Patent Publication Number: US-4483706-A

Title: Haloacyl and thiohaloacyl aryl-substituted oxazolidines and thiazolidines herbicidal antidotes

Description:
CROSS-REFERENCE TO PRIOR APPLICATION 
     This is a division of application Ser. No. 317,957, filed Nov. 4, 1981 which in turn is a divisional of U.S. Ser. No. 840,973, filed Oct. 11, 1977, now U.S. Pat. No. 4,322,240, issued Mar. 30, 1982, which in turn is a divisional of U.S. Ser. No. 627,986, filed Nov. 3, 1975, now U.S. Pat. No. 4,072,688, issued Feb. 7, 1978, which in turn is a continuation-in-part of U.S. Ser. No. 550,069, filed Feb. 14, 1975, now abandoned. 
    
    
     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, thiocarbamates and the like. Some examples of these compounds are described in U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314. 
     The side effect of injury to a cultivated crop by various herbicides is particularly inconvenient and unfortunate. When used in the recommended amounts in the soil 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 &#34;hormonal&#34; antagonistic agents prior to planting is described; see U.S. Pat. Nos. 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. The 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. 
     DESCRIPTION OF THE INVENTION 
     It has been discovered that cultivated crop plants can be protected against injury by thiocarbamate-type herbicides and by halogenated acetanilide herbicides, each alone or in mixtures or combination with other compounds. Further, as an alternative effect, the tolerance of the plants to these herbicides can be substantially increased by adding to the soil an antidote compound corresponding to the following formula ##STR2## wherein X and Y are independently oxygen or sulfur; R is halo-alkyl or chloro alkenyl; R 1  is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are mono-fluoro, mono- or di- chloro, nitro, methyl, methoxy or hydroxyl; R 2  is hydrogen or lower alkyl; R 3  is hydrogen or lower alkyl; R 4  is hydrogen, lower alkyl, hydroxymethyl, N-methyl carbamoyloxymethyl or dichloroacetoxymethyl; R 5  is hydrogen, lower alkyl or phenyl; and R 6  is hydrogen; provided that at least one of R 1  or R 5  is phenyl, substituted phenyl or naphthyl. 
     Certain of the compounds disclosed herein are considered new compositions and correspond to the following formula ##STR3## in which X and Y are independently oxygen or sulfur; R is halo-alkyl or chloroalkenyl; R 1  is hydrogen, lower alkyl or phenyl; R 2  is hydrogen or lower alkyl; R 3  is hydrogen or lower alkyl; R 4  is hydrogen or lower alkyl; R 5  is phenyl and R 6  is hydrogen. 
     In the above description, the following embodiments are intended for the various substituent groups: For R, halo-alkyl preferably includes those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain configurations and the term halo includes chloro and bromo as mono, di, tri and tetra substitutions. As exemplary of the alkyl portion within the preferred embodiment are the following: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, amyl, isoamyl, n-hexyl and isohexyl. For R, chloro alkenyl preferably includes those members which contain from 2 to 4 carbon atoms and at least one olefinic double bond and the chloro substituents are present as mono-, di-, tri-, or tetra- substitutions, such as trichlorovinyl. For R 1 , R 2 , R 3 , R 4  and R 5 , lower alkyl in each instance preferably includes those members which contain from 1 to 4 carbon atoms, inclusive, in both straight chain and branched chain configurations, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl and the like. 
     As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate-type and other herbicides to render them selective in their action. Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiocarbamate with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter. 
     Therefore, the terms herbicide antidote or antidotal amount, is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soild in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpose. 
     The compounds of this invention represented by the above formula can be prepared by several different procedures depending upon the starting materials. 
     The oxazolidine and thiazolidine intermediates were prepared by the condensation of the amino alcohol or mercaptan with a suitable aldehyde or ketone in boiling benzene with the continuous separation of water. This method is described by Bergmann et al., JACS 75 358 (1953). Usually, the oxazolidines and thiazolidines intermediates were pure enough to be used directly without further purification. Aliquots of these solutions were then used to prepare the compounds of this invention. 
     Compounds having a 3-thioacyl substitution may be prepared from the corresponding oxygen analogues by methods known in the synthetic organic literature, such as treatment with P 2  S 5  in benzene at reflux. 
     The appropriate intermediate was reacted with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine, to prepare the desired compound. Work-up and purification procedures involved standard methods of extraction, distillation or crystallization. 
    
    
     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-m-nitrophenyl-3-dichloroacetyl oxazolidine 
     Five and eight tenths (5.8) grams of 2-m-nitrophenyl oxazolidine was dissolved in 50 ml. methylene chloride containing 3.5 g. of triethylamine. Dichloroacetyl chloride 4.4 g. was added dropwise with stirring to the reaction flask and cooled in a water bath at room temperature. When addition was complete, the mixture was stirred at room temperature for about 30 minutes, washed with water, separated and dried over anhydrous magnesium sulfate. The solvent was stripped off under vacuum. There was obtained a yield of 8.6 g. of the title compound, N D   30  =1.5590. 
     EXAMPLE II 
     Preparation of 2-ethyl-3-dichloroacetyl-5-phenyl oxazolidine 
     Twenty-one and three tenths (21.3) ml. of a solution containing 5.3 g. of 2-ethyl-5-phenyl oxazolidine was diluted with 25 ml. of benzene and 3.1 g. of triethylamine was added. The mixture was cooled in a room temperature water bath and 4.4 g. of dichloroacetyl chloride was added dropwise with stirring. The stirring was continued for about 30 minutes after addition was complete. The solution was washed with water, separated, dried over magnesium sulfate and removed under vacuum. There was obtained a yield of 8.7 g. of the title compound, an oil, N D   30  =1.5600. 
     EXAMPLE III 
     Preparation of 2,2-dimethyl-3-dichloroacetyl-5-phenyl oxazolidine 
     One hundred (100) grams of 1-phenyl-2-amino ethanol was dissolved in 250 ml. of benzene and 45 g. of acetone was added. The mixture was heated at reflux for several hours while about 15 ml. of water was removed with a modified Dean-Stark apparatus. The mixture was cooled and 75 ml. of triethylamine was added, followed by 108 g. of dichloroacetyl chloride added dropwise with stirring and cooling in a room temperature water bath. The solution was allowed to stand after addition was complete, washed with water, dried over anhydrous magnesium sulfate, and the solvent stripped under vacuum. The thick oil wt. 170 g. crystallized on standing and was triturated with dry ether to give 132 g. of the title compound, a white solid, m.p. 99.5°-100.5° C. 
     EXAMPLE IV 
     Preparation of 2-α-naphthyl-3-chloroacetyl oxazolidine 
     Nineteen and nine tenths (19.9) ml of a benzene solution containing 5 g. of 2-α-naphthyl oxazolidine was combined with 50 ml. of benzene and 2.8 g. of chloroacetyl chloride. To this was added 2.6 g. of triethylamine, dropwise with stirring in an ice bath. The mixture was stirred at room temperature for 30 minutes after addition was complete, washed with water, separated and dried over magnesium sulfate. The solvent was stripped under vacuum. There was obtained a yield of 6.7 g. of an oil, the title compound, N D   30  =1.6030. 
     EXAMPLE V 
     Preparation of 2-phenyl-3-chloroacetyl-4,4-dimethyl oxazolidine 
     Twenty-one and three tenths (21.3) ml. of a benzene solution containing 5.3 g. of 2-phenyl-4,4-dimethyl oxazolidine was mixed with 50 ml. of benzene and 3.4 g. of chloroacetyl chloride. To this solution was added 3.1 g. of triethylamine, dropwise with stirring in an ice bath. The mixture was stirred for about 30 minutes after addition was complete and then washed with water, separated and dried over magnesium sulfate and the solvent stripped. There was obtained a yield of 6.5 g. of an oil, the title compound, N D   30  =1.5364. 
     EXAMPLE VI 
     Preparation of 2-phenyl-3-dichloroacetyl thiazolidine 
     Five (5) grams of 2-phenyl thiazolidine was dissolved in 50 ml. of acetone, 3.1 g. of thiethylamine was added and the mixture stirred in a room temperature water bath, while 4.4 g. of dichloroacetyl chloride was added dropwise. The mixture was allowed to stand for about 30 minutes and then poured into water, extracted with methylene chloride, separated, dried over magnesium sulfate, and the solvent stripped under vacuum. There was obtained a yield of 7.3 g. of an oil, the title compound, N D   30  =1.5836. 
     EXAMPLE VII 
     Preparation of 2-m-chlorophenyl-3-dichloroacetyl thiazolidine 
     Five (5) grams of 2-m-chlorophenyl thiazolidine was dissolved in 50 ml. of benzene and 2.6 g. of triethylamine and the mixture was stirred in a room temperature water bath, while 3.7 g. of dichloroacetyl chloride was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated and dried over magnesium sulfate and the benzene stripped under vacuum. There was obtained a yield of 7.2 g. of an oil, the title compound, N D   30  =1.5805. 
     EXAMPLE VIII 
     Preparation of 2(2&#39;,6&#39;-dichlorophenyl)3-chloroacetyl thiazolidine 
     Twenty-three and five tenths (23.5) ml. of a benzene solution containing 5.9 g. of 2(2&#39;,6&#39;-dichlorophenyl) thiazolidine was combined with 25 ml. of benzene and 2.8 g. of chloroacetyl chloride and the mixture stirred in an ice bath, while 2.6 g. of triethylamine was added dropwise. After standing for about 30 minutes the mixture was washed with water, separated, dried over magnesium sulfate and the benzene stripped off under vacuum. There was obtained a yield of 8 g. of an oil, the title compound, N D   30  =1.6041. 
     EXAMPLE IX 
     Preparation of 3(3-bromopropionyl)5-phenyl oxazolidine 
     Four and five tenths (4.5) grams of 5-phenyl oxazolidine contained in 44.7 g. of benzene solution was mixed with 3.1 g. of triethylamine and stirred in a room temperature water bath, while 5.2 g. of 3-bromopropionyl chloride was added dropwise. After standing for about 30 minutes, the solution was washed with water, separated, dried over magnesium sulfate and the solvent stripped under vacuum. There was obtained a yield of 6 g. of an oil, the title compound, N D   30  =1.5591. 
     EXAMPLE X 
     Preparation of 2,2,4-trimethyl-3-dichloroacetyl-5-phenyl oxazolidine 
     Twenty-three (23) ml. of a benzene solution containing 5.7 g. of 2,2,4-trimethyl-5-phenyl oxazolidine was mixed with 25 ml. of benzene and 3.1 g. of triethylamine and stripped at room temperature, while 4.4 g. of dichloroacetyl chloride was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated, dried over magnesium sulfate and stripped under vacuum. The product which crystallized was extracted with ether and precipitated with pentane. There was obtained 3.9 g. of a solid, the title compound, m.p. 126° C. 
     EXAMPLE XI 
     Preparation of 2-p-chlorophenyl-3-dichloroacetyl oxazolidine 
     Twenty-two (22) ml. of a benzene solution containing 5.5 g. of 2-p-chlorophenyl oxazolidine was mixed with 25 ml. of benzene and 3.1 g. of triethylamine and stirred at room temperature, while 4.4 g. of dichloroacetyl chloride was added dropwise. The mixture was allowed to stand for about 30 minutes, washed with water, separated, dried over magnesium sulfate and then stripped. There was obtained a yield of 8.4 g. of an oil, the title compound, N D   30  =1.5668. 
     EXAMPLE XII 
     Preparation of 2,5-diphenyl-3(2,3-dibromopropionyl) oxazolidine 
     Four and five tenths (4.5) grams of 2,5-diphenyl oxazolidine was dissolved in 50 ml. of methylene chloride and 5 g. of 2,3-dibromopropionyl chloride was added and the mixture stirred in an ice bath, while 2.1 g. of triethylamine was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated and dried over magnesium sulfate and stripped under vacuum. There was obtained a yield of 7.1 g. of an oil, the title compound, N D   30  =1.5734. 
     The following is a table of the compounds which are prepared according to the aforementioned procedures. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification. 
     
                                           TABLE I                                 
__________________________________________________________________________
 ##STR4##                                                                 
COMPOUND                                         M.P. or                  
NUMBER  R       R.sub.1   R.sub.2                                         
                             R.sub.3 R.sub.4                              
                                        R.sub.5                           
                                           R.sub.6                        
                                             X Y N.sub.D.sup.30           
__________________________________________________________________________
1       CHCl.sub.2                                                        
                m-NO.sub.2C.sub.6 H.sub.4                                 
                          H  H       H  H  H O O 1.5590                   
2       CHCl.sub.2                                                        
                m-NO.sub.2C.sub.6 H.sub.4                                 
                          H  CH.sub.3                                     
                                     CH.sub.3                             
                                        H  H O O 1.5448                   
3       CH.sub.2 Cl                                                       
                m-NO.sub.2C.sub.6 H.sub.4                                 
                          H  CH.sub.3                                     
                                     CH.sub.3                             
                                        H  H O O 1.5484                   
4       CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H O O 1.5490                   
5       CCl.sub.3                                                         
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H O O 1.5398                   
6       CHBrCH.sub.3                                                      
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H O O 1.5490                   
7       CCl.sub.2CH.sub.3                                                 
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H O O 1.5301                   
8       CHBr.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H O O 1.5808                   
9       CHBrCH.sub.2 Br                                                   
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H O O 1.5712                   
10      CClCCl.sub.2                                                      
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H O O 1.5615                   
11      CHCl.sub.2                                                        
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5550                   
12      CCl.sub.3                                                         
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5475                   
13      CH.sub.2 Cl                                                       
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5590                   
14      CH.sub.2 Br                                                       
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5720                   
15      CHBrCH.sub.3                                                      
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5590                   
16      CHBr.sub.2                                                        
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5833                   
17      CHBrCH.sub.2 Br                                                   
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5718                   
18      CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  C.sub.2 H.sub.5                              
                                     H  H  H O O 1.5353                   
19      CCl.sub.3                                                         
                C.sub.6 H.sub.5                                           
                          H  C.sub.2 H.sub.5                              
                                     H  H  H O O 1.5310                   
20      CHCl.sub.2                                                        
                C.sub.2 H.sub.5                                           
                          H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5600                   
21      CCl.sub.3                                                         
                C.sub.2 H.sub.5                                           
                          H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5455                   
22      CHCl.sub.2                                                        
                CH.sub.3  CH.sub.3                                        
                             H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5438                   
23      CH.sub.2 Cl                                                       
                CH.sub.3  CH.sub.3                                        
                             H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5450                   
24      CHCl.sub.2                                                        
                p-CH.sub.3C.sub.6 H.sub.4                                 
                          H  H       H  H  H O O 1.5440                   
25      CCl.sub.3                                                         
                p-CH.sub.3C.sub.6 H.sub.4                                 
                          H  H       H  H  H O O 1.5430                   
26      CHBrCH.sub.2 Br                                                   
                p-CH.sub.3C.sub.6 H.sub.4                                 
                          H  H       H  H  H O O 1.5627                   
27      CCl.sub.2 CH.sub.3                                                
                p-CH.sub.3C.sub.6 H.sub.4                                 
                          H  H       H  H  H O O 1.5370                   
28      CH.sub.2 Cl                                                       
                p-CH.sub.3C.sub.6 H.sub.4                                 
                          H  H       H  H  H O O 1.5600                   
29      CH.sub.2 Cl                                                       
                m-CH.sub.3 OC.sub.6 H.sub.4                               
                          H  H       H  H  H O O 1.5570                   
30      CHCl.sub.2                                                        
                m-CH.sub.3 OC.sub.6 H.sub.4                               
                          H  H       H  H  H O O 1.5557                   
31      CCl.sub.3                                                         
                m-CH.sub.3 OC.sub.6 H.sub.4                               
                          H  H       H  H  H O O 1.5479                   
32      CCl.sub.2 CH.sub.3                                                
                m-CH.sub.3 OC.sub.6 H.sub.4                               
                          H  H       H  H  H O O 1.5380                   
33      CHBrCH.sub.2 Br                                                   
                m-CH.sub.3 OC.sub.6 H.sub.4                               
                          H  H       H  H  H O O 1.5688                   
34      CH.sub.2 Cl                                                       
                 ##STR5## H  H       H  H  H O O 1.6030                   
  35    CHCl.sub.2                                                        
                 ##STR6## H  H       H  H  H O O 1.5980                   
  36    CCl.sub.3                                                         
                 ##STR7## H  H       H  H  H O O 1.5132                   
  37    CCl.sub.2 CH.sub.3                                                
                 ##STR8## H  H       H  H  H O O 1.5921                   
  38    CH.sub.2 Cl                                                       
                C.sub.6 H.sub.5                                           
                          H  H       H  CH.sub.3                          
                                           H O O 1.5486                   
39      CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  H       H  CH.sub.3                          
                                           H O O 1.5423                   
40      CCl.sub.3                                                         
                C.sub.6 H.sub.5                                           
                          H  H       H  CH.sub.3                          
                                           H O O 1.5376                   
41      CCl.sub.2 CH.sub.3                                                
                C.sub.6 H.sub.5                                           
                          H  H       H  CH.sub.3                          
                                           H O O 1.5530                   
42      CH.sub.2 Cl                                                       
                C.sub.6 H.sub.5                                           
                          H  CH.sub.3                                     
                                     CH.sub.3                             
                                        CH.sub.3                          
                                           H O O 1.5364                   
43      CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  CH.sub.3                                     
                                     CH.sub.3                             
                                        CH.sub.3                          
                                           H O O 1.5343                   
44      CCl.sub.3                                                         
                C.sub.6 H.sub.5                                           
                          H  CH.sub.3                                     
                                     CH.sub.3                             
                                        CH.sub.3                          
                                           H O O 1.5310                   
45      CCl.sub.2 CH.sub.3                                                
                C.sub.6 H.sub.5                                           
                          H  CH.sub.3                                     
                                     CH.sub.3                             
                                        CH.sub.3                          
                                           H O O 1.5213                   
46      CH.sub.2 Cl                                                       
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H S O 1.5804                   
47      CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H S O 1.5836                   
48      CCl.sub.3                                                         
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H S O 1.5950                   
49      CCl.sub.2 CH.sub.3                                                
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H S O 1.5798                   
50      CH.sub.2 CH.sub.2 Br                                              
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H S O 1.5983                   
51      CHBrCH.sub.2 Br                                                   
                C.sub.6 H.sub.5                                           
                          H  H       H  H  H S O 110-112                  
52      CH.sub.2 Cl                                                       
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.5925                   
53      CHCl.sub.2                                                        
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.5805                   
54      CCl.sub.3                                                         
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.5940                   
55      CCl.sub.2 CH.sub.3                                                
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.5850                   
56      CH.sub.2 CH.sub.2 Br                                              
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.5931                   
57      CHBrCH.sub.2 Br                                                   
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.6038                   
58      CH.sub.2 CH.sub.2 Cl                                              
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.5920                   
59      CH.sub.2 Cl                                                       
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H O O 1.5748                   
60      CHCl.sub.2                                                        
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H O O 1.5663                   
61      CCl.sub.3                                                         
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H O O 1.5613                   
62      CCl.sub.2 CH.sub.3                                                
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H O O 1.5530                   
63      CH.sub.2 Cl                                                       
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H S O 1.6041                   
64      CHCl.sub.2                                                        
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H S O 1.6038                   
65      CCl.sub.3                                                         
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H S O 1.5962                   
66      CCl.sub.2 CH.sub.3                                                
                3,5-Cl.sub.2C.sub.6 H.sub.3                               
                          H  H       H  H  H S O 1.5908                   
67      CH.sub.2 Cl                                                       
                H         H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5640                   
68      CHCl.sub.2                                                        
                H         H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5593                   
69      CCl.sub.3                                                         
                H         H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5558                   
70      CHBrCH.sub.2 Br                                                   
                H         H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5738                   
71      CCl.sub.2 CH.sub.3                                                
                H         H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5433                   
72      CH.sub.2CH.sub.2 Br                                               
                H         H  H       H  C.sub.6 H.sub.5                   
                                           H O O 1.5591                   
73      CHCl.sub.2                                                        
                m-OHC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O Waxy Solid               
74      CCl.sub.2 CH.sub.3                                                
                m-OHC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5453                   
75      CHCl.sub.2                                                        
                p-NO.sub.2C.sub.6 H.sub.4                                 
                          H  H       H  H  H S O 1.6008                   
76      CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  C.sub.2 H.sub.5                              
                                     H  H  H S O 1.5352                   
77      CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  CH.sub.3                                     
                                     CH.sub.3                             
                                        H  H S O 1.5366                   
78      CH.sub.2 Cl                                                       
                CH.sub.3  CH.sub.3                                        
                             CH.sub.3                                     
                                     H  C.sub.6 H.sub.5                   
                                           H O O 1.5021                   
79      CHCl.sub.2                                                        
                CH.sub.3  CH.sub.3                                        
                             CH.sub.3                                     
                                     H  C.sub.6 H.sub.5                   
                                           H O O 126° C.           
80      CCl.sub.3                                                         
                CH.sub.3  CH.sub.3                                        
                             CH.sub.3                                     
                                     H  C.sub.6 H.sub.5                   
                                           H O O 1.5080                   
81      CH.sub.2 BrCH.sub.2                                               
                CH.sub.3  CH.sub.3                                        
                             CH.sub.3                                     
                                     H  C.sub.6 H.sub.5                   
                                           H O O 1.5051                   
82      CH.sub.2 BrCHBr                                                   
                CH.sub.3  CH.sub.3                                        
                             CH.sub.3                                     
                                     H  C.sub.6 H.sub.5                   
                                           H O O 1.5450                   
83      CH.sub.2 Cl                                                       
                o-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5578                   
84      CHCl.sub.2                                                        
                o-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5595                   
85      CH.sub.2 BrCHBr                                                   
                o-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5794                   
86      CH.sub.2 Cl                                                       
                p-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5688                   
87      CHCl.sub.2                                                        
                p-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5668                   
88      CH.sub.2 BrCHBr                                                   
                p-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5814                   
89      CCl.sub.2CCl                                                      
                p-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H O O 1.5754                   
90      CCl.sub.2CCl                                                      
                m-ClC.sub.6 H.sub.4                                       
                          H  H       H  H  H S O 1.6008                   
91      CHCl.sub.2                                                        
                C.sub.6 H.sub.5                                           
                          H  H       H  C.sub.6 H.sub.5                   
                                           H S O 1.5653                   
92      CH.sub.2 BrCHBr                                                   
                C.sub.6 H.sub.5                                           
                          H  H       H  C.sub.6 H.sub.5                   
                                           H S O 1.5734                   
93      CH.sub.2 Cl                                                       
                C.sub.6 H.sub.5                                           
                          H  H       H  C.sub.6 H.sub.5                   
                                           H S O 1.5723                   
94      CHCl.sub.2                                                        
                3,4-di-ClC.sub.6 H.sub.4                                  
                          H  H       H  H  H S O 1.5600                   
95      Cl.sub.2 CH                                                       
                p-φ-OCH.sub.3                                         
                          H  H       H  H  H S O 1.5740                   
96      Cl.sub.2 CH                                                       
                o-Clφ H  H       H  H  H S O 97-102° C.        
97      Cl.sub.2 CH                                                       
                m-Fφ  H  H       H  H  H S O 1.5650                   
98      Cl.sub.2 CH                                                       
                CH.sub.3  CH.sub.3                                        
                             CH.sub.2 OH                                  
                                     H  φ                             
                                           H O O 1.5190                   
                             O                                            
99      Cl.sub.2 CH                                                       
                CH.sub.3  CH.sub.3                                        
                             CH.sub.2 OCNHCH.sub.3                        
                                     H  φ                             
                                           H O O 1.5070                   
                             O                                            
100     Cl.sub.2 CH                                                       
                CH.sub.3  CH.sub.3                                        
                             CH.sub.2 OCCHCl.sub.2                        
                                     H  φ                             
                                           H O O 1.5180                   
101     CH.sub.2 Cl                                                       
                CH.sub.3  CH.sub.3                                        
                             CH.sub.2 OH                                  
                                     H  φ                             
                                           H O O 1.5182                   
102     CHCl.sub.2                                                        
                m-Clφ H  CH.sub.3                                     
                                     H  CH.sub.3                          
                                           H O O 1.5243                   
103     CH.sub.2 BrCHBr                                                   
                m-Clφ H  CH.sub.3                                     
                                     H  CH.sub.3                          
                                           H O O 1.5406                   
__________________________________________________________________________
 
    
     Other examples of compounds falling within the generic formula presented herein, which are preparable by the aforedescribed procedures and which may be formulated into herbicidal compositions and applied as herein illustrated, are: 
     
         ______________________________________                                    
R        R.sub.1    R.sub.2                                               
                           R.sub.3                                        
                               R.sub.4                                    
                                    R.sub.5                               
                                         R.sub.6                          
                                             X   Y                        
______________________________________                                    
CH.sub.2 Cl                                                               
         C.sub.6 H.sub.5                                                  
                    H      H   H    H    H   O   S                        
CHCl.sub.2                                                                
         C.sub.6 H.sub.5                                                  
                    H      H   H    H    H   O   S                        
CCl.sub.3                                                                 
         C.sub.6 H.sub.5                                                  
                    H      H   H    H    H   O   S                        
CH.sub.2 Cl                                                               
         C.sub.6 H.sub.5                                                  
                    H      H   H    H    H   S   S                        
CHCl.sub.2                                                                
         C.sub.6 H.sub.5                                                  
                    H      H   H    H    H   S   S                        
CCl.sub.3                                                                 
         C.sub.6 H.sub.5                                                  
                    H      H   H    H    H   S   S                        
CH.sub.2 Cl                                                               
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   O   S                        
CHCl.sub.2                                                                
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   O   S                        
CCl.sub.3                                                                 
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   O   S                        
CH.sub.2 Cl                                                               
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   S   S                        
CHCl.sub.2                                                                
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   S   S                        
CCl.sub.3                                                                 
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   S   S                        
CH.sub.2 BrCHBr                                                           
         m-Cl--C.sub.6 H.sub.4                                            
                    H      H   H    CH.sub.3                              
                                         H   O   S                        
CH.sub.2 BrCHBr                                                           
         C.sub.6 H.sub.5                                                  
                    H      H   H    CH.sub.3                              
                                         H   S   S                        
CH.sub.2 BrCHBr                                                           
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   O   S                        
CH.sub.2 BrCHBr                                                           
         CH.sub.3   CH.sub.3                                              
                           H   H    C.sub.6 H.sub.5                       
                                         H   S   S                        
______________________________________                                    
 
    
     The herbicides indicated in the tables and elsewhere are used at rates which produce effective control of undesirable vegetation. The range of rates employed herein produce representative results within the recommended amounts set forth by the supplier. Therefore, the weed control in each instance is commercially acceptable within the desired or recommended amount. 
     It is clear that the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbicidal activity varies among specific compounds and among combinations of specific compounds within the classes. Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus, selection of a specific herbicidal compound or combination to control undesirable plant species readily may be made. Within the present invention are prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by this method is not intended to be limited by the specific crops employed in the examples. The herbicidal compounds employed in the utility of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effective against a wide range of plant species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the herein described herbicidal compounds to the area or plant locus where control is desired. The compositions as set forth in this invention include those wherein the preferred active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichloroallyl-diisopropyl thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, 2-chloro-2&#39;,6&#39;-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-1H-azepine-1-carbothioate, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl diethyl thiocarbamate, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis(ethylamino)-3-triazine, 2(4-chloro-6-ethylamine-s-triazine-2-yl-amino)-2-methylpropionitrile, 2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine, 2,4-dichlorophenoxyacetic acid, its esters and salts, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea and combinations thereof. 
     An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By &#34;plants&#34;, it is meant germinant seeds, emerging seedlings and established vegetation including the roots and above-ground portions. 
     Evaluation Procedures 
     Flats to be used for growing the crops and weed species were filled with loamy sand soil. Stock solutions of herbicides and antidotes were prepared as follows: 
     A. Herbicide-2-chloro-2&#39;,6&#39;-diethyl-N-(methoxymethyl) acetanilide-LASSO 4E-6.25 g. of LASSO 4E was diluted in 1000 ml. of water. 100 ml. of this solution was applied using a linear spray table, such that the equivalent of 2 lb/A of LASSO was applied in 80 gal. of water per acre to each flat. 
     B. Antidote-of each candidate 95 mg. was dissolved in 15 ml. of acetone with 1% Tween 20® (polyoxyethylene sorbitan monolaurate) so that 11/2ml. equals 5 lb/A per flat (based on 1/2 surface area of a flat). 
     PES and PPI Tank Mixes 
     In-furrow application of the antidote employed the above stock solutions (A and B). 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 additives. The soil was leveled before planting. 
     Rows one-quarter inch deep were made lengthweise in each treated flat, preparatory to seeding. After seeding, the flats were sectioned into two equal portions using a wooden barrier and one and one-half ml. of additive stock solution (B) was atomized directly onto the exposed seed and into the 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. 
     The herbicide was applied initially on an individual flat basis by spraying on the soil on a linear spray table the required amount of the herbicide stock solution onto the soil, after seeding and antidote treatment of the furrow. 
     For tank mixes to be applied as pre-emergence surface application or as pre-plant incorporation, application of the following solutions were used. For 2-chloro-2&#39;,6&#39;-diethyl-N-methoxymethyl) acetanilide at 2 lb/A 800 mg. 4E was diluted to 200 ml. with deionized water. To prepare a combined tank mix, 4 ml. of the acetanilide stock solution and 3 ml. of the antidote stock solution (B) were mixed. For the pre-plant incorporation, the same mixed stock solution was injected into the soil during incorporation in a 5 gallon rotary mixer. For pre-emergence surface application, the same stock solution was applied to soil surface after seeding. 
     The 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 flats treated with the herbicide alone were included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. 
     Some of the candidate antidotes were assayed as antidotes to protect various crops against injury from thiocarbamate herbicides. Selected as representative thiocarbamate herbicides were S-ethyl N,N-dipropylthiocarbamate (EPTC, EPTAM®) and S-propyl N,N-dipropylthiocarbamate (VERNAM®). Stock solutions of herbicides and antidotes were prepared and applied in a variety of ways. Soil incorporation, pre-emergence surface application and in-furrow treatment were employed. 
     Stock solutions for EPTAM® were prepared as follows: 
     A. 1/2lb/A: 670 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 1/2lb/A/flat. 
     B. 5 lb/A: 6700 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 5 lb/A/flat. 
     Stock solutions for VERNAM®: 
     C. 3/4lb/A: 95 mg. of VERNAM° (75% a.i.) was diluted with 100 ml. of deionized water so that 4 ml. applied pre-plant incorporated is equivalent to 3/4 lb/A per flat. 
     D. 1 lb/A: 633 mg. of VERNAM® (75% a.i.) was diluted with 500 ml. of deionized water so that 4 ml. applied is equivalent to 1 lb/A per flat. 
     E. 5 lb/A: 633 mg. of VERNAM® (75 % a.i.) was diluted with 100 ml. of deionized water so that 4 ml. is equivalent to 5 lb/A per flat. 
     The following table includes results as percent protection of various crops according to the various procedures discussed above. The percent protection is determined by a comparison with flats not treated with the candidate antidotes of this invention. 
     
                                           TABLE II                                
__________________________________________________________________________
Application Method:  In-Furrow - IF                                       
                     Pre-Plant Incorporation - PPI (Tank Mix)             
                     Pre-Emergence Surface Application - PES              
                     (Tank Mix)                                           
Crop Species:        Milo - (Sorghum vulgare)                             
Weed Species:        Shatter cane - SC (Sorghum bicolor)                  
                     Foxtail - ft (Sataria viridis)                       
                     Crabgrass - CG (Digitaria sanguinalis)               
                     Watergrass - WG (Echinochloa crusgalli)              
__________________________________________________________________________
               PPI (5 lb/A)    PES (5 lb/A)                               
COMPOUND                                                                  
        5 lb/A - IF                                                       
               (Tank Mix)      (Tank Mix)                                 
NUMBER  Milo                                                              
           SC  Milo                                                       
                   Ft  CG  WG  Milo                                       
                                   Ft  CG  WG                             
__________________________________________________________________________
LASSO 2 lb/A                                                              
        100*                                                              
           100*                                                           
               50  100 100 100 70  100 100 100                            
  1**   70 0   0   0   0   0   0   0   0   0                              
 2      20 0   0   0   0   0   0   0   0   0                              
 3      50 0   0   0   0   0   0   0   0   0                              
 4      60 50  100 0   0   0   70  0   0   0                              
 6      20 0   0   0   0   0   0   0   0   0                              
10       0 0   80  0   0   0   14  0   0   0                              
11      60 0   60  0   0   0   0   0   0   0                              
14       0 0   40  0   0   0   0   0   0   0                              
15      15 0   60  0   0   0   14  0   0   0                              
18       0 0   40  0   0   0   14  0   0   0                              
20      80 90  100 0   20  10  85  0   0   0                              
21      15 0   0   0   0   0   0   0   0   0                              
22      90 90  100 0   0   0   100 0   0   0                              
23      70 70  0   0   0   0   0   0   0   0                              
24      15 0   40  0   0   0   28  0   0   0                              
27       0 0   40  0   0   0   0   0   0   0                              
29       0 0   40  0   0   0   0   0   0   0                              
32       0 0   40  0   0   0   14  0   0   0                              
35      30 0   0   0   0   0   0   0   0   0                              
42      50 0   20  0   0   0   0   0   0   0                              
43      60 0   0   0   0   0   0   0   0   0                              
46      25 0   40  0   0   0   14  0   0   0                              
47      50 0   0   0   0   0   0   0   0   0                              
48      30 0   0   0   0   0   0   0   0   0                              
49      40 0   0   0   0   0   0   0   0   0                              
50      50 0   40  0   0   0   0   0   0   0                              
51      30 0   0   0   0   0   0   0   0   0                              
52       0 0   40  0   0   0   28  0   0   0                              
53      50 0   0   0   0   0   0   0   0   0                              
54      20 0   0   0   0   0   0   0   0   0                              
55      60 0   20  0   0   0   28  0   0   0                              
56      20 0   20  0   0   0   0   0   0   0                              
57      30 0   0   0   0   0   0   0   0   0                              
58      60 0   0   0   0   0   0   0   0   0                              
59      30 0   80  0   30  0   0   0   0   0                              
63      20 0   80  0   0   0   14  0   0   0                              
64      50 0   0   0   0   0   0   0   0   0                              
65      30 0   0   0   0   0   0   0   0   0                              
67       0 0   40  0   0   0   28  0   0   0                              
68      80 0   0   0   0   0   0   0   0   0                              
70      40 0   0   0   0   0   0   0   0   0                              
72      50 0   0   0   0   0   0   0   0   0                              
73      15 0   60  0   0   0   0   0   0   0                              
75      40 0   80  0   0   0   65  0   0   0                              
76      40 0   0   0   0   0   0   0   0   0                              
77      40 0   0   0   0   0   0   0   0   0                              
78       5 --  16  0   0   0   20  0   0   0                              
79      80 --  50  0   0   0   50  0   0   0                              
80      20 --  0   0   0   0   16  0   0   0                              
81      15 --  0   0   0   0   0   0   0   0                              
83      15 --  0   0   0   0   16  0   0   0                              
84      60 --  50  0   0   0   50  0   0   0                              
85       0 --  20  0   0   0   50  0   0   0                              
87      50 --  40  0   0   0   67  0   0   0                              
88       0 --  30  0   0   0   16  0   0   0                              
89      30 --  30  0   0   0   16  0   0   0                              
90      30 --  0   0   0   0   0   0   0   0                              
91      15 --  0   0   0   0   16  0   0   0                              
92      40 --  0   0   0   0   0   0   0   0                              
94      40 --  50  0   0   0   40  0   0   0                              
__________________________________________________________________________
 -- = not tested.                                                         
 * = % injury                                                             
 ** = % protection                                                        
 
    
     Thiocarbamate Herbicide Multicrop Screen 
     Treated flats were seeded with DeKalb XL-44 corn (Zea maize), sugarbeets (Beta vulgare), small seeded gray striped sunflower (Helianthus annus), soybeans (Glycine max) and oilseed rape (Brassica napus), milo [sorghum] (sorgum vulgare), wheat (Triticum aestivum), green foxtail (Sataria viridis), rice (Oryza sativa) and barley (Hordeum vulgare). Seeds were then covered with the pint soil sample removed prior to seeding. 
     The flats were then 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 treatments were applied. Soil treated with the herbicide alone at the indicated rate was included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The percent protection of various representative crops is reported in Table III. The percent protection is determined by a comparison with flats not treated with the candidate antidote. 
     
                       TABLE III                                                   
______________________________________                                    
MULTICROP SCREEN RESULTS                                                  
COM-    Method of                                                         
POUND   Antidote  Herbicide/                                              
                            Crop     Percent                              
NUMBER  Application                                                       
                  Rate lb/A Protected                                     
                                     Protection                           
______________________________________                                    
1       PPI       EPTC/1/2  Milo     30                                   
                            Rice     63                                   
                            Barley   30                                   
2       PPI       EPTC/5    Corn     100 (2 wks)                          
3       PPI       EPTC/5    Rice     63                                   
                            Corn     100                                  
4       PPI       EPTC/1/2  Milo     50                                   
6       PPI       EPTC/1/2  Milo     40                                   
9       PPI       EPTC/1/2  Rice     100                                  
                            Barley   50                                   
11      PPI       EPTC/1/2  Milo     50                                   
                            Corn     100                                  
13      PPI       EPTC/5    Sunflower                                     
                                     67                                   
15      PPI       EPTC/1/2  Rice     100                                  
                  EPTC/5    Corn     65                                   
16      PPI       EPTC/1/2  Rice     100                                  
                  EPTC/5    Corn     65                                   
17      PPI       EPTC/1/2  Rice     100                                  
22      PPI       EPTC/1/2  Milo     90                                   
                  EPTC/5    Corn     100                                  
23      PPI       EPTC/1/2  Milo     67                                   
                  EPTC/1/2  Rice     55                                   
                  EPTC/5    Sunflower                                     
                                     30                                   
28      PPI       EPTC/5    Sunflower                                     
                                     67                                   
31      PPI       EPTC/5    Sugarbeet                                     
                                     70                                   
33      PPI       EPTC/1/2  Rice     44                                   
                  EPTC/1/2  Barley   40                                   
34      PPI       EPTC/1/2  Milo     10                                   
35      PPI       EPTC/1/2  Milo     45                                   
36      PPI       EPTC/5    Sugarbeet                                     
                                     80                                   
38      PPI       EPTC/5    Corn     33                                   
39      PPI       EPTC/1/2  Barley   40                                   
                  EPTC/5    Corn     55                                   
40      PPI       EPTC/5    Corn     22                                   
41      PPI       EPTC/5    Sunflower                                     
                                     67                                   
42      PPI       EPTC/5    Corn     22                                   
47      PPI       EPTC/1/2  Milo     75                                   
                            Wheat    67                                   
                            Rice     78                                   
                            Barley   63                                   
                  EPTC/5    Corn     100                                  
48      PPI       EPTC/1/2  Milo     25                                   
51      PPI       EPTC/1/2  Barley   67                                   
53      PPI       EPTC/1/2  Barley   50                                   
                  EPTC/5    Corn     100                                  
54      PPI       EPTC/5    Corn     40                                   
57      PPI       EPTC/5    Oilseed rape                                  
                                     67                                   
60      PPI       EPTC/5    Corn     100                                  
65      PPI       EPTC/5    Corn     50                                   
67      PPI       EPTC/1/2  Rice     100                                  
68      PPI       EPTC/1/2  Rice     100                                  
70      PPI       EPTC/1/2  Wheat    78                                   
                            Barley   85                                   
                            Rice     100                                  
72      PPI       EPTC/1/2  Rice     85                                   
                  EPTC/1/2  Barley   85                                   
73      PPI       EPTC/1/2  Barley   50                                   
75      PPI       EPTC/1/2  Rice     85                                   
                            Barley   72                                   
                  EPTC/5    Corn     50                                   
76      IF/5 lb/A EPTC/5    Corn     100                                  
77      IF/5 lb/A EPTC/5    Corn     50                                   
VERNAM/           VERNAM/5  Corn     60* Injury                           
6E                          Milo     100                                  
                            Wheat    98                                   
                            Barley   90                                   
2       IF/5 lb/A VERNAM/5  Corn     50                                   
3       IF/5 lb/A VERNAM/5  Corn     50                                   
4       IF/5 lb/A VERNAM/5  Corn     100                                  
11      IF/5 lb/A VERNAM/5  Corn     100                                  
                  VERNAM/3/4                                              
                            Milo     50                                   
18      IF/5 lb/A VERNAM/5  Corn     100                                  
20      IF/5 lb/A VERNAM/5  Corn     100                                  
                  VERNAM/3/4                                              
                            Milo     60                                   
22      IF/5 lb/A VERNAM/5  Corn     100                                  
                  VERNAM/3/4                                              
                            Milo     90                                   
23      IF/5 lb/A VERNAM/5  Corn     100                                  
24      IF/5 lb/A VERNAM/5  Corn     84                                   
                  VERNAM/3/4                                              
                            Milo     40                                   
26      IF/5 lb/A VERNAM/3/4                                              
                            Barley   67                                   
35      IF/5 lb/A VERNAM/3/4                                              
                            Corn     67                                   
                  VERNAM/3/4                                              
                            Milo     40                                   
38      IF/5 lb/A VERNAM/5  Corn     50                                   
39      IF/5 lb/A VERNAM/5  Corn     100                                  
                  VERNAM/3/4                                              
                            Barley   55                                   
40      IF/5 lb/A VERNAM/5  Corn     67                                   
47      IF/5 lb/A VERNAM/5  Corn     100                                  
                  VERNAM/3/4                                              
                            Milo     50                                   
53      IF/5 lb/A VERNAM/5  Corn     100                                  
60      IF/5 lb/A VERNAM/5  Corn     100                                  
78      IF/5 lb/A VERNAM/1  Milo     50                                   
                  VERNAM/5  Corn     22                                   
79      IF/5 lb/A VERNAM/1  Milo     60                                   
                  VERNAM/5  Corn     88                                   
80      IF/5 lb/A VERNAM/1  Milo     30                                   
                  VERNAM/5  Corn     88                                   
81      IF/5 lb/A VERNAM/5  Corn     20                                   
82      IF/5 lb/A VERNAM/5  Corn     45 (2 wks)                           
83      IF/5 lb/A VERNAM/1  Barley   50                                   
84      IF/5 lb/A VERNAM/1  Milo     40                                   
                  VERNAM/5  Corn     88                                   
85      IF/5 lb/A VERNAM/1  Wheat    40                                   
                  VERNAM/1  Barley   45                                   
                  VERNAM/5  Corn     67                                   
86      IF/5 lb/A VERNAM/1  Barley   55                                   
                  VERNAM/5  Corn     78                                   
87      IF/5 lb/A VERNAM/1  Milo     50                                   
                  VERNAM/1  Barley   45                                   
                  VERNAM/5  Corn     67                                   
88      IF/5 lb/A VERNAM/1  Barley   55                                   
90      IF/5 lb/A VERNAM/1  Barley   33                                   
                  VERNAM/5  Soybeans 30                                   
91      IF/5 lb/A VERNAM/5  Corn     36                                   
94      IF/5 lb/A VERNAM/5  Corn     23                                   
95      IF/5 lb/A VERNAM/1  Wheat    44                                   
                  VERNAM/1  Barley   44                                   
                  VERNAM/5  Corn     100                                  
96      IF/5 lb/A VERNAM/1  Wheat    67                                   
                  VERNAM/1  Barley   44                                   
                  VERNAM/5  Corn     37.5                                 
97      IF/5 lb/A VERNAM/5  Corn     87.5                                 
98      IF/5 lb/A VERNAM/5  Corn     37.5                                 
99      IF/5 lb/A VERNAM/5  Corn     75                                   
100     IF/5 lb/A VERNAM/1  Milo     20                                   
                  VERNAM/1  Barley   22                                   
101     IF/5 lb/A VERNAM/1  Milo     20                                   
                  VERNAM/1  Barley   44                                   
102     IF/5 lb/A VERNAM/6**                                              
                            Corn     100                                  
103     IF/5 lb/A VERNAM/1  Wheat    33                                   
                  VERNAM/1  Barley   33                                   
______________________________________                                    
 **Stock solution for VERNAM 6E at 6 lb/A PPI (preplant incorporated) 3800
 mg/500 ml. water; such that 4 ml. = 6 lb/A PPI                           
 
    
     The compounds and compositions of this invention were employed in effective herbicidal compositions comprising the antidote and a representative thiocarbamate herbicide and the antidote and a representative helogenated acetanilide herbicide, as described hereinabove. The herbicidal compositions were tested in the following manner. 
     The compositions of the present invention for the protection of cultivated crop plants comprise an active herbicidal compound and an antidote therefor selected from the abovedescribed 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. Thus, the antidote compounds 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 herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The addition of the antidote compound does not affect the herbicidal activity of the herbicides. 
     The amount of antidote compound present can range between about 0.0001 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 quantity of antidote compound will be employed in the herbicidal compositions described herein.