Non-phytotoxic antidotally effective amounts of compounds having the formula ##STR1## in which R is selected from the group consisting of haloalkyl having 1-4 carbon atoms and alkylamino having 1-4 carbon atoms; PA1 R.sub.1 is selected from the group consisting of alkyl having 1-4 carbon atoms, haloalkyl having 1-4 carbon atoms and chloro; and PA1 R.sub.2 is selected from the group consisting of haloalkyl having 1-4 carbon atoms and N-dichloroacetylethylamino protect crops from thiolcarbamate herbicidal injury.

BACKGROUND OF THE INVENTION 
A herbicide is a compound which controls or modifies plant growth, e.g., 
killing, retarding, defoliating, desiccating, regulating, stunting, 
tillering, stimulating, and dwarfing. "Plant" refers to all physical 
parts, including seeds, seedlings, saplings, roots, tubers, stems, stalks, 
foliage, and fruits. "Plant growth" is meant to include all phases of 
development from seed germination to natural or induced cessation of life. 
Herbicides are generally used to control or eradicate undesirable 
vegetation. They have gained a high degree of commercial success because 
it has been shown that such control can increase crop yield and reduce 
harvesting costs. 
Herbicidal effectiveness is dependent upon several variables. One of these 
is the time or growth related method of application. The most popular 
methods of application include: pre-plant incorporation into the soil; 
pre-emergence surface treatment of seeded soil; and post-emergence 
treatment of the plant and soil. 
The most important determinant of herbicidal effectiveness is the 
susceptibility of the beneficial crop and selectivity toward weeds. 
Certain herbicidal compounds are phytotoxic to some weed species but not 
to others. 
A manufacturer of a herbicide generally recommends a range of rates and 
concentrations calculated to maximize weed control. The range of rates 
varies from approximately 0.01 to 50 pounds per acre (lb/A) (0.0112 to 56 
kilograms per hectare (k/ha)), usually from 0.1 to 25 lb/A (0.112 to 28 
k/ha). The actual amount used depends upon several considerations, 
including, crop tolerance, particular weed susceptibility and overall cost 
limitations. 
Some herbicides display exclusive selectivity toward weed species. Many are 
toxic to both weeds and the intended crop beneficiary. Therefore, a 
particular herbicide may proscribe its injurious effect on the cultivated 
crop even though it may otherwise provide excellent control of weeds found 
in the crop field. 
To preserve the beneficial aspects of herbicide use and to mitigate crop 
damage, many herbicidal antidotes have been prepared. These antidotes 
reduce or eliminate damage to the crop without substantially impairing the 
beneficial effect of the herbicide. See U.S. Pat. Nos. 4,021,224, 
4,021,229 and Belgian Pat. No. 846,894. 
Although several explanatory theories have been advanced, the precise 
mechanism by which an antidote reduces herbicidal crop injury while 
retaining weed injury has not been conclusively established. An antidote 
compound may in fact be a remedy, interferent, protectant, or antagonist. 
As used herein, "antidote" describes a compound which has the effect of 
establishing herbicidal selectivity or herbicidal phytotoxicity toward 
weed species and reduced or non-phytotoxicity to cultivated crop species. 
As an alternative mode of action, the compounds of this invention may 
interfere with the normal herbicidal action of the thiolcarbamate-type 
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 thiolcarbamate with the 
accompanying decreased herbicidal effect on desired crop species. This 
advantage and utility will become more apparent hereinafter. 
Therefore, the terms herbicide antidotes or antidotal amount is meant to 
describe that effect or the amount which produces the effect which tends 
to counteract the normal injurious herbicidal response that the herbicide 
might otherwise produce. Whether it is to be termed a remedy, interferent, 
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 soil in which a crop is planted. 
Thiolcarbamate herbicides are particularly effective in the control of 
grassy type weeds which interfere with the cultivation of a wide variety 
of crops, e.g., barley, corn, lentils, peanuts, peas, potatoes, soybeans, 
spinach, tobacco and tomatoes. Frequently, the beneficent use of 
thiolcarbamates requires the addition of an antidote.

DESCRIPTION OF THE INVENTION 
It has been discovered that the tolerance of several crops to 
thiolcarbamate herbicides can be increased by the use of a non-phytotoxic 
antidotally effective amount of a s-triazine compound of the formula 
##STR2## 
in which 
R is selected from the group consisting of haloalkyl having 1-4 carbon 
atoms, preferably dichloromethyl or trichloromethyl, and alkylamino having 
1-4 carbon atoms, preferably ethylamino and propylamino; 
R.sub.1 is selected from the group consisting of alkyl having 1-4 carbon 
atoms, preferably methyl, haloalkyl having 1-4 carbon atoms, preferably 
dichloromethyl, and chloro; and 
R.sub.2 is selected from the group consisting of haloalkyl having 1-4 
carbon atoms, preferably dichloromethyl and trichloromethyl, and 
N-dichloroacetylethylamino. 
This invention embodies a two-part herbicidal composition comprising 
(a) a non-phytotoxic antidotally effective amount of a compound of the 
formula 
##STR3## 
in which 
R is selected from the group consisting of haloalkyl having 1-4 carbon 
atoms, preferably dichloromethyl or trichloromethyl, and alkylamino having 
1-4 carbon atoms, preferably ethylamino and propylamino; 
R.sub.1 is selected from the group consisting of alkyl having 1-4 carbon 
atoms, preferably methyl, haloalkyl having 1-4 carbon atoms, preferably 
dichloromethyl, and chloro; and 
R.sub.2 is selected from the group consisting of haloalkyl having 1-4 
carbon atoms, preferably dichloromethyl and trichloromethyl, and 
N-dichloroacetylethylamino. 
(b) a herbicidally effective amount of a thiolcarbamate of the formula 
##STR4## 
in which 
R.sub.3 is selected from the group consisting of alkyl having 1-6 carbon 
atoms and alkenyl having 2-6 carbon atoms; 
R.sub.4 is selected from the group consisting of alkyl having 1-6 carbon 
atoms, alkenyl having 2-6 carbon atoms, cyclohexyl and phenyl; or 
R.sub.3 and R.sub.4 together form an alkylene group having 5-10 carbon 
atoms; and 
R.sub.5 is selected from the group consisting of alkyl having 1-6 carbon 
atoms, haloalkyl having 1-4 carbon atoms, cycloalkyl having 5-10 carbon 
atoms, phenyl, substituted phenyl, wherein the substituents are alkyl 
having 1-4 carbon atoms, haloalkyl having 1-4 carbon atoms, and halo, 
benzyl and substituted benzyl, wherein the substituents are alkyl having 
1-4 carbon atoms, haloalkyl having 1-4 carbon atoms and halo. 
The terms alkyl and alkenyl as used herein are intended to include both 
straight- and branched-chain groups. The term halo is intended to include 
mono- and polyhalo groups and includes, chloro, bromo, iodo, fluoro and 
mixtures thereof. All carbon atom ranges are intended to be inclusive of 
both upper and lower limits. Exemplary of alkyl are methyl, ethyl, 
n-propyl, isopropyl, n-butyl, isobutyl, tertiarybutyl, pentyl, hexyl and 
the like. Exemplary of alkenyl are such groups as vinyl, proenyl, butenyl, 
pentyl, hexenyl and the like. Exemplary of cycloalkyl are cyclopentyl, 
cyclohexyl, 2,2 dimethyl cyclohexyl, cycloheptyl and the like. 
By way of exemplification, the active thiolcarbamate herbicides employed in 
the invention may include the following: EPTC, S-ethyl diisobutyl 
thiolcarbamate, S-propyl dipropyl thiolcarbamate, 
S-2,3,3-trichloroallyldiisopropyl thiolcarbamate, S-ethyl cyclohexyl ethyl 
thiolcarbamate, S-ethyl hexahydro-1H-azepine-1-carbothioate, 
S-4-chlorobenzyl diethyl thiolcarbamate and combinations thereof. 
The present invention also includes the method of selectively controlling 
undesirable vegetation in the presence of cultivated crops which comprises 
applying to a locus where control is desired an antidotally effective 
amount of a compound of the formula 
##STR5## 
in which 
R is selected from the group consisting of haloalkyl having 1-4 carbon 
atoms, preferably dichloromethyl or trichloromethyl, and alkylamino having 
1-4 carbon atoms, preferably ethylamino and propylamino; 
R.sub.1 is selected from the group consisting of alkyl having 1-4 carbon 
atoms, preferably methyl, haloalkyl having 1-4 carbon atoms, preferably 
dichloromethyl, and chloro; and 
R.sub.2 is selected from the group consisting of haloalkyl having 1-4 
carbon atoms, preferably dichloromethyl and trichloromethyl, and 
N-dichloroacetylethylamino. 
The thiolcarbamate herbicides are generally incorporated into the soil 
prior to planting. The antidote compound may be combined with the 
herbicide as a tank mix as it is incorporated into the soil. This is 
referred to as the "Pre-plant Incorporation" (PPI) Method of Application. 
The antidote may also be applied by the "In-furrow" (IF) Method of 
Application which consists of spraying the seeds and the herbicidally 
treated soil with the antidote compound prior to covering the seeds with 
soil. 
Preparation 
The thiolcarbamates of the present compositions can be prepared by the 
procedures described in U.S. Pat. Nos. 2,913,327, 2,983,747, 3,133,947, 
3,185,720 and 3,198,786. 
The s-triazines can be prepared by a variety of methods depending upon the 
starting materials. Tris-dichloromethyl-s-triazine and 
2,6'-trichloromethyl-4'-methyl-s-triazine are commercially available. 
The acetylamino-triazines may be prepared by the reaction of the 
appropriate aminotriazine and an acetyl chloride in a suitable solvent. 
The reaction is generally carried out at a temperature range of 50.degree. 
to 150.degree. C. 
For example, 
2-isopropylamino-4-chloro-6-(N-dichloroacetylethylamino)-s-triazine 
(Compound No. 4) was prepared in the following manner. 
2-chloro-4-ethylamino-6-isopropylamino-s-triazine (5.4 grams (g)) or 0.025 
mole (m), and 7.4 g (0.05 m) of dichloroacetyl chloride were combined in 
50 milliliters (ml) of 1,2-dichloroethane. The mixture was refluxed for 
several hours, cooled and stripped, yielding 8.6 g of a dark viscous 
liquid which slowly crystallized (n.sub.D.sup.30 1.5506). Structure was 
confirmed by infrared spectrophotometric analysis and nuclear magnetic 
resonance spectrum. 
Table I contains representative s-triazine antidote compounds which were 
tested as part of the herbicidal compositions of this invention. Compound 
No. 1 can be found described in U.S. Pat. No. 2,525,714. 
TABLE I 
__________________________________________________________________________ 
S-TRIAZINE HERBICIDAL ANTIDOTES 
##STR6## 
Compound Physical 
Number 
R R.sub.1 
R.sub.2 
Chemical Name Constant 
__________________________________________________________________________ 
1 CHCl.sub.2 
CHCl.sub.2 
CHCl.sub.2 
Tris-dichloromethyl-s-triazine 
m.p. 50-60.degree. C. 
2 CCl.sub.3 
CH.sub.3 
CCl.sub.3 
2',6'-trichloromethyl-4'-methyl- 
m.p. 88-90.degree. C. 
s-triazine 
3 NHC.sub.2 H.sub.5 
Cl 
##STR7## 
2-ethylamino-4-chloro-6-(N- dichloroacetylethylamino 
)-s- triazine n .sub.D.sup.30 1.5312 
##STR8## 
Cl 
##STR9## 
2-isopropylamino-4-chloro-6- (N-dichloroacetylethyla 
mino)-s- triazine 
n .sub.D.sup.30 1.5312 
__________________________________________________________________________ 
Stock solutions of the various thiolcarbamate herbicides were prepared by 
dissolving the requisite amount of the herbicide in water. 
Stock solutions of each antidote compound were prepared by dissolving the 
requisite amount in acetone. The herbicide and antidote compositions and 
their equivalent rates of application appear in Table II and III. 
TABLE II 
______________________________________ 
Herbicidal Stock Solutions 
Composition 
Herbicide A Water Application 
(mg) (ml) ml soln .about. 
lb/A 
______________________________________ 
EPTAM.RTM. 
S-ethyl-N,N- 
dipropyl 
thiolcarbamate 
53 100 5 0.50 
533 100 5 5.00 
______________________________________ 
TABLE III 
______________________________________ 
Antidote Stock Solutions 
Antidote: s-triazines 
Composition 
Antidote Acetone Application 
(mg) (ml) ml soln .about. 
lb/A 
______________________________________ 
Stock Solution A: 
200 50 1.0 1.00 
200 50 5.0 5.00 
Dilutions: 
1 ml of A 99 5.0 0.05 
______________________________________ 
All of the soil used in the tests described herein was loamy sand soil 
treated with 50 parts per million (ppm) each of a commercially available 
fungicide, cis-N[trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide, 
and an 18-18-18 fertilizer which contains 18% by weight equivalent each of 
nitrogen, phosphorus pentoxide, and potassium oxide. 
The herbicide and the antidote of each test group were pre-plant 
incorporated (PPI) into the treated soil. Control flats used for injury 
rating comparisons contained only the herbicide treated soil. 
The flats were placed on greenhouse benches where temperature was 
maintained between 70.degree. and 90.degree. F. (21.11.degree. to 
32.22.degree. C.). The soil was watered by sprinkling as needed to assure 
good plant growth. 
Control flats contained crops treated with herbicides only at the various 
rates and methods of application. 
Injury ratings were taken four weeks after application of the antidote. The 
effectiveness of the antidote was determined by visual comparison of 
injuries to crops and weeds in the control and test flats to those in 
untreated flats. 
The treated crops initially screened for diminution of herbicidal injury 
were milo (Sorghum bicolor (L.) Moench), barley (Hordeum vulgare (L.)) and 
corn (Zea mays (L.)). The herbicides and antidote compositions were 
screened on the weed species, foxtail (Setaria viridis). 
KEY TO TABLES IV AND V 
Compound numbers in these tables correspond to antidote compound numbers 
and their chemical description in Table I. 
______________________________________ 
Application: PPI = Pre-plant incorporation of 
herbicide and antidote 
Herbicide: EPTAM.RTM. or S-ethyl N,N-dipropyl- 
thiolcarbamate, described in 
U.S. Pat. No. 2,913,327 
Rates: All rates are shown in pounds per 
acre 
Injury Ratings: 
U = Antidotally untreated; 
% injury 4 weeks after 
herbicide application 
T = Antidotally treated; 
% injury 4 weeks after 
treatment with herbicide 
plus antidote compound 
-- = Indicates no change 
______________________________________ 
TABLE IV 
__________________________________________________________________________ 
Antidotal Effectiveness 
Antidote 
Cmpd. Herbicide 
Milo Barley Corn 
No. Rate 
Method 
Name Rate 
U T U T U T 
__________________________________________________________________________ 
1 5.00 
PPI EPTAM 
0.50 
93 -- 94 -- 
5.00 
PPI EPTAM 
5.00 98 30 
2 5.00 
PPI EPTAM 
0.50 
75 20 55 50 
5.00 
PPI EPTAM 
5.00 97 0 
3 5.00 
PPI EPTAM 
0.50 
75 -- 50 0 93 -- 
1.00 
PPI EPTAM 
0.50 90 70 
5.00 
PPI EPTAM 
0.50 90 50 
4 5.00 
PPI EPTAM 
0.50 
97 100 95 100 
5.00 
PPI EPTAM 
5.00 85 0 
__________________________________________________________________________ 
TABLE V 
______________________________________ 
Herbicidal Effectiveness 
Antidote % Weed Injury 
Cmpd. Herbicide Foxtail 
No. Rate Method Name Rate U T 
______________________________________ 
1 5.00 PPI EPTAM 0.50 70 -- 
2 5.00 PPI EPTAM 0.50 70 -- 
3 5.00 PPI EPTAM 0.50 75 -- 
1.00 PPI EPTAM 0.50 70 -- 
5.00 PPI EPTAM 0.50 70 -- 
4 5.00 PPI EPTAM 0.50 75 100 
0.05 PPI EPTAM 0.05 98 -- 
______________________________________ 
Formulations 
The object of the formulation is to apply the compounds and compositions to 
the locus where control is desired by a conventional method. The "locus" 
may include soil, seeds, seedlings, and vegetation. The compounds and 
compositions can be formulated in the same manner in which herbicides are 
generally formulated. 
The amount of an antidote compound which comprises part of a herbicidal 
composition will generally range from approximately 0.001 to 30 parts by 
weight per weight of the active herbicidal compound. 
Formulations will generally contain several additives. Among these are some 
inert ingredients, diluent carriers, organic solvents, water, oil and 
water, water in oil emulsions, carriers of dusts and granules, and surface 
active wetting, dispersing, and emulsifying agents. Fertilizers, e.g., 
ammonium nitrate, urea and superphosphate, may also be included. Aids to 
rooting and growth, e.g., compost, manure, humus, sand, etc., may likewise 
be included. The formulations are commonly dusts, wettable powders, 
granules, solutions or emulsifiable concentrates. 
Dusts are free-flowing powder compositions containing the herbicidal 
compound impregnated on a particulate carrier. The particle size of the 
carriers is usually in the approximate range of 30 to 50 microns. Examples 
of suitable carriers are talc, bentonite, diatomaceous earth, and 
pyrophyllite. Anticaking and anti-static agents can be added, if desired. 
The composition generally contains up to 50% of active ingredient. Dusts, 
like liquid compositions, can be applied by spraying from boom and hand 
sprayers or airplanes. 
Wettable powders are finely divided compositions comprising a particulate 
carrier impregnated with the herbicidal compound and additionally 
containing one or more surface active agents. The surface active agent 
promotes rapid dispersion of the powder in aqueous medium to form stable, 
sprayable suspensions. A wide variety of surface active agents can be 
used, for example, long chain fatty alcohols and alkali metal salts of the 
sulfated fatty alcohols; salts of sulfonic acid; esters of long chain 
fatty acids; and polyhydric alcohols; in which the alcohol groups are 
free, omega-substituted polyethylene glycols of relatively long chain 
length. A list of surface active agents suitable for use in agriculture 
formulations can be found in Wade Van Valkenburg, Pesticide Formulations 
(Marcel Dekker, Inc., N.Y., 1973) at pages 79-84. 
Granules comprise the herbicidal composition impregnated on a particulate 
inert carrier having a particle size of about 1 to 2 millimeters (mm) in 
diameter. The granules can be made by spraying a solution of the active 
ingredient in a volatile solvent onto the granular carrier. Suitable 
carriers in preparation of granules include clay, vermiculite, sawdust, 
granular carbon, etc. 
The herbicidal compositions can also be applied to the soil in the form of 
a solution in a suitable solvent. Solvents frequently used in herbicidal 
formulations include kerosene, fuel oil, xylene, petroleum fractions with 
boiling ranges above xylene, and aromatic petroleum fractions rich in 
methylated naphthalenes. 
Emulsifiable concentrates consist of an oil solution of the herbicide along 
with an emulsifying agent. Prior to use the concentrate is diluted with 
water to form a suspended emulsion of oil droplets. The emulsifiers used 
are usually a mixture of anionic and nonionic surfactants. Other additives 
such as spreading agents and stickers can be included in the emulsifiable 
concentrate. 
The compounds and compositions of this invention can also be applied by 
addition to irrigation water supplied to the field to be treated. This 
method of application permits the penetration of the compositions into the 
soil as the water is absorbed therein. 
It is not necessary that the compounds and compositions be admixed with the 
soil particles. After application by the above discussed methods, they may 
be distributed below the surface to a depth of at least one-half inch by 
conventional means such as discing, dragging, or mixing.