical Number R XR1 R2 R3 Constant nD 30 76 CH3OC(O)CH2CH2 OC5H11 phenyl H 1.4940 77 CH2C1 SC2H5 phenyl H 1.5410 78 CH2BrCHBr SC2H5 phenyl H 1.5580 79 CH2BrCH2 SC2H5 phenyl H 1.5461 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, plant locus 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, Sethyl hexahydro-1H-azepine-l-carbothioate, 2,3,3-trichloroallyl N,-diisopropyl thiolcarbamate, S-isopropyl-1-(5-ethyl3-methyl-piperidine) carbothioate and S-4-chlorobenzyl dimethyl thiolcarbamate. As an embodiment within the scope of the present invention its a two-part or package herbicide system consisting essentially of a first-part of one or more thiolcarbamate 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'estab- lished 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 and 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 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-propyl thiolcarbamate EPTC - EPTAM R 6E - 4133 mg. dissolved in 800 ml. water such that 5 ml. applied to the soil from a planting flat is equiva lent 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. 5-isopropyl 1(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 R 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 amount. D. S-ethyl hexahydro-1H-azepine-1-carbothioate ORDRAM R 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 flat pre-plant incorporated. E. S-propyl di-n-propyl thiolcarbamate VERNAM R - 6E (80%), the following is a listing of various stock solutions prepared, also included is the 1b/A equivalence for 5 ml. pre-plant incorporated: 122 mg/125 ml H2O; 5 ml = 1 lb/A PPI 183 mg/ISO ml H2O; 5 ml = 1.25 lb/A PPI 975 mg/250 ml H2O; 5 ml = 4 'lb/A PPI 2632 mg/450 ml H2O; 5 ml = 6 lb/A PPI 3412 mg/500 ml H2O; 5 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 2.5 ml. acetone, with 1% Tween 20 z (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 "in-furrow" method of application, 95 mg. of active ingredient was dissolved in 15 ml. of acetone with 1% Tween 20R, such that 1.5 ml. applied to the seed and soil in the furrow, in one-half of the flat was equivalent to 5 1b/A. When 1.0 1b/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 200t, such that when 10 ml. of the stock solution was further dissolved in 90 ml. of acetone, 4 ml. was equivalent to 1/20 1b/A PPI. When 30 mg. of the com pound was dissolved in 10 ml. of acetone, 5 ml. was equivalent to 5 1b/A PPI, and 1 ml. was equivalent to 1 lb/A PPI. When 16 mg. was dissolved in 20 ml., 10 ml. was equivalent to 2 lb/A PPI and when 16 mg. was dissolved in 40 ml., 5 ml. was equiva lent 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 seeds 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 incor-, porated application, the following solutions and procedureswere 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 IbIA 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 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 70-900F. 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 provided 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 tHordeum 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 - FT [Setaria viridis] Johnson Grass - JG [Sorghum halepense] Nutsedge - NS [Cyperus esulentus] Shattercane - SC [Sorghum bicolor] Watergrass - WG [Echinochloa crusgalli] Wild Oats - WO [Avena fatua (L.)] Percent injury with antidote present Result = Percent injury of herbicide alone TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 1 VERNAM PPI-TM 6+0.5 SOY 35/60 WG 100/100 FT 90/90 VERNAM PPI-TM 6+1 SOY 40/60 WG 100/100 FT 90/90 RONEET IF 4+5 WH 40/60 FT 80/80 JG 100/100 2 VERNAM IF 6+5 CN 10/70 VERNAM IF 1+5 RC 50/95 R-12001 PPI 6+1/80 CN 30/50 WG 95/95 FT 95/95 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 3 VERNAM IF 1+5 BA 30/50 VERNAM IF 6+5 CN 20/70 4 VERNAM IF 1+5 WH 50/70 VERNAM PPI 4+5 SOY 35/50 WG 100/100 FT 90/90 5 VERNAM IF 6+5 SOY 40/55 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 6 VERNAM IF 1+5 CT 40/70 IF 6+5 CN 0/70 VERNAM PPI 4+1 SOY 30/50 WG 100/100 FT 90/90 EPTAM PPI-TM 5+5 CN 0/80 WG 100/100 FT 100/100 7 VERNAM IF 1+5 MO 50/95 IF 6+5 CN 0/70 ORDRAM ST 2+0.5% MO 10/70 WG 90/90 SC 70/70 RONEET ST 3+0.5% MO 10/70 WG 80/80 SC 80/80 EPTAM PPI-TM 5+0.05 CN 0/80 WG 100/100 PPI-TM 5+5 CN 0/80 FT 100/100 R-12001 ST 2+0.5% MO 50/90 WG 95/95 SC 95/95 RONEET PPI-TM 3+1 MO 10/80 WG 100/100 FT 100/100 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 3+2 MO 0/80 WG 100/100 FT 100/100 3+5 MO 0/80 WG 100/100 FT 100/100 8 VERNAM IF 6+5 CN 10/70 RONEET IF 3+5 MO 40/75 WG 85/85 SC 95/95 9 VERNAM IF 1+5 WH 40/70 CT 50/70 RC 30/95 BA 30/50 6+5 CN 30/70 R-12001 IF 5+5 CT 0/50 WG 95/95 FT 95/95 10 VERNAM IF 6+5 SOY 30/55 IF 4+1 SOY 20/50 WG 100/100 FT 100/100 TABLE IJ (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) RONEET IF 4+5 MO 30/60 FT 80/80 JG 100/100 11 VERNAM IF 1+5 MO 50/95 IF 6+5 CN 0/90 EPTAM PPI 5+0.5 CN 0/80 WG 100/100 FT 100/100 PPI 5+5 CN 0/80 WG 100/100 FT 100/100 RONEET IF 4+5 MO 20/60 FT 80/80 SC 100/100 PPI-TM 3+1 MO 10/80 WG 100/100 FT 100/100 3+5 MO 0/80 WG 100/100 FT 100/100 12 VERNAM IF 1+5 WH 50/75 IF 6+5 CN 0/90 EPTAM PPI 5+0.5 CN 0/80 WG 100/100 FT 100/100 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) PPI 5+5 CN 0/80 WG 100/100 FT 100/100 13 VERNAM IF 1+5 RC 30/95 14 VERNAM IF 1.25+5 MO 10/100 IF 1.25+5 BA 40/95 IF 6+5 CN 20/85 RONEET IF 3+1 MO 40/90 WG 95/95 SC 100/100 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 15 VERNAM IF 1.25+5 MO 50/100 6+5 CN 0/85 RONEET IF 3+5 MO 30/90 WG 95/95 SC 100/100 EPTAM PPI 5+0.5 CN 0/80 WG 100/100 FT 100/100 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 16 VERNAM IF 1.25+5 BA 30/95 17 VERNAM IF 1.25+5 MO 30/100 IF 1.25+5 BA 30/90 IF 6+5 CN 0/90 EPTAM PPI 5+0.5 CN 0/95 FT 100/100 WO 100/100 RONEET PPI 3+1 MO 10/90 WG 100/100 SC 100/100 18 VERNAM IF 1.25+5 BA 30/90 IF 6+5 CN 0/90 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 19 VERNAM IF 6+5 CN 0/90 IF 6+5 SOY 20/50 EPTAM PPI 5+0.5 CN 0/80 WG 100/100 FT 100/100 20 VERNAM IF 6+5 CN 0/90 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 21 VERNAM IF 6+5 CN 50/90 22 VERNAM IF 1.25+5 MO 30/100 IF 6+5 CN 0/90 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 RONEET PPI 3+2 NO 10/90 WG 100/100 SC 100/100 23 VERNAM IF 6+5 CN 0/90 IF 1.25+5 WH 60/95 IF 1.25+5 BA 60/90 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 24 VERNAM IF 6+5 CN 0/90 EPTAM PPI 5+0.5 CN 0/80 WG 100/100 FT 100/100 25 VERNAM IF 6+5 CN 0/90 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 26 VERNAM IF 6+5 CN 0/90 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 RONEET PPI-TM 3+5 MO 0/80 WG 85/100 FT 100/100 27 VERNAM IF 6+5 CN 0/90 EPTAM PPI 5+0.5 CN 0/80 WG 100/100 FT 100/100 VERNAM IF 1.25+5 BA 60/90 28 VERNAM IF 6+5 CN 0/90 EPTAM PPI 5+5 CN 0/80 WG 100/100 FT 100/100 29 VERNAM IF 6+5 CN 60/90 30 VERNAM IF 6+5 CN 60/90 31 VERNAM IF 1.25+5 MO 50/100 IF 6+5 CN 0/90 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) EPTAM PPI 5+5 CN 0/70 WG 100/100 FT 100/100 RONEET PPI-TM 3+5 MO 40/80 WG 100/100 FT 100/100 32 VERNAM IF 1.25+5 MO 40/100 IF 1.25+5 WH 50/100 IF 1.25+5 BA 20/90 IF 6+5 CN 10/90 RONEET PPI-TM 3+5 MO 35/80 WG 100/100 FT 100/100 EPTAM PPI 5+5 CN 0/70 WG 100/100 FT 100/100 33 VERNAM IF 1.25+5 BA 30/90 IF 6+5 CN 0/90 EPTAM PPI 5+5 CN 0/70 WG 100/100 FT 100/100 VERNAM PPI-TM 1.25+5 WH 30/80 WG 95/95 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 34 VERNAM IF 6+5 CN 10/90 SUTAN PPI-TM 6+1 CT 30/50 JG 100/100 NS 90/90 EPTAM PPI 5+0.5 CN 0/70 WG 100/100 FT 100/100 RONEET PPI-TM 3+5 MO 15/80 WG 100/100 FT 100/100 35 VERNAM IF 6+5 CN 70/90 36 VERNAM IF 6+5 CN 40/90 IF 6+5 SOY 50/70 37 VERNAM IF 6+5 CN 20/90 EPTAM PPI-TM 6+5 CN 10/85 WG 98/98 JG 98/98 38 VERNAM IF 1.25+5 BA 40/85 IF 6+5 CN 0/90 EPTAM PPI-TM 5+5 CN 0/85 WG 98/98 FT 98/98 TABLE II (Cont'd) Antidote Compound Herbicide Method of Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 39 VERNAM IF 6+5 CN 0/90 EPTAM PPI-TM 5+0.5 CN 0/85 WG 98/98 JG 98/98 40 VERNAM IF 1.25+5 BA 40/85 IF 6+5 CN 30/90 EPTAM PPI-TM 5+5 CN 0/85 WG 98/98 JG 98/98 41 VERNAM PPI-TM 1.25+5 WH 50/80 WG 50/90 42 VERNAM IF 6+5 SOY 50/65 VERNAM IF 1.25+5 NO 30/100 IF 1.25+5 BA 40/85 IF 6+5 CN 20/90 EPTAM PPI-TM 5+0.05 CN 0/85 WG 90/98 JG 75/98 RONEET PPI-TM 3+2 MO 0/80 WG 100/100 FT 100/100 43 VERNAM IF 6+5 CN 60/95 IF 6+5 SOY 50/60 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 44 VERNAM IF 6+5 CN 20/95 45 VERNAM IF 6+5 SOY 40/60 IF 6+5 CN 50/95 46 VERNAM IF 6+5 CN 30/95 47 VERNAM IF 6+5 CN 35/95 IF 6+5 SOY 40/60 48 VERNAM IF 6+5 CN 75/95 49 VERNAM IF 1.25+5 BA 45/75 IF 6+5 SOY 20/40 50 VERNAM IF 1.25+5 BA 50/75 51 VERNAM IF 6+5 CN 65/90 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 52 VERNAM IF 6+5 CN 10/90 EPTAM PPI 5+5 CN 50/70 WG 100/1000 FT 100/100 53 VERNAM IF 1.25+5 BA 20/90 VERNAM IF 1 1/4+1 BA 30/80 54 VERNAM IF 6+5 SOY 20/70 55 VERNAM IF 6+5 SOY 30/70 IF 5+5 SOY 30/60 56 VERNAM IF 6+5 SOY 30/70 VERNAM IF 5+1 SOY 20/60 WG 95/95 FT 95/95 5+5 SOY 0/60 WG 95/95 FT 95/95 57 VERNAM IF 6+5 CN 40/90 58 VERNAM IF 1.25+5 BA 30/90 IF 1.25+1 BA 30/80 FT 70/70 WO 95/95 59 VERNAM IF 1.25+5 BA 75/90 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 60 VERNAM IF 6+5 SOY 60/70 61 VERNAM IF 6+5 SOY 10/70 IF 5+1 SOY 40/60 WG 95/95 FT 95/95 62 VERNAM IF 6+5 CN 0/90 SUTAN PPI-TM 6+1 CT 10/50 JG 100/100 NS 90/90 PPI-TM 6+5 CT 0/50 JG 100/100 NS 90/90 EPTAM PPI 5+0.5 CN 50/70 WG 100/100 FT 100/100 5+5 CN 0/70 WG 100/100 FT 100/100 63 VERNAM IF 6+5 CN 80/90 64 VERNAM IF 6+5 SOY 30/70 IF 5+5 SOY 30/60 WG 95/95 FT 95/95 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 65 VERNAM IF 6+5 SOY 30/70 IF 5+5 SOY 30/60 WG 95/95 FT 95/95 66 VERNAM IF 6+5 CN 10/90 EPTAM PPI 5+5 CN 0/70 WG 100/100 FT 100/100 67 SUTAN PPI-TM 6+1 CT 20/50 JG 100/100 NS 90/90 68 VERNAM IF 6+5 SOY 30/70 69 VERNAM IF 6+5 SOY 50/70 70 VERNAM IF 6+5 SOY 50/70 SUTAN PPI-TM 6+5 CT 40/50 JG 100/100 NS 90/90 71 VERNAM PPI 1.25+5 MO 45/100 RONEET IF 3+1 MO 40/75 FT 80/80 SC 95/95 TALBE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) SUTAN PPI-TM 6+1 CT 40/50 JG 100/100 NS 90/90 RONEET PPI-TM 3+5 MO 30/80 WG 100/100 FT 100/100 72 SUTAN PPI-TM 6+1 CT 40/50 JG 100/100 NS 90/90 73 VERNAM IF 6+5 SOY 30/70 VERNAM IF 5+5 SOY 30/60 WG 95/95 FT 95/95 74 VERNAM IF 1.25+5 WH 80/90 75 VERNAM IF 1.25+5 WH 80/100 BA 75/90 76 VERNAM IF 6+5 SOY 40/70 77 VERNAM IF 6+5 CN 0/90 EPTAM PPI-TM 5+5 CN 0/85 WG 98/98 JG 98/98 TABLE II (Cont'd) Antidote Compound Herbicide Method of % Injury Number PPI Application Rate Crop Result Weed Result (Herb. + Anti.) (1bs/A or % ST.) 78 VERNAM IF 1.25+5 BA 30/85 PPI-TM 1.25+5 WH 60/80 WG 90/90 79 VERNAM IF 1.25+5 BA 60/85 IF 6+5 CN 60/90 The compounds and 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 antidotally effective amount of an antidote compound therefor corresponding to the formula described hereinabove, and knawn 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 compositions 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 thiolcar bamate 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 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. 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.

Claims: CLAIMS: 1. Compounds according to the formula EMI54.1 wherein XRl is phenoxy, R is selected from the group consisting of haloalkyl containing from 1 to 5 carbon atoms, inclusive, where halo is chloro or bromo, and p-methyl phenylsulfonylamido; and R2 and R3 are independently selected from lower alkyl containing from 1 to 3 carbon atoms, inclusive; or wherein X is oxygen or sulfur, R1 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 XR1 is thioethyl, 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; and a compound selected from the group consisting of 2,2-dimethyl-3-(3-bromopropionyl)5-pentoxymethyl oxazolidine, 2,2-dimethyl-3 (5-chlorovaleryl)5- isopropoxymethyl oxazolidine, and 2,2-dimethyl-3(5-chlorovaleryl) 5-allyloxymethyl oxazólidine; or wherein X is oxygen or sulfur and R1 is alkyl containing from 1 to 6 carbon atoms, inclusive; R is selected from the group consisting of haloalkyl containing from I to 4 carbon atoms, inclusive, and the term halo includes chloro and bromo and alkoxycarboalkyl containing 3 to 6 carbon atoms, inclusive; R2 is selected from the group consisting of phenyl, p-chlorophenyl and p-bromophenyl; and R3 is selected from the group consisting of hydrogen and methyl. 2. Compounds according to the formula EMI55.1 wherein XR1 is phenoxy, R is selected from the group consisting of haloalkyl containing from 1 to 5 carbon atoms, inclusive, where halo is chloro or bromo, and p-methyl phenyl- sulfonylamido; and R2 and R3 are independently selected from lower alkyl containing from 1 to 3 carbon atoms, inclusive. 3. Compounds according to the formula EMI55.2 wherein X is oxygen or sulfur, R1 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 XR1 is thioethyl, 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; and a compound selected from the group consisting of 2,2-dimethyl-3- (3-bromopropionyl)5-pentoxymethyl oxazolidine, 2 ,2-dimethyl-3(5-chlorovaleryl)5-isopropoxy- methyl oxazolidine, and 2,2-dimethyl-3(5-chlorovaleryl) 5-allyloxymethyl oxazolidine. 4. Compounds according to the formula EMI55.3 wherein X is oxygen or sulfur and R1 is alkyl containing from 1 to 6 carbon atoms, inclusive; R is selected from the group consisting of haloalkyl containing from 1 to 4 carbon atoms, inclusive, and the term halo includes chloro and bromo and alkoxycarboalkyl containing 3 to 6 carbon atoms, inclusive; R2 is selected from the group consisting of phenyl, p-chloro-phenyl and p-bromophenyl; and R3 is selected from the group consisting of hydrogen and methyl. 5. A process for the preparation of compounds of the formula: - EMI56.1 wherein XR1 is phenoxy, R is selected from the group consisting of haloalkyl containing from 1 to 5 carbon atoms, inclusive, where halo is chloro or bromo, and p-methyl phenylsulfonylamido; and R2 and R3 are independently selected from lower alkyl containing from 1 to 3 carbon atoms, inclusive; or wherein X is oxygen or sulfur, R1 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 and R2 is less than or equal to 6 carbon atoms and further provided that when XR1 is thioethyl, 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; and a compound selected from the group consisting of 2,2-dimethyl-3 (3-bromopropionyl)5-pentoxymethyl oxazolidine, 2, 2-dimethyl 3 (5-chlorovaleryl) 5-isopropoxymethyl oxazolidine, and 2,2-dimethyl-3(5-chlorovaleryl) 5-allyloxymethyl oxazolidine; or wherein X is oxygen or sulfur and R1 is alkyl containing from 1 to 6 carbon atoms, inclusive; R is selected from the group consisting of haloalkyl containing from 1 to 4 carbon atoms, inclusive, and the term halo includes chloro and bromo and alkoxycarboalkyl containing 3 to 6 carbon atoms, inclusive; R2 is selected from the group consisting of phenyl, p-chlorophenyl and p-bromophenyl; and R3 is selected from the group consisting of hydrogen and methyl which comprises treating an intermediate of the formula EMI57.1 in which X, R1, R2 and 23 have the meanings given above by one of the following procedures namely: : 1. for the production of compounds in which R is haloalkyl or alkoxycarboalkyl, direct acylation of the compound of formula XI; 2. for the production of compounds in which R is alkylthio, direct alkylformulation of a compound of formula XI; 3. for the production of compounds in which R is p-toluene sulphonyl direct carbamylation of the compound of formula XI. 6. A herbicidal composition comprising a thiolcarbamate herbicide and a non-phytotoxic antidotally effective amount of an antidote compound therefor as claimed in claim 1, 2, 3 or 4. 7. 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 a compound as claimed in claim 1, 2, 3 or 4. 8. A method of decreasing injury to crops, said injury due to a thiolcarbamate herbicide, which comprises 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 as claimed in claim 1,2, 3 or 4. 9. A method of protecting a plant crop from injury due to an active herbicidal thiolcarbamate compound comprising applying to the plant seed prior to planting, a non-phytotoxic antidotally effective amount of a compound as claimed in claim 1, 2, 3 or 4. 10. Plant seeds to which have been applied a compound as defined in claim 1. Claims for Austria 1. A process for the preparation of compounds of the formula: EMI59.1 wherein XR1 is phenoxy, R is selected from the group consisting of haloalkyl containing from 1 to 5 carbon atoms, inclusive, where halo is chloro or bromo, and p-methyl phenylsulfonylamido; and R2 and R3 are independently selected from lower alkyl containing from 1 to 3 carbon atoms, inclusive; or 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 and R2 is less than or equal to 6 carbon atoms and further provided that when XR1 is thioethyl, 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; and a compound selected from the group consisting of 2,2 dimethyl-3- (3-bromopropionyl) 5-pentoxymethyl oxazolidine, 2, 2-dimethyl-3 (5-chlorovaleryl) 5-isopropoxymethyl oxazolidine, and 2,2-dimethyl-3(5-chlorovaleryl) 5-allyloxymethyl oxazolidine; or wherein X is oxygen or sulfur and R1 is alkyl containing from 1 to 6 carbon atoms, inclusive; R is selected from the group consisting of haloalkyl containing from 1 to 4 carbon atoms, inclusive, and the term halo includes chloro and bromo and alkoxycarboalkyl containing 3 to 6 carbon atoms, inclusive; R2 is selected from the group consisting of phenyl, pchlorophenyl and p-bromophenyl; and R3 is selected from the group consisting of hydrogen and methyl which comprises treating an intermediate of the formula EMI60.1 in which X, R1, R2 and R3 have the meanings given above by one of the following procedures namely:1. for the production of compounds in which R is haloalkyl or alkoxycarboalkyl, direct acylation of the compound of formula XI; 2. for the production of compounds in which R is ,alkylthio, direct alkylformulation or a compound of formula XI; 3. for the production of compounds in which R is p-toluene sulphonyl direct carbamylation of the compound of formula XI. 2. A herbicidal composition comprising a thiolcarbamate herbicide and a non-phytotoxic antidotally effective amount of an antidote compound therefor. of formula I defined in claim 1 the preparation of which is claimed in claim 1. 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 a compound of formula I defined in claim 1. 4. A method of decreasing injury to crops, said injury due to a thiolcarbamate herbicide, which comprises 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 of formula I as defined in claim 1, the preparation of which is claimed in claim 1. 5. A method of protecting a plant crop from injury due to an active herbicidal thiolcarbamate compound comprising applying to the plant seed prior to planting, a non-phytotoxic antidotally effective amount of a compound of formula I as defined in claim 1. 6. Plant seeds to which have been applied a compound of formula I as defined in claim 1.

Inventors: TEACH, EUGENE GORDON
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1980
Main classification: C07D263
IPC codes: C07D263, A01N25, C07C323, C07D303, A01N43