Synergistic herbicidal activity is displayed by compositions comprising the following two components: PA1 (a) an anilide of the formula ##STR1## in which R is a member selected from the group consisting of C.sub.1 -C.sub.10 alkyl, C.sub.2 -C.sub.4 alkenyl, and C.sub.3 -C.sub.5 cycloalkyl; and PA1 (b) a thiocarbamate of the formula ##STR2## in which R.sup.1 and R.sup.2 are independently C.sub.1 -C.sub.4 alkyl, or R.sup.1 and R.sup.2 conjointly form C.sub.2 -C.sub.7 alkylene; and R.sup.3 is C.sub.1 -C.sub.4 alkyl, in a weight ratio of anilide to thiocarbamate of 0.001-50:1.

DESCRIPTION OF THE INVENTION 
This invention relates to synergistic herbicidal compositions. 
It has been discovered that synergism in the control of undesired 
vegetation is exhibited by compositions comprising the following two 
components: 
(a) an anilide of the formula 
##STR3## 
in which R is a member selected from the group consisting of C.sub.1 
-C.sub.10 alkyl, C.sub.2 -C.sub.4 alkenyl, and C.sub.3 -C.sub.5 
cycloalkyl; and 
(b) a thiocarbamate of the formula 
##STR4## 
in which R.sup.1 and R.sup.2 are independently C.sub.1 -C.sub.4 alkyl, or 
R.sup.1 and R.sup.2 conjointly form C.sub.2 -C.sub.7 alkylene; and R.sup.3 
is C.sub.1 -C.sub.4 alkyl, in a weight ratio of anilide to thiocarbamate 
of 0.001-50:1. 
Within the scope of the above-defined general formulae, certain embodiments 
are preferred, as indicated below: 
In Formula I, R is preferably a member selected from the group consisting 
of C.sub.2 -C.sub.4 alkenyl and C.sub.3 -C.sub.5 cycloalkyl. 
In Formula II, R.sup.1 and R.sup.2 preferably conjointly form C.sub.2 
-C.sub.7 alkylene, and more preferably C.sub.4 -C.sub.7 alkylene. 
The terms "alkyl" and "alkylene" as used herein are intended to include 
both straight- and branched-chain groups. All carbon atom ranges are 
intended to be inclusive of both upper and lower limits. 
The term "herbicide", as used herein, means a compound which controls or 
modifies the growth of plants. By the term "herbicidally effective amount" 
is meant an amount of compound which causes a modifying effect upon the 
growth of plants. By "plants" is meant germinating seeds, emerging 
seedlings and established vegetation, including roots and above ground 
portions. Such modifying effects include all deviations from natural 
development, for example, killing, retardation, defoliation, desiccation, 
regulation, stunting, tillering, stimulation, leaf burn, dwarfing and the 
like. The compositions of the present invention are particularly effective 
in controlling weeds in flooded rice paddies. 
The term "synergism" is employed in its traditional sense and describes a 
herbicidal effect of a composition containing two or more active 
herbicidal compounds which is greater than the sum of the herbicidal 
effects of the individual compounds when used alone. 
The anilides of the present compositions can be prepared by the procedures 
described in commonly assigned co-pending application Ser. No. 807,940, 
filed June 21, 1977. Examples of such anilides are: 
3-chloro-4-(2,2-dichloro-1-methyl-cyclopropyl) methoxy crotonyl anilide 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl) methoxy methacrylyl anilide 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl) methoxy cyclopropane 
carboxylic acid anilide 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl) methoxy propionyl anilide 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl) methoxy iso butyryl anilide 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl) methoxy butyryl anilide 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl) methoxy 2'-methyl butyryl 
anilide 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl) methoxy 2',2'-dimethyl 
valeryl anilide 
The thiocarbamates of the present compositions are well known herbicides 
and can be prepared by the procedures described in U.S. Pat. No. 
3,198,786. Examples of such thiocarbamates are: 
S-ethyl hexahydro-1H-azepine-1-carbothioate 
S-ethyl di-n-propylthiocarbamate 
S-ethyl diisobutylthiocarbamate 
S-n-propyl di-n-propylthiocarbamate 
S-n-propyl n-butylethylthiocarbamate. 
The anilide and thiocarbamate herbicides are used in a weight ratio of 
anilide to thiocarbamate of 0.001-50:1, preferably 0.01-10:1, and most 
preferably 0.1-8:1. 
Application rates will depend upon the weeds to be controlled and the 
degree of control desired. In general, the compositions of this invention 
are most efficiently employed at a rate of 0.01 to 50 pounds per acre 
(0.011 to 56 kilograms per hectare), preferably 0.1 to 25 pounds per acre 
(0.011 to 28 kilograms per hectare). 
Herbicidal compositions illustrative of those embodied in the instant 
application were prepared and synergistic effect evaluated in the 
following examples.

EXAMPLES 
The compositions of the present invention were tested for herbicidal 
activity and synergism by a postflood-postemergence test in a simulated 
rice paddy as follows: 
Plastic tubs measuring 10.times.7.5.times.5.75 inches 
(25.4.times.19.0.times.14.6 centimeters) were filled to a depth of 2 
inches (5.1 centimeters) with 8 pounds (3.6 kilograms) of a loamy sand 
soil, containing 50 parts per million (ppm) each of 
cis-N[(trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide (a commercial 
fungicide designated as Captan.RTM.) and 18-18-18 fertilizer (containing 
18% N, 18% P.sub.2 O.sub.5, and 18% K.sub.2 O on a weight basis). One pint 
(0.47 liter) of the soil was removed, the remaining soil was leveled and 
seven rows were impressed across the width of the flat. Yellow nutsedge 
tubers (Cyperus esculentus), and seeds of annual morning glory (Ipomoea 
purpurea), curly dock (Rumex crispus), sesbania (Sesbania spp.) and rice 
(Oryza sativa) were planted in separate rows. The pint of soil was then 
used to place a 0.5 inch (1.27 centimeter) layer over the seeds and 
tubers. The planted soil was placed in a greenhouse, and irrigated by 
sprinkling as needed to keep the soil moist. Three days after the initial 
seeding another row was impressed 0.5 inches (1.27 centimeters) deep 
across the width of the flat and seeds of watergrass (Echinochloa 
crusgalli) were planted and covered by pinching together the soil on 
either side of the seeder row. Seven to ten days after the original 
seeding, the soil was flooded with 2 inches (5.1 centimeters) of water. At 
flooding time the grass species were in the two leaf stage 1 to 2 inches 
(2.54 to 5.1 centimeters) high and the nutsedge was 1 inch (2.54 
centimeters) high. 
Test compounds or combinations were then applied by pipeting into the flood 
water a prescribed volume of stock solution to produce the desired 
application rate in pounds of active ingredient per acre (lb/A) or its 
equivalent in kilograms per hectare. For the particular tubs used, 5.5 
milligrams (mg) of active ingredient per tub is equivalent to 1.0 lb/A. 
The anilide stock solution for an application rate of 1.0 lb/A consisted 
of 22 mg of the anilide dissolved in 20 milliliters (ml) of acetone 
containing 1% "Tween 20.RTM." (a commercial emulsifying agent defined as a 
polyoxyethylene sorbitan monolaurate). The thiocarbamate stock solution 
for an application rate of 1.0 lb/A was prepared by dissolving 31 mg of an 
emulsifiable concentrate of the thiocarbamate in 20 ml of water. The 
emulsifiable concentrate was comprised of 71.3% thiocarbamate. The 
prescribed pipet volume was 5.0 ml. Stock solutions for other application 
rates were made with proportional amounts of the anilide or thiocarbamate. 
Combinations were achieved by pipeting 5.0 ml from each of the 
appropriately selected stock solutions. 
The tubs were allowed to stand for three weeks after the application of the 
test compounds and water was added as needed to maintain the water level. 
At the end of three weeks, the species were rated visually as percent 
control from 0 to 100%, where 0% represents no injury and 100% represents 
complete kill when compared to an untreated check tub. The percent control 
was based on the total injury to the plants due to all factors. 
The anilides tested were 3-chloro-4-(2,2-dichloro-1-methyl 
cyclopropyl)methoxy methacrylyl anilide (Table 1) and 
3-chloro-4-(2,2-dichloro-1-methyl cyclopropyl)methoxy cyclopropane 
carboxylic acid anilide (Table 2) in combination with the thiocarbamate 
S-ethyl hexahydro-1H-azepine-1-carbothioate (ORDRAM.RTM.). 
The results of each test are reported in Tables 1 and 2 in the columns 
headed by the symbol "O" (indicating observed results). These results were 
then compared with the expected results, shown in the columns headed by 
the symbol "E", derived from Limpel's formula (Limpel et al., 1962, "Weed 
Control by Dimethylchloroterephthalate Alone and in Certain Combinations," 
Proc. NEWCC, Vol. 16, pp. 48-53): 
EQU E=X+Y-(XY/100) 
where 
X=observed percent injury when one of the herbicides is used alone, and 
Y=observed percent injury when the other herbicide is used alone. 
The relationship between the observed result and the expected result for 
each combination tested is indicated in the columns headed by the symbol 
"R". When the observed result exceeds the expected result, synergism has 
been shown, which is represented by the symbol "S". When the observed 
result is less than the expected result, there is antagonism between the 
herbicides, represented by the symbol "A". When the observed result equals 
the expected result, the relationship of the herbicides in the combination 
is merely additive, as represented by the symbol "Ad." 
Table 1 
__________________________________________________________________________ 
Postflood Test Results - Percent Control 
Annual 
Yellow Morning 
lb/A lb/A 
Watergrass 
Nutsedge 
Sesbania 
Glory Curly Dock 
Thiocarbamate 
Anilide 
O E R 0 E R 0 E R 0 E R 0 E R 
__________________________________________________________________________ 
1/2 -- 0 0 O 0 0 
1 -- 30 0 0 0 0 
2 -- 50 0 0 0 0 
-- 1/16 
0 0 0 0 0 
-- 1/8 20 0 0 0 40 
-- 1/4 80 0 0 60 60 
-- 1/2 98 0 70 80 98 
1/2 1/16 
10 
0 
S 0 0 -- 
0 0 -- 
0 0 -- 
0 0 -- 
1/2 1/8 30 
20 
S 0 0 -- 
20 0 S 60 0 S 50 40 S 
1/2 1/4 75 
80 
A 0 0 -- 
10 0 S 70 60 S 80 60 S 
1/2 1/2 * -- 0 -- 
80 70 S 90 80 S 100 
98 S 
1 1/16 
20 
30 
A 0 0 -- 
0 0 -- 
60 0 S 30 0 S 
1 1/8 40 
44 
A 0 0 -- 
0 0 -- 
30 0 S 60 40 S 
1 1/4 85 
86 
A 0 0 -- 
0 0 -- 
60 60 Ad 
80 60 S 
1 1/2 * 50 0 S 40 70 A 80 80 Ad * 
2 1/16 
70 
50 
S 40 0 S 0 0 -- 
0 0 -- 
30 0 S 
2 1/8 60 
60 
Ad 
70 0 S 20 0 S 60 0 S 60 40 S 
2 1/4 85 
90 
A 20 0 S 70 0 S 80 60 S 80 60 S 
2 1/2 * 60 0 S 70 70 Ad 
98 80 S 100 
98 S 
__________________________________________________________________________ 
*Observed and expected results were too close to 100% for synergism 
evaluation. 
TABLE 2 
__________________________________________________________________________ 
Postflood Test Results - Percent Control 
Annual 
Yellow Morning 
lb/A lb/A 
Watergrass 
Nutsedge 
Sesbania 
Glory Curly Dock 
Thiocarbamate 
Anilide 
0 E R O E R 0 E R 0 E R 0 E R 
__________________________________________________________________________ 
1/2 -- 0 0 0 0 0 
1 -- 60 10 0 0 
-- 1/16 
0 0 60 40 
-- 1/8 0 0 100 60 
-- 1/4 30 0 98 100 
1/2 1/16 
40 0 
S 0 0 -- 
100 
60 S 98 40 
S 
1/2 1/8 65 0 
S 0 0 -- 100 
60 S 
1/2 1/4 90 30 
S 10 0 S 
1 1/16 
75 60 
S 70 10 S 60 60 Ad 
90 40 
S 
1 1/8 85 60 
S 60 10 S 100 
60 
S 
1 1/4 100 
72 
S 50 10 S 
1/2 -- 0 0 0 0 
1 -- 10 0 0 0 
2 -- 80 65 0 0 
4 -- 99 75 0 0 
-- 1/8 30 0 20 100 
-- 1/4 95 0 40 90 
-- 1/2 98 0 100 100 
-- 1 100 0 100 100 
-- 2 100 0 100 100 
1/2 1/4 78 95 
A 0 0 75 40 S 100 
90 
S 
1/2 1/2 0 0 
1/2 1 0 0 
1/2 2 0 0 
1 1/8 95 37 
S 30 0 S 90 20 S 
1 1/4 98 75 
S 10 0 S 100 
40 S 100 
90 
S 
1 1/2 100 
95 
S 30 0 S 90 100 
A 
1 1 30 0 S 
1 2 95 0 S 
2 1/8 98 86 
S 80 65 S 85 20 S 
2 1/4 80 65 S 100 
40 S 
2 1/2 70 65 S 
2 1 100 
65 S 
2 2 98 65 S 
__________________________________________________________________________ 
On watergrass, sesbania, and morning glory tests, both observed and 
expected results were too close to 100% for synergism evaluation, except 
as indicated. All curly dock tests produced 100% kill. 
The compositions of the present invention are useful as herbicides in 
controlling the growth of undesirable vegetation by pre-emergence or 
post-emergence application to the locus where control is desired, 
including pre-plant and post-plant soil incorporation as well as surface 
application. The compositions are generally embodied in formulations 
suitable for convenient application. In general, such formulations will 
contain inert or occasionally active ingredients or diluent carriers in 
addition to the active compound. Examples of such ingredients or carriers 
are water, organic solvents, dust carriers, granular carriers, surface 
active agents, oil and water, water in oil emulsions, wetting agents, 
dispersing agents, and emulsifying agents. The herbicidal formulations 
generally take the form of 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 
carrier is usually in the range of from about 30 to 50 microns. Examples 
of suitable carriers are talc, bentonite, diatomaceous earth, and 
pyrophyllite. Anticaking and antistatic agents can be added, if desired. 
The composition generally contains up to 50% of active ingredient. 
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 Pesticide Formulations by Wade Van 
Valkenburg, 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 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, and the like. 
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 formulations described above, employing phytotoxic or herbicidally 
effective amounts of the compositions described herein, are applied to the 
loci where control is desired in any conventional manner. The loci 
referred to above include soil, seeds, seedlings, and the actual plants, 
as well as flooded fields. Dusts and liquid compositions can be applied by 
the use of powder dusters, boom and hand sprayers and spray dusters. The 
compositions can also be applied from airplanes as dusts or sprays because 
they are effective in very low dosages. In order to modify or control 
growth of germinating seeds or emerging seedlings, as a typical example, 
the dust and liquid compositions are applied to the soil according to 
conventional methods and are distributed in the soil to a depth of at 
least one-half inch below the soil surface. It is not necessary that the 
phytotoxic compositions be admixed with the soil particles. Instead, these 
compositions can be applied merely by spraying or sprinkling the surface 
of the soil. The phytotoxic 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. Dust 
compositions, granular compositions or liquid formulations applied to the 
surface of the soil can be distributed below the surface of the soil by 
conventional means such as discing, dragging or mixing operations. 
The phytotoxic compositions of this invention can also contain other 
additaments, for example, fertilizers, pesticides and the like, used as 
adjuvants or in combination with any of the above-described adjuvants. 
Other phytotoxic compounds useful in combination with the above-described 
compositions include, for example, 2,4-dichlorophenoxyacetic acids, 
2,4,5-trichlorophenoxy acetic acid, 2-methyl-4-chlorophenoxyacetic acid, 
and the salts, esters and amides thereof; triazine derivatives, such as 
2,4-bis (3-methoxypropylamino)-6-methyl-thio-s-triazine; 
2-chloro-4-ethylamino-6-isopropylamino-s-triazine, and 
2-ethylamino-4-isopropylamino-6-methylmercapto-s-triazine, urea 
derivatives such as 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, and 
acetamides such as N,N-diallyl-.alpha.-chloroacetamide, 
N-(.alpha.-chloroacetyl) hexamethyleneimine, and 
N,N-diethyl-.alpha.-bromoacetamide, and the like; benzoic acids such as 
3-amino-2,5-dichlorobenzoic; S-ethyl-dipropylthiocarbamate; S-ethyl 
hexahydro-1H-azepine-1-carbothioate and the like. Fertilizers useful in 
combination with the active ingredients include, for example, ammonium 
nitrate, urea and superphosphate. Other useful additaments include 
materials in which plant organisms take root and grow, such as compost, 
manure, humus, sand and the like. 
The amount of a composition of the present invention which constitutes a 
phytotoxic or herbicidally effective amount depends upon the nature of the 
seeds or plants to be controlled. The rate of application of active 
ingredient varies from about 0.01 to about 50 pounds per acre, preferably 
about 0.1 to about 25 pounds per acre with the actual amount used 
depending on the overall cost and the desired results. It will be readily 
apparent to one skilled in the art that compositions exhibiting lower 
herbicidal activity will require a higher dosage rate for the same degree 
of control than more active compounds.