N-(substituted benzenesulfonyl) carbamates as new compositions of matter useful as active herbicidal antidotes to protect against and decrease crop injury when used with a thiocarbamate herbicide when applied in various methods; improved herbicidal compositions and utility of said compositions to protect against and decrease phytotoxic crop injury when employing thiocarbamate herbicides and a two-part herbicide system comprising a first-part of one or more thiocarbamate herbicide and a second part of an effective antidote therefor compound said antidote compounds of the class N-benzene sulfonyl carbamates having the formula ##STR1## wherein X is hydrogen, bromo, chloro, methoxy, trifluoromethyl, and methyl; n is an integer from 1 to 3 inclusive, provided that when X is bromo, trifluoromethyl, or methoxy, n is 1; and R is selected from alkyl, haloalkyl wherein halo is chloro or fluoro, alkenyl, haloalkenyl and wherein halo is chloro, alkynyl, trifluoroacetamidomethyl, dialkylamino cyanoalkylthioalkyl, phosphonomethyl, lower alkyl substituted phenyl, 4-chlorophenylthiomethyl, alkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkoxycarbonylalkyl, formamidoalkyl, alkoxycarbonylalkenyl, alkylcarbonylalkyl, 1,3-dioxacyclohexane-5,5-methylene, phenyl, chlorophenyl, benzyl, 4-chlorobenzyl, 4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn-2-yl, methylthioacetimino, acetone imino and benzaldimino.

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 sometimes result. This abnormal growth 
in the crop plants results in loss of crop yield. The search continues for 
good selective herbicides. 
Previous attempts are described to overcome this problem. The treatment of 
the crop seed with certain "hormonal" antagonistic agents prior to 
planting is described; see U.S. 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 or in the nature of 
the 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. Pat. Nos. 3,799,760 and 3,933,894, and East German Patent DL No. 74982 
disclose certain N-benzenesulfonyl carbamate compounds, disclosed herein. 
Also, in Berichte, Vol. 37 at Page 699, certain compounds are specifically 
disclosed. None of these references anticipate or make obvious the utility 
of the compounds as herbicidal antidotes for thiocarbamate herbicides, in 
particular for S-n-propyl N,N-di-n-propylthiocarbamate. None of the 
references anticipate or make obvious the improved herbicidal compositions 
for use employing N-benzenesulfonyl carbamates and an active thiocarbamate 
herbicide, particularly S-n-propyl N,N-di-n-propylthiocarbamate. 
DESCRIPTION OF THE INVENTION 
It has been discovered that cultivated crop plants, can be protected 
against injury by thiocarbamate-type herbicides, and said injury can be 
decreased when the thiocarbamate-type herbicides, each alone or in 
mixtures or combination with other compounds, are applied in a variety of 
ways. Further, as an alternative effect, the tolerance of the plants, to 
these herbicides, can be substantially increased by adding to the soil an 
antidote compound of the type N-(substituted benzenesulfonyl) carbamates, 
therefore, the present invention also includes a two-part herbicide system 
comprising a first part of one or more thiocarbamate herbicide and a 
second part of an effective antidote compound therefore, said antidote 
compounds corresponding to the following formula 
##STR2## 
in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl, and 
methyl; n is an integer from 1 to 3 inclusive, provided that when X is 
bromo, trifluoromethyl, or methoxy, n is 1; and R is selected from alkyl 
having 1 to 4 carbon atoms, inclusive, haloalkenyl having 3 to 6 carbon 
atoms, inclusive and wherein halo is chloro from 1 to 4, inclusive, 
alkynyl having 3 to 6 carbon atoms, inclusive, trifluoracetamidomethyl, 
dialkylamino having a total of 2 to 8 carbon atoms, inclusive, 
cyanoalkylthioalkyl having a total of 3 to 6 carbon atoms, inclusive, 
phosphonomethyl, lower alkyl substituted phenyl said lower alkyl each 
having 1 to 4 carbon atoms, inclusive, 4-chlorophenylthiomethyl, 
alkoxyalkyl having 2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2 
to 6 carbon atoms, inclusive cyanoalkyl having 2 to 6 carbon atoms, 
inclusive, alkoxycarbonylalkyl having 3 to 7 carbon atoms, inclusive, 
formamidoalkyl having 2 to 6 carbon atoms, inclusive, 
alkoxycarbonylalkenyl having 4 to 7 carbon atoms, inclusive, 
alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 
1,3-dioxacyclohexane-5,5-methyl methylene, phenyl, chlorophenyl, benzyl, 
4-chlorobenzyl, 4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 
3-phenylpropyn-2-yl, methylthioacetimino, acetone imino and benzaldimino. 
Certain compounds disclosed herein are considered new compositions of 
matter and correspond to the following formula 
##STR3## 
in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl, and 
methyl; n is an integer from 1 to 3 inclusive, provided that when X is 
bromo, trifluoromethyl, or methoxy, n is 1; and R is selected from 
haloalkyl having 2 to 6 carbon atoms, inclusive, wherein halo is chloro or 
fluoro from 1 to 6, inclusive, haloalkenyl having 3 to 6 carbon atoms, 
inclusive and wherein halo is chloro from 1 to 4, inclusive, dialkylamino 
having a total of 2 to 8 carbon atoms, inclusive, cyanoalkylthioalkyl 
having a total of 3 to 6 carbon atoms, inclusive, phosphonomethyl, 
trifluoroacetamidomethyl, lower alkyl substituted phenyl said lower alkyl 
each having 1 to 4 carbon atoms, inclusive, 4-chlorophenylthiomethyl, 
alkoxyalkyl having 2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2 
to 6 carbon atoms, inclusive cyanoalkyl having 2 to 6 carbon atoms, 
inclusive, alkoxycarbonylalkyl having 3 to 7 carbon atoms, inclusive, 
formamidoalkyl having 2 to 6 carbon atoms, inclusive, 
alkoxycarbonylalkenyl having 4 to 7 carbon atoms, inclusive, 
alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 
1,3-dioxacyclohexane-5,5-methyl methylene, chlorophenyl, 4-chlorobenzyl, 
4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn-2-yl, 
methylthioacetimino, acetone imino and benzaldimino. 
Also provided that when X is trifluoromethylyl and n is 1, then R can be 
alkyl having 1 to 4 carbon atoms inclusive, alkenyl having 3 to 6 carbon 
atoms, inclusive, and alkynyl having 3 to 6 carbon atoms, inclusive. 
In the above descriptions, the following embodiments are intended for the 
various substituent groups: For R, haloalkyl 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, bromo and fluoro, as mono, di, tri, tetra, or hexa 
substitutions that is from 1 to 6 halo substituents. As exemplary of the 
alkyl portion within the preferred embodiment are the following: Methyl, 
ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl and tert.-butyl. 
For R, alkynyl preferably includes those members which contain from 3 to 6 
carbon atoms and at least one acetylenic or triple bond such as in 
propargyl (propynyl), 2-butynyl, 3-butynyl, 1,1-dimethyl-3-butynyl, and 
the like. Chloroalkenyl preferably includes those members which contain 
from 3 to 6 carbon atoms, inclusive, and at least one olefinic double 
bond. Other substituent groups are as indicated in carbon content in the 
above description. 
As an alternative mode of action, the compounds of this invention may 
interfere with the normal herbicidal action of the thiocarbamate-type and 
other herbicides to render them selective in their action. The observation 
noted with the presence of the herein described antidote is a decrease in 
phytotoxuity with respect to various crops, otherwise observed when 
various thiocarbamate herbicides are used for weed control. Whichever mode 
of action is present, the corresponding beneficial and desirable effect is 
the continued herbicidal effect of the 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, antagonist 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 seed, soil or furrow 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 formulas can be 
prepared by several different procedures depending upon the starting 
materials. 
One general method for preparing N-benzenesulfonyl alkynyl carbamates is 
the reaction of an appropriate alkynol with benzenesulfonyl isocyanate. 
More particularly, the reaction is performed in the presence of a solvent 
such as benzene or chloroform with catalytic amounts of triethylamine and 
dibutyl tin dilaurate. In some instances, a catalyst is not required. 
After the reaction is complete, the product is recovered by filtration or 
evaporation of the solvent. If necessary, the product can be 
recrystallized from a suitable solvent. 
A general method for preparing N-benzenesulfonyl alkyl carbamates is the 
reaction of an appropriate benzenesulfonamide with an alkyl chloroformate 
in the presence of a catalyst, such as potassium carbonate. A solvent is 
normally employed to facilitate the reaction and aid in the work-up of the 
product. After filtration, extraction and drying, the product can be 
purified further by trituration with hexane or recrystallization from a 
suitable solvent. In most instances, the structure was confirmed by 
infrared, nuclear magnetic resonance or mass spectroscopy.