Compositions and methods for reducing herbicidal injury

Abstract

A method and compositions for reducing injury to crops, especially wheat and sorghum, by acetanilide selective herbicides employing compounds having in common the base structure ##STR1## wherein Y and Y' are oxygen or sulfur.

Description

This invention relates to novel compositions and methods for reducing or nullifying injury to young crop plants by selective herbicides. More specifically, this invention relates to novel compositions and methods for reducing injury to young crop plants by selective herbicides, such as acetanilide herbicides, which comprises treating the habitat of the crop plant or the seed of the crop plant prior to planting, with an antagonistic agent for the selective herbicide.

The acetanilide herbicides such as alachlor, propachlor, butachlor and the like are very useful for controlling certain weeds in the presence of other growing plants. However, many of these herbicides injure certain crop plants, slowing growth and development at application rates necessary to stunt or kill the weeds. As a consequence, certain of these herbicides can not be employed for controlling weeds in the presence of certain crops, some of which crops are important commodities in the world food supply. Obviously, there is a need for a method of reducing or nullifying the injury of the crop plant by the selective acetanilide herbicide while not affecting the herbicidal action on the weed to be controlled.

There is provided by this invention a novel method of reducing or nullifying injury to the desired crop plant by selective acetanilide herbicides which does not interfere with the herbicidal action on the weed to be controlled. There are also provided novel compositions for treating the soil or the crop seed to reduce or nullify injury to the crop by selective acetanilide herbicides.

The compounds which are useful in reducing or eliminating crop injury are sometimes referred to as antagonistic agents, antidote compounds, or safening agents. Antagonistic agents for the purpose of this invention are defined as compounds which counteract the herbicidal action of selective acetanilide herbicides, thereby reducing or nullifying injury to the plant, yet, which exhibit little or no toxicity to the crop or crop seed at effective rates of application. Although the mechanism by which these compounds reduce the herbicidal activity of the acetanilide herbicide on crop plants without reducing the effective control of undesired plants or weeds, is not fully understood, the herbicide test program has confirmed the phenomenon for a wide variety of compounds having in common the base structure ##STR2## wherein Y and Y' are oxygen or sulfur. These compounds when employed with an acetanilide herbicide reduced the injury to crop plants by the acetanilide herbicide, particularly the injury to wheat and sorghum. The compounds which are preferred antagonistic agents with acetanilide hericides for the selective control of undesired plants in the presence of wheat and sorghum are described by the formula ##STR3## wherein Y and Y' are each independently oxygen or sulfur and, when Y and Y' are both oxygen, R is alkyl, alkenyl, haloalkenyl or haloalkynyl. R.sup.1 is hydrogen, alkyl or alkenyl and R.sup.2 is alkyl, phenyl or substituted phenyl, or R.sup.1 and R.sup.2 when taken together are alkylene of the emperical formula --C.sub.n H.sub.2n -- wherein n is an integer of from 4 through 8, inclusive, having from 4 through 8 carbons in a continuous chain between the nitrogen terminal bonds or a group of the formula --C.sub.2 H.sub.4 OC.sub.2 H.sub.4 --; when one of Y and Y' is oxygen, R is alkyl, alkenyl or haloalkenyl, R.sup.1 is hydrogen, alkyl or ##STR4## wherein m is an integer of from 1 to 4 and R.sup.2 is hydrogen, alkyl, phenyl or substituted phenyl or R.sup.1 and R.sup.2 when taken together are a group of the formula --C.sub.2 H.sub.4 OC.sub.2 H.sub.4 --or R.sup.1 and R.sup.2 when taken together, provided that Y is oxygen, are alkylene of the empirical formula --C.sub.n H.sub.2n -- wherein n is an integer of from 4 through 8, inclusive, having from 4 through 8 carbons in a continuous chain between the nitrogen terminal bonds, or R.sup.1 and R.sup.2 when taken together, provided that Y' is oxygen, are an unsaturated hydrocarbon of the empirical formula --C.sub.n H.sub.2n-2 wherein n is an integer of from 4 through 8, inclusive, having from 4 through 8 carbons in a continuous chain between the nitrogen terminal bonds; and when both Y an Y' are sulfur, R is alkyl, substituted alkyl, alkenyl, haloalkenyl, phenyl or substituted phenyl, R.sup.1 is alkyl, phenyl or substituted phenyl and R.sup.2 is hydrogen, alkyl, alkenyl or haloalkenyl or R and R.sup.1 when taken together are alkylene of the empirical formula --C.sub.n H.sub.2n -- wherein n is an integer of from 4 through 8, inclusive, having from 4 through 8 carbons in a continuous chain between the nitrogen terminal bonds, an unsaturated hydrocarbon of the empirical formula --C.sub.n H.sub.2n-2 wherein n is an integer of from 4 through 8, inclusive, having from 4 through 8 carbons in a continuous chain between the nitrogen terminal bonds or a group of the formula ##STR5## wherein each R.sup.3 is independently hydrogen, halo or lower alkyl.

The amount of such antagonistic agents employed in methods and compositions of this invention will vary according to the particular acetanilide herbicide with which the agent is employed and the rate of application of the herbicide. In each instance the amount of antagonistic agent employed is a safening effective amount. By a safening effective amount is meant an amount which reduces crop injury by the acetanilide herbicide. In the tests employed in illustrating this invention, the amount of crop injury was reduced by at least 15 percent. In certain instances, a significant level of reduction of crop injury may be as low as about 10 percent and in other instances no lower than 20 percent. The reduction in level of crop injury is defined as the difference between the observed percentage of crop injury by the acetanilide herbicide without the safening agent and the observed percentage of crop injury by the acetanilide herbicide employed in conjunction with a safening effective amount of an antagonistic agent as defined herein.

Preferred alkyl are aliphatic hydrocarbons having from 1 through 18, inclusive, carbons. The configuration of the structure can be straight-chain, branched-chain, cyclic or a mixed configuration having both branched and cyclic moieties. More preferred alkyl have from 1 through 6, inclusive, carbons.

As employed herein, the terms "lower alkyl" and "lower alkoxy" designate those groups wherein the aliphatic chain is straight or branched and has from 1 through 4 carbons, inclusive.

As employed herein, the term "substituted phenyl" designates phenyl groups of the formula ##STR6## wherein each Z is independently halo, trihalomethyl, hydroxyl, nitro, lower alkyl or lower alkoxy, and x is an integer from 1 through 3, inclusive, provided that no more than two Z's are nitro and that no more than one Z is hydroxyl. The term "halo" designates a halogen atom selected from fluorine, chlorine, bromine and iodine. Preferred halo are chloro and bromo. Preferred trihalomethyl is trifluoromethyl.

Preferred alkenyl have from 2 through 8, inclusive, carbons. More preferred alkenyl have from 3 through 6, inclusive, carbons. Still more preferred alkenyl have 3 carbons and have the unsaturated bond in the 2-position.

Preferred haloalkenyl have from 2 through 8, inclusive, carbons and 1 through 3, inclusive, halogens. More preferred haloalkenyl have from 3 through 6, inclusive, carbons and 1 through 3, inclusive, halogens. Still more preferred haloalkenyl have from 3 through 6, inclusive, carbons and 1 through 3, inclusive, chlorines.

Preferred haloalkynyl have from 2 through 8, inclusive, carbons and 1 through 3, inclusive, halogens. More preferred haloalkynyl have from 3 through 6, inclusive, carbons and 1 through 3, inclusive, halogens. Still more preferred haloalkynyl have from 3 through 6, inclusive, carbons and 1 through 3, inclusive, chlorines.

Preferred substituted alkyl have from 1 through 3, inclusive, substituents selected from the group consisting of cyano, hydroxyl, phenyl, substituted phenyl, phenoxyl and substituted phenoxyl. More preferred substituted alkyl have, in the aliphatic portion of the group, from 1 through 6, inclusive, carbons. Still more preferred substituted alkyl have one substituent selected from the aforementioned group.

The compounds employed herein as antagonistic agents are either known compounds or are readily prepared from known compounds by old methods known to the skilled chemist.

Acetanilide herbicides are widely known in the art. U.S. Pat. No. 2,863,752, 3,442,945, 3,547,620, 3,630,716, and 3,637,847 are but a few of the many patents disclosing acetanilide herbicides which have published in the United States and other countries. Although it has been taught that a wide variety of acetanilides are useful as selective herbicides, it is evident from the prior art that alpha-haloacetanilides are most commercially significant herbicidal acetanilides. Because of the wide usage of alpha-haloacetanilides, these herbicides are the preferred herbicides for safening by the methods and compositions of the present invention. Nevertheless, the present safening methods and compositions are useful for safening the herbicidal acetanilide family of compounds and the instant invention is not limited to only alpha-haloacetanilide herbicides.

Particularly effective safening properties are obtained with selective alpha-haloacetanilides of the formula ##STR7## wherein X is halo, Q is alkylene of the empirical formula --C.sub.y H.sub.2y wherein y is an integer of from 1 through 8, inclusive, A is oxygen or sulfur, each Z.sup.3 independently is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, polyalkoxy, alkoxyalkyl, polyalkoxyalkyl, haloalkyl, hydroxyalkyl, haloalkenyl, oxoalkyl, alkenyloxy and alkyl each of a maximum of 18 carbon atoms; aryl, aryloxyalkyl, haloaryl, haloaryloxyalkyl and arylalkyl of from 6 to 24 carbon atoms; furfuryl; and tetrahydrofurfuryl; or two groups are combined to form a cyclic group of from 2 to 6 carbon atoms selected from the group consisting of ##STR8## wherein T is chlorine, bromine or fluorine, T' is alkyl of a maximum of 6 carbon atoms or acyl of a maximum of 4 carbon atoms, m is an integer of from 0 to 3, inclusive, n is an integer of from 0 to 5, inclusive, and p is an integer of 0 or 1 and each Z.sup.1 independently is hydrogen, halogen, or alkyl each of a maximum of 10 carbon atoms, and each Z.sup.2 independently is hydrogen, alkyl or alkoxy each of a maximum of 10 carbon atoms.

Particularly good safening of alachlor, propachlor and butachlor herbicides with regard to wheat and sorghum has been found employing the safening methods and compositions of the present invention. These particularly good results with regard to wheat and sorghum are likewise obtained with herbicides of the formula ##STR9## wherein each Z.sup.5 is independently lower alkyl or hydrogen, Z.sup.4 is lower alkyl and Q.sup.2 is alkylene of the empirical formula --C.sub.z H.sub.2z -- wherein z is an integer of from 1 through 4, inclusive, preferably from 1 through 4, inclusive.

The method and compositions of this invention are illustrated by the following examples.

EXAMPLES 1 THROUGH 180

The safening effectiveness of representative antagonistic agents on representative acetanilide herbicides with respect to wheat and sorghum is shown by the test results presented in Table I. For each antagonistic agent, there is shown the percent inhibition of the plants by the acetanilide herbicide and the antagonistic agent and the safening effect of the antagonistic agent in terms of reduction in percent control which is determined by subtracting the percent control of the acetanilide herbicide in a specified amount and the antagonistic agent in a specified amount from the percent control of the acetanilide herbicide in the same specified amount but with no antagonistic agent. These results are obtained by the following procedure:

A good grade of top soil is placed in an aluminum pan and compacted to a depth of 3/8 to 1/2 inch from the top of the pan. A predetermined number of seeds of each of the plant species to be tested are placed on top of the soil in the pans. A quantity of soil sufficient to substantially fill the pan is measured and placed in suitable container. A measured quantity of the antagonistic agent dispersed or dissolved in a suitable carrier is sprayed on the soil in the container. A measured quantity of the acetanilide herbicide dispersed or dissolved in a suitable carrier is then sprayed on the soil in the container already treated with the safening agent.

The quantity of acetanilide herbicide and antagonistic agent is expressed in terms of kilograms per hectare for ease of comparing the greenhouse test results with field results. The soil containing the antagnostic agent and acetanilide herbicide is thoroughly mixed. This mixing is sometimes referred to as incorporation of the herbicide and antagonistic agent into the soil. The mixing or incorporation provides a substantially uniform distribution of the antagonistic agent and herbicide throughout the soil. The seeds are covered with the soil containing the antagonistic agent and acetanilide herbicide and the pans are leveled. The pans are then placed on a sand bench in the greenhouse and watered from below as needed. The plants are observed at the end of approximately 21 days and the results in terms of percent inhibition of each seed lot are recorded. For each test series a pan of plants is also prepared containing no acetanilide herbicide and no antagonistic agent as a control. Additionally, for each test, a pan of plants is prepared with soil covering the seed containing no acetanilide herbicide and only the measured amount of antagonistic agent being incorporated into the soil covering the seeds to ascertain any herbicidal effect of the antagonistic agent alone. For each series of tests the herbicidal effect of the acetanilide herbicide is observed from pans of plants treated with the same quantity of herbicide alone.

TABLE I (A)__________________________________________________________________________ Amount of alachlor Antag- Per-Example Herbicide onistic Amount cent In- SafeningNo. (kg./ha.) Agent (kg./ha.) Crop hibition Effect (%)__________________________________________________________________________ 1 0.14 Ethyl-N- 4.48 Wheat 10 13 isopropyl- carbamate 0.14 Ethyl-N- 4.48 Sorghum 0 35 isopropyl- carbamate 2 0.14 Ethyliso- 4.48 Wheat 10 13 butyl-car- bamate 0.14 Ethyliso- 4.48 Sorghum 15 20 butyl-car- bamate 3 0.14 Ethyl-1,2- 4.48 Wheat 0 23 dimethyl- butylcar- bamate 0.14 Ethyl-1,2- 4.48 Sorghum 15 20 dimethyl- butylcar- bamate 4 0.14 Ethyl-N- 4.48 Wheat 0 23 ethyl,N- t-butyl- thiolcar- bamate 1.12 Ethyl-N- 4.48 Wheat 10 25 ethyl,N- t-butyl- thiolcar- bamate 5 0.14 Ethyldi- 4.48 Wheat 0 23 methyl- thionocar- bamate 0.14 Ethyldi- 4.48 Sorghum 15 20 methyl- thionocar- bamate 6 0.14 Butylcar- 4.48 Wheat 0 5 banilate 0.14 Butylcar- 4.48 Sorghum 30 35 banilate 7 0.14 Methyl- 4.48 Sorghum 40 25 carbanilate 8 0.14 Isopropyl- 4.48 Sorghum 10 55 N-butyl- carbanilate 1.12 Isopropyl- 4.48 Sorghum 40 60 N-butyl- carbanilate 9 0.14 Butylthiol- 2.24 Sorghum 10 55 carbanilate10 0.14 Methyl-N- 4.48 Sorghum 35 30 methylthiol- carbanilate 1.12 Methyl-N- 4.48 Sorghum 80 20 methylthiol- carbanilate11 1.12 Methyl- 4.48 Sorghum 75 25 thiono- carbanilate12 1.12 Methyl-2, 4.48 Sorghum 80 20 6-diethyl- thionocar- banilate13 1.12 Allyl-N- 4.48 Sorghum 70 30 ethyldithio- carbanilate14 0.14 Butyl-N- 4.48 Sorghum 35 30 ethyldithio- carbanilate 1.12 Butyl-N- 4.48 Sorghum 80 20 ethyldithio- carbanilate15 0.14 Methyl-N- 4.48 Sorghum 5 60 ethyldithio- carbanilate 1.12 Methyl-N- 4.48 Sorghum 35 65 ethyldithio- carbanilate16 0.14 Hexyl-N- 4.48 Wheat 0 5 ethyldithio- carbanilate 1.12 Hexyl-N- 4.48 Wheat 0 20 ethyldithio- carbanilate 0.14 Hexyl-N- 4.48 Sorghum 25 40 ethyldithio- carbanilate17 0.14 Methyldi- 4.48 Sorghum 35 30 thiocar- banilate18 0.14 2-chloro- 4.48 Sorghum 35 30 allyl-N- methyldi- thiocar- banilate 1.12 2-chloro- 4.48 Sorghum 75 25 allyl-N- methyldi- thiocar- banilate19 1.12 2-chloro- 4.48 Sorghum 65 35 ethyl-N- ethylthiono- carbanilate20 0.28 Ethyl-N- 4.48 Wheat 0 30 isopropyl- carbamate 0.56 Ethyl-N- 4.48 Wheat 10 30 isopropyl- carbamate21 0.28 Ethyldi- 4.48 Wheat 0 30 methylthiono- carbamate 0.56 Ethyldi- 4.48 Wheat 10 30 methylthiono- carbamate 1.12 Ethyldi- 4.48 Wheat 10 15 methylthiono- carbamate 2.24 Ethyldi- 4.48 Wheat 20 10 methylthiono- carbamate 0.28 Ethyldi- 4.48 Sorghum 45 28 methylthiono- carbamate22 0.28 Ethyliso- 4.48 Wheat 0 30 butylcar- bamate 0.56 Ethyliso- 4.48 Wheat 20 20 butylcar- bamate 1.12 Ethyliso- 4.48 Wheat 10 15 butylcar- bamate 2.24 Ethyliso- 4.48 Wheat 20 10 butylcar- bamate 0.28 Ethyliso- 4.48 Sorghum 55 18 butylcar- bamate23 0.28 Isopropyl- 4.48 Sorghum 25 48 N-butylcar- banilate 0.56 Isopropyl- 4.48 Sorghum 75 20 N-butylcar- banilate 1.12 Isopropyl- 4.48 Sorghum 60 38 N-butylcar- banilate 2.24 Isopropyl- 4.48 Sorghum 60 35 N-butylcar- banilate24 0.28 2-chloro- 4.48 Sorghum 50 23 allyl-p- methylthiol- carbanilate 0.56 2-chloro- 4.48 Sorghum 65 30 allyl-p- methylthiol- carbanilate25 0.28 Methyl-N- 4.48 Sorghum 15 58 ethyldithio- carbanilate 0.56 Methyl-N- 4.48 Sorghum 35 60 ethyldithio- carbanilate 1.12 Methyl-N- 4.48 Sorghum 35 63 ethyldithio- carbanilate 2.24 Methyl-N- 4.48 Sorghum 70 25 ethyldithio- carbanilate26 0.28 Hexyl-N- 4.48 Wheat 10 20 ethyldithio- carbanilate 0.56 Hexyl-N- 4.48 Wheat 20 20 ethyldithio- carbanilate27 0.28 Methyl-N- 0.28 Sorghum 65 20 ethyldithio- carbanilate 0.28 Methyl-N- 1.12 Sorghum 45 40 ethyldithio- carbanilate 0.28 Methyl-N- 4.48 Sorghum 10 75 ethyldithio- carbanilate 0.56 Methyl-N- 1.12 Sorghum 35 53 ethyldithio- carbanilate 0.56 Methyl-N- 4.48 Sorghum 25 63 ethyldithio- carbanilate 1.12 Methyl-N- 4.48 Sorghum 35 60 ethyldithio- carbanilate 2.24 Methyl-N- 4.48 Sorghum 50 45 ethyldithio- carbanilate28 0.28 Isobutyl-N- 4.48 Sorghum 20 65 butylcar- banilate 0.56 Isobutyl-N- 4.48 Sorghum 30 58 butylcar- banilate 1.12 Isobutyl-N- 4.48 Sorghum 20 75 butylcar- banilate 2.56 Isobutyl-N- 4.48 Sorghum 65 30 butylcar- banilate29 0.28 Isobutyl- 4.48 Sorghum 15 60 carbanilate 0.84 Isobutyl- 4.48 Sorghum 60 30 carbanilate 1.12 Isobutyl- 4.48 Sorghum 65 25 carbanilate30 0.28 t-butyl- 4.48 Sorghum 40 35 carbanilate 0.84 t-butyl- 4.48 Sorghum 70 20 carbanilate31 0.28 t-butyl- 4.48 Sorghum 60 15 thiolcar- banilate 0.84 t-butyl- 4.48 Sorghum 75 15 thiolcar- banilate32 0.28 Sec-butyl- 4.48 Sorghum 55 20 N-ethyldi- thiocar- banilate33 2.24 Ethyl-N- 4.48 Wheat 30 45 ethyldithio- carbanilate 0.28 Ethyl-N- 4.48 Sorghum 35 53 ethyldithio- carbanilate 0.84 Ethyl-N- 4.48 Sorghum 40 53 ethyldithio- carbanilate 2.24 Ethyl-N- 4.48 Sorghum 75 23 ethyldithio- carbanilate34 2.24 Propyl-N- 4.48 Wheat 15 60 ethyldithio- carbanilate 0.28 Propyl-N- 4.48 Sorghum 45 43 ethyldithio- carbanilate35 2.24 Butyldithio- 2.24 Wheat 35 40 carbanilate 0.28 Butyldithio- 2.24 Sorghum 60 28 carbanilate36 0.28 Methyl-N- 2.24 Sorghum 50 38 isopropyl- thiolcar- banilate 0.84 Methyl-N- 2.24 Sorghum 70 23 isopropyl- thiolcar- banilate37 0.28 Isopropyl- 0.56 Sorghum 75 13 N-propyl- thiolcar- banilate 0.84 Isopropyl- 0.56 Sorghum 75 18 N-propyl- thiolcar- banilate38 0.28 t-butyl- 4.48 Sorghum 40 48 N-isopropyl- thiolcar- banilate 0.84 t-butyl- 4.48 Sorghum 60 33 N-isopropyl- thiolcar- banilate 2.24 t-butyl- 4.48 Sorghum 70 28 N-isopropyl- thiolcar- banilate39 0.28 Ethyl-N-t- 4.48 Sorghum 45 43 butylcar- banilate 0.84 Ethyl-N-t- 4.48 Sorghum 75 18 butylcar- banilate40 2.24 Propyl-N- 4.48 Sorghum 50 25 isopropyl- dithiocar- banilate41 0.28 Allylthiono- 4.48 Wheat 0 20 carbanilate 0.84 Allylthiono- 4.48 Wheat 0 65 carbanilate 2.24 Allylthiono- 4.48 Wheat 0 70 carbanilate 0.28 Allylthiono- 4.48 Sorghum 20 30 carbanilate 0.84 Allylthiono- 4.48 Sorghum 40 55 carbanilate 2.24 Allylthiono- 4.48 Sorghum 75 19 carbanilate42 0.28 2-methyl- 4.48 Wheat 0 20 allylcar- banilate 2.24 2-methyl- 4.48 Wheat 50 20 allylcar- banilate 0.28 2-methyl- 4.48 Sorghum 25 25 allylcar- banilate 0.84 2-methyl- 4.48 Sorghum 45 50 allylcar- banilate 2.24 2-methyl- 4.48 Sorghum 70 24 allylcar- banilate43 2.24 Allyl-N- 4.48 Wheat 30 40 methylcar- banilate 0.28 Allyl-N- 4.48 Sorghum 15 35 methylcar- banilate 0.84 Allyl-N- 4.48 Sorghum 65 30 methylcar- banilate 2.24 Allyl-N- 4.48 Sorghum 85 9 methylcar- banilate44 0.84 Pentyl-3, 4.48 Wheat 0 5 4-dichloro- thionocar- banilate 2.24 Pentyl-3, 4.48 Wheat 0 20 4-dichloro- thionocar- banilate45 0.28 Ethyl-3,4- 4.48 Sorghum 35 54 dichlorothiol- carbanilate46 0.28 Methyl-p- 2.24 Wheat 0 5 chlorothiono- carbanilate 0.84 Methyl-p- 2.24 Wheat 0 5 chlorothiono- carbanilate 2.24 Methyl-p- 2.24 Wheat 0 20 chlorothiono- carbanilate47 0.28 2-chloro- 4.48 Sorghum 60 29 allyl-p-methyl- thiolcarbanilate48 0.28 2-chloro- 4.48 Sorghum 30 59 allyl-N-methyl- dithiocar- banilate 0.84 2-chloro- 4.48 Sorghum 35 53 allyl-N-methyl- dithiocar- banilate 2.24 2-chloro- 4.48 Sorghum 60 37 allyl-N-methyl- dithiocar- banilate49 0.28 Hexyl-m- 4.48 Sorghum 65 24 methylcar- banilate50 0.28 2-chloro- 4.48 Sorghum 60 29 allyl-N- propyldithio- carbanilate51 0.28 2-chloro- 4.48 Sorghum 30 59 allyl-N-iso- propyldithio- carbanilate52 0.28 Allyl-N- 4.48 Sorghum 10 79 methyldithio- carbanilate 0.84 Allyl-N- 4.48 Sorghum 15 73 methyldithio- carbanilate 2.24 Allyl-N- 4.48 Sorghum 30 67 methyldithio- carbanilate53 0.28 Butyl-3,4- 4.48 Sorghum 50 29 dichloro- thiolcar- banilate54 0.28 Allyl-N- 4.48 Sorghum 50 20 ethyldithio- carbanilate 0.84 Allyl-N- 4.48 Sorghum 75 23 ethyldithio- carbanilate55 0.28 2-chloro- 4.48 Sorghum 40 15 ethyl-N- methylthiono- carbanilate56 0.28 2-chloro- 4.48 Wheat 0 80 allyl-o-chloro- N-(2-chloroallyl) dithiocarbanilate 0.28 2-chloro- 4.48 Sorghum 15 40 allyl-o-chloro- N-(2-chloroallyl) dithiocarbanilate 0.84 2-chloro- 4.48 Sorghum 50 35 allyl-o-chloro- N-(2-chloroallyl) dithiocarbanilate57 0.84 Ethyl-N- 4.48 Sorghum 60 25 (2-carbamoylethyl)- thiolcarbanilate 2.24 Ethyl-N- 4.48 Sorghum 70 28 (2-carbamoylethyl)- thiolcarbanilate58 0.28 Allyldi- 4.48 Wheat 20 18 thiocarbanilate 0.28 Allyldi- 4.48 Sorghum 50 10 thiocarbanilate 0.84 Allyldi- 4.48 Sorghum 65 23 thiocarbanilate59 0.28 Methyl-p- 4.48 Wheat 20 18 t-butyl- thionocar- banilate 0.28 Methyl-p- 4.48 Sorghum 25 35 t-butyl- thionocar- banilate 0.84 Methyl-p- 4.48 Sorghum 55 33 t-butyl- thionocar- banilate 2.24 Methyl-p- 4.48 Sorghum 85 8 t-butyl- thionocar- banilate60 0.28 Ethyl-3- 4.48 Wheat 20 18 hydroxy-N- isopropyl- thiolcar- banilate 0.28 Ethyl-3- 4.48 Sorghum 45 15 hydroxy-N- isopropyl- thiolcar- banilate 0.84 Ethyl-3- 4.48 Sorghum 75 13 hydroxy-N- isopropyl- thiolcar- banilate61 0.28 Isopropyl- 4.48 Sorghum 40 30 N-butyl- carbanilate 0.56 Isopropyl- 4.48 Sorghum 55 33 N-butyl- carbanilate 1.12 Isopropyl- 4.48 Sorghum 55 38 N-butyl- carbanilate 2.24 Isopropyl- 4.48 Sorghum 55 43 N-butyl- carbanilate62 0.28 Methyl-N- 4.48 Sorghum 50 20 ethyldi- thiocar- banilate 0.56 Methyl-N- 4.48 Sorghum 50 38 ethyldi- thiocar- banilate 1.12 Methyl-N- 4.48 Sorghum 70 23 ethyldi- thiocar- banilate 2.24 Methyl-N- 4.48 Sorghum 90 8 ethyldi- thiocar- banilate63 0.28 Isobutyl- 4.48 Sorghum 30 40 carbanilate 0.56 Isobutyl- 4.48 Sorghum 70 18 carbanilate 1.12 Isobutyl- 4.48 Sorghum 70 23 carbanilate 2.24 Isobutyl- 4.48 Sorghum 70 28 carbanilate64 0.28 t-butyl- 4.48 Sorghum 55 15 carbanilate 0.56 t-butyl- 4.48 Sorghum 75 13 carbanilate 1.12 t-butyl- 4.48 Sorghum 80 13 carbanilate 2.24 t-butyl- 4.48 Sorghum 85 13 carbanilate65 0.28 Ethyl-N- 4.48 Sorghum 45 25 ethyldithio- carbanilate 0.56 Ethyl-N- 4.48 Sorghum 60 28 ethyldithio- carbanilate 1.12 Ethyl-N- 4.48 Sorghum 70 23 ethyldithio- carbanilate 2.24 Ethyl-N- 4.48 Sorghum 70 28 ethyldithio- carbanilate66 0.56 t-butyl-N- 4.48 Sorghum 50 38 isopropyl- thiolcar- banilate 1.12 t-butyl-N- 4.48 Sorghum 65 28 isopropyl- thiolcar- banilate67 0.28 Allyl- 4.48 Sorghum 45 25 thionocar- banilate 0.56 Allyl- 4.48 Sorghum 65 23 thionocar- banilate 1.12 Allyl- 4.48 Sorghum 65 28 thionocar- banilate 2.24 Allyl- 4.48 Sorghum 75 23 thionocar- banilate68 0.28 2-methyl- 4.48 Sorghum 50 20 allylcar- banilate 0.56 2-methyl- 4.48 Sorghum 65 23 allylcar- banilate 1.12 2-methyl- 4.48 Sorghum 60 33 allylcar- banilate 2.24 2-methyl- 4.48 Sorghum 70 28 allylcar- banilate69 0.28 Allyl-N- 2.24 Sorghum 35 35 methyldi- thiocar- banilate 0.28 Allyl-N- 4.48 Sorghum 30 40 methyldi- thiocar- banilate 0.56 Allyl-N- 2.24 Sorghum 55 33 methyldi- thiocar- banilate 0.56 Allyl-N- 4.48 Sorghum 35 53 methyldi- thiocar- banilate 1.12 Allyl-N- 2.24 Sorghum 60 33 methyldi- thiocar- banilate 1.12 Allyl-N- 4.48 Sorghum 45 48 methyldi- thiocar- banilate 2.24 Allyl-N- 2.24 Sorghum 80 18 methyldi- thiocar- banilate 2.24 Allyl-N- 4.48 Sorghum 55 43 methyldi- thiocar- banilate70 0.28 Ethyl-3,4- 4.48 Sorghum 55 15 dichloro- thiolcar- banilate 0.56 Ethyl-3,4- 4.48 Sorghum 65 23 dichloro- thiolcar- banilate71 0.28 2-chloro- 4.48 Sorghum 45 25 allyl-N- methyldi- thiocar- banilate 0.56 2-chloro- 4.48 Sorghum 60 28 allyl-N- methyldi- thiocar- banilate 1.12 2-chloro- 4.48 Sorghum 70 23 allyl-N- methyldi- thiocar- banilate 2.24 2-chloro- 4.48 Sorghum 80 18 allyl-N- methyldi- thiocar- banilate72 0.28 2-chloro- 4.48 Sorghum 50 20 allyl-o- chloro-N- (2-chloroallyl) dithiocar- banilate 0.56 2-chloro- 4.48 Sorghum 70 18 allyl-o- chloro-N- (2-chloroallyl) dithiocar- banilate73 0.28 Methyl-p- 4.48 Sorghum 35 35 t-butyl- thionocar- banilate 0.56 Methyl-p- 4.48 Sorghum 60 28 t-butyl- thionocar- banilate 1.12 Methyl-p- 4.48 Sorghum 70 23 t-butyl- thionocar- banilate 2.24 Methyl-p- 4.48 Sorghum 75 23 t-butyl- thionocar- banilate74 0.28 Cyclohexyl- 4.48 Sorghum 50 49 N-allyl-cyclo- hexanecarbamate75 2.24 Cyclo- 4.48 Wheat 60 20 hexyldi- ethyldithio- carbamate76 0.28 Isopropyl- 4.48 Wheat 60 20 N-ethylcyclo- hexanecar- bamate 2.24 Isopropyl- 4.48 Sorghum 75 24 N-ethylcyclo- hexanecar- bamate77 0.28 Methyl-N- 4.48 Sorghum 60 39 isopropyldi- thiocyclo- hexanecar- bamate78 2.24 Methyl-N- 4.48 Wheat 50 30 methylthiono- cyclohexane- carbamate 0.28 Methyl-N- 4.48 Sorghum 80 19 methylthiono- cyclohexane- carbamate79 0.28 Ethyl-N- 4.48 Sorghum 75 24 methylthiono- cyclohexane- carbamate80 0.28 Ethyl-N- 4.48 Sorghum 60 39 ethylthiono- cyclohexane- carbamate81 2.24 Propyl-N- 4.48 Wheat 40 40 butylthiono- cyclohexane- carbamate82 0.28 Phenyldi- 4.48 Sorghum 65 33 ethyldithio- carbamate83 0.28 Ethyl- 4.48 Sorghum 75 23 pyrrolidine- thionocarboxy- late84 0.28 2-chloro- 4.48 Sorghum 75 22 allyl-3,6- dihydro-1(2H) pyridinecar- bodithioate 2.24 2-chloro- 4.48 Sorghum 70 30 allyl-3,6- dihydro-1(2H) pyridinecar- bodithioate85 0.28 2-chloro- 4.48 Sorghum 75 22 allyl-3,6- dihydro-1(2H) pyridinecar- bothiolate 2.24 2-chloro- 4.48 Sorghum 65 35 allyl-3,6- dihydro-1(2H) pyridinecar- bothiolate86 0.28 2-hydroxy- 4.48 Sorghum 75 22 ethyl-5-ethyl- 2-methyl-1- piperidinecarbo- dithioate87 0.28 Ethyl- 4.48 Wheat 10 15 piperidinethio- carboxylate 2.24 Ethyl- 4.48 Wheat 60 20 piperidinethio- carboxylate 0.28 Ethyl- 4.48 Sorghum 80 17 piperidinethio- carboxylate88 2.24 2-cyclo- 4.48 Wheat 35 25 hexen-1-yldiiso- propylthiolcar- bamate89 0.28 Allyldithio- 4.48 Wheat 0 10 2-cyclohexene- 1-carbamate 2.24 Allyldithio- 4.48 Wheat 35 25 2-cyclohexene- 1-carbamate90 0.28 Methyl- 4.48 Sorghum 60 35 N-isopropyl- thiol-2-cyclo- hexene-1-car- bamate91 0.28 Ethyl-4- 4.48 Wheat 20 30 morpholine- carbothionate 2.24 Ethyl-4- 4.48 Wheat 75 23 morpholine- carbothionate92 0.28 3-chloro- 4.48 Wheat 25 25 2-butyl-4- morpholine- carbodithioate 2.24 3-chloro- 4.48 Wheat 80 8 2-butyl-4- morpholine- cardodithioate93 0.28 Allyl-4- 4.48 Wheat 20 30 morpholinecarbo- thionate 2.24 Allyl-4- 4.48 Wheat 80 8 morpholinecarbo- thionate94 0.28 2-chloro- 4.48 Wheat 30 20 allyl-2,6-di- methyl-4- morpholinecar- bodithioate 0.28 2-chloro- 4.48 Sorghum 75 22 allyl-2,6-di- methyl-4- morpholinecar- bodithioate95 0.28 Ethylhexa- 4.48 Wheat 20 30 hydro(1H)azepine- 1-carbothionate 2.24 Ethylhexa- 4.48 Wheat 75 13 hydro(1H)azepine- 1-carbothionate96 0.28 Methylhexa- 4.48 Wheat 25 25 hydro(1H)azepine- 1-carboxylate97 0.28 Pentylhexa- 4.48 Wheat 15 35 hydro(1H)azepine- 1-carboxylate 2.24 Pentylhexa- 4.48 Wheat 70 18 hydro(1H)azepine- 1-carboxylate 0.28 Pentylhexa- 4.48 Sorghum 70 27 hydro(1H)azepine- 1-carboxylate98 0.28 Isopropyl- 4.48 Wheat 20 30 hexahydro(1H) azepine-1- carboxylate 2.24 Isopropyl- 4.48 Wheat 80 8 hexahydro(1H) azepine-1- carboxylate99 0.28 Octylocta- 1.12 Wheat 30 20 hydro(1H)azonine- 1-carbothiolate 2.24 Octylocta- 1.12 Wheat 75 13 hydro(1H)azonine- 1-carbothiolate100 0.28 Isopropyl- 4.48 Wheat 30 20 hexahydroazocine- 1(2H)azoninethiono- carboxylate 2.24 Isopropyl- 4.48 Wheat 65 23 hexahydroazocine- 1(2H)azoninethiono- carboxylate101 0.28 Ethylocta- 4.48 Wheat 20 30 hydro(1H)azonine- thionocarboxylate 2.24 Ethylocta- 4.48 Wheat 60 28 hydro(1H)azonine- thionocarboxylate102 0.07 Allyl-N- 4.48 Wheat 0 10 methyldi- thiocar- banilate 0.28 Allyl-N- 4.48 Wheat 15 23 methyldi- thiocar- banilate 1.12 Allyl-N- 4.48 Wheat 35 40 methyldi- thiocar- banilate 0.07 Allyl-N- 4.48 Sorghum 15 35 methyldi- thiocar- banilate 0.28 Allyl-N- 4.48 Sorghum 40 58 methyldi- thiocar- banilate 1.12 Allyl-N- 4.48 Sorghum 80 20 methyldi- thiocar- banilate103 0.07 Methyl-N- 4.48 Wheat 0 10 methyldi- thiocar- banilate 0.28 Methyl-N- 4.48 Wheat 0 38 methyldi- thiocar- banilate 1.12 Methyl-N- 4.48 Wheat 20 55 methyldi- thiocar- banilate 4.48 Methyl-N- 4.48 Wheat 40 50 methyldi- thiocar- banilate 0.07 Methyl-N- 4.48 Sorghum 20 30 methyldi- thiocar- banilate 0.28 Methyl-N- 4.48 Sorghum 50 48 methyldi- thiocar- banilate 1.12 Methyl-N- 4.48 Sorghum 85 15 methyldi- thiocar- banilate104 0.07 Butyl-N- 4.48 Wheat 0 10 methylcar- banilate 0.28 Butyl-N- 4.48 Wheat 15 23 methylcar- banilate 1.12 Butyl-N- 4.48 Wheat 40 35 methylcar- banilate 0.07 Butyl-N- 4.48 Sorghum 25 25 methylcar- banilate 0.28 Butyl-N- 4.48 Sorghum 75 23 methylcar- banilate105 0.14 2-chloro- 4.48 Wheat 0 20 allyl-3,4-di- chloro-N-(2- chloroallyl) dithiocar- banilate 0.84 2-chloro- 4.48 Wheat 45 40 allyl-3,4-di- chloro-N-(2- chloroallyl) dithiocar- banilate 0.14 2-chloro- 4.48 Sorghum 50 40 allyl-3,4-di- chloro-N-(2- chloroallyl) dithiocar- banilate106 0.14 2-chloro- 4.48 Sorghum 50 40 allyl-N-allyl-3,4- dichlorodithio- carbanilate107 0.14 Methyl-N- 4.48 Wheat 0 20 allyl-3,4- dichlorodithio- carbanilate 0.14 Methyl-N- 4.48 Sorghum 65 25 allyl-3,4- dichlorodithio- carbanilate108 0.14 Allyl-3,4- 4.48 Wheat 10 10 dichloro-N- (2-chloroallyl) dithiocarbanilate 0.84 Allyl-3,4- 4.48 Wheat 70 15 dichloro-N- (2-chloroallyl) dithiocarbanilate 0.14 Allyl-3,4- 4.48 Sorghum 65 25 dichloro-N- (2-chloroallyl) dithiocarbanilate109 0.14 2-chloro- 4.48 Sorghum 75 15 allyl-p-chloro- N-ethyldithio- carbanilate110 0.14 2,3,3-tri- 4.48 Sorghum 60 30 chloroallyl-o- chlorocarbanilate111 0.14 2,3,3-tri- 4.48 Sorghum 70 20 chloroallyl-p- chlorocarbanilate112 0.14 2-chloro-3- 4.48 Wheat 10 50 butenyl-p-bromo- carbanilate 0.84 2-chloro-3- 4.48 Wheat 70 24 butenyl-p-bromo- carbanilate 0.14 2-chloro-3- 4.48 Sorghum 65 25 butenyl-p-bromo- carbanilate113 0.14 Allyl-p- 4.48 Wheat 35 25 chlorodi- thiocar- banilate 0.84 Allyl-p- 4.48 Wheat 70 24 chlorodi- thiocar- banilate 0.14 Allyl-p- 4.48 Sorghum 65 24 chlorodi- thiocar- banilate114 0.14 2-chloro- 4.48 Wheat 0 60 allyl-p- chlorodi- thiocar- banilate 0.84 2-chloro- 4.48 Wheat 55 39 allyl-p- chlorodi- thiocar- banilate115 0.14 2-chloro- 4.48 Wheat 25 35 allyl-3,4-di- chlorodithio- carbanilate116 0.14 2-chloro- 4.48 Wheat 30 30 allyl-p-nitro- dithiocarbanilate 0.84 2-chloro- 4.48 Wheat 75 19 allyl-p-nitro- dithiocarbanilate117 0.14 2-chloro- 4.48 Wheat 25 35 allyl-3-nitro- carbanilate118 0.14 3-chloro- 4.48 Wheat 35 25 allyl-3-nitro- carbanilate 0.14 3-chloro- 4.48 Sorghum 75 15 allyl-3-nitro- carbanilate119 0.14 2-chloro- 4.48 Wheat 10 50 allyl-p-fluoro- dithiocarbanilate 0.84 2-chloro- 4.48 Wheat 70 24 allyl-p-fluoro- dithiocarbanilate120 0.14 4-iodo-2- 4.48 Wheat 15 35 butynyl-p- methoxycar- banilate 0.84 4-iodo-2- 4.48 Wheat 50 44 butynyl-p- methoxycar- banilate 4.48 4-iodo-2- 4.48 Wheat 75 20 butynyl-p- methoxycar- banilate 0.14 4-iodo-2- 4.48 Sorghum 75 15 butynyl-p- methoxycar- banilate121 0.07 Allyl-N- 4.48 Wheat 0 30 methyldithio- carbanilate 0.28 Allyl-N- 4.48 Wheat 10 25 methyldithio- carbanilate 1.12 Allyl-N- 4.48 Wheat 30 35 methyldithio- carbanilate 0.07 Allyl-N- 4.48 Sorghum 15 80 methyldithio- carbanilate 0.28 Allyl-N- 4.48 Sorghum 30 65 methyldithio- carbanilate 1.12 Allyl-N- 4.48 Sorghum 50 49 methyldithio- carbanilate 4.48 Allyl-N- 4.48 Sorghum 75 24 methyldithio- carbanilate122 0.07 Benzyldi- 4.48 Wheat 0 30 isopropylcar- bamate 0.28 Benzyldi- 4.48 Wheat 20 15 isopropylcar- bamate 1.12 Benzyldi- 4.48 Wheat 35 30 isopropylcar- bamate 4.48 Benzyldi- 4.48 Wheat 80 18 isopropylcar- bamate 0.07 Benzyldi- 4.48 Sorghum 20 75 isopropylcar- bamate 0.28 Benzyldi- 4.48 Sorghum 40 55 isopropylcar- bamate 1.12 Benzyldi- 4.48 Sorghum 65 34 isopropylcar- bamate123 0.07 Benzyliso- 2.24 Wheat 0 30 butyldithio- carbamate 0.28 Benzyliso- 2.24 Wheat 10 25 butyldithio- carbamate 1.12 Benzyliso- 2.24 Wheat 45 20 butyldithio- carbamate 4.48 Benzyliso- 2.24 Wheat 75 23 butyldithio- carbamate 0.07 Benzyliso- 2.24 Sorghum 55 40 butyldithio- carbamate 0.28 Benzyliso- 2.24 Sorghum 70 25 butyldithio- carbamate124 0.07 Cyclo- 4.48 Wheat 0 30 hexyl-N-allyl- cyclohexane- carbamate 0.28 Cyclo- 4.48 Wheat 15 20 hexyl-N-allyl- cyclohexane- carbamate 0.07 Cyclo- 4.48 Sorghum 30 65 hexyl-N-allyl- cyclohexane- carbamate 0.28 Cyclo- 4.48 Sorghum 70 25 hexyl-N-allyl- cyclohexane- carbamate125 0.07 Ethyl-N- 2.24 Wheat 0 30 ethylthiono- cyclohexane- carbamate 0.28 Ethyl-N- 2.24 Wheat 10 25 ethylthiono- cyclohexane- carbamate 0.07 Ethyl-N- 2.24 Sorghum 30 65 ethylthiono- cyclohexane- carbamate 0.28 Ethyl-N- 2.24 Sorghum 70 25 ethylthiono- cyclohexane- carbamate126 0.07 Ethylthiol- 4.48 Wheat 0 30 cyclohexane- carbamate 0.07 Ethylthiol- 4.48 Sorghum 40 55 cyclohexane- carbamate127 0.07 Propyl-N- 4.48 Wheat 0 30 butylthiono- cyclohexane- carbamate 0.28 Propyl-N- 4.48 Wheat 15 20 butylthiono- cyclohexane- carbamate 0.07 Propyl-N- 4.48 Sorghum 70 25 butylthiono- cyclohexane- carbamate128 0.07 Phenyldi- 4.48 Wheat 0 30 ethyldithio- carbamate 0.28 Phenyldi- 4.48 Wheat 10 25 ethyldithio- carbamate 0.07 Phenyldi- 4.48 Sorghum 0 95 ethyldithio- carbamate 0.28 Phenyldi- 4.48 Sorghum 40 55 ethyldithio- carbamate129 0.07 2-chloro- 4.48 Wheat 0 30 allyl-3,6-dihydro- 1(2H)pyridine carbo- thiolate 0.07 2-chloro- 4.48 Sorghum 60 35 allyl-3,6-dihydro- 1(2H)pyridine carbo- thiolate130 0.07 Ethyl- 4.48 Wheat 0 30 piperidinethio- carboxylate 0.28 Ethyl- 4.48 Wheat 20 15 piperidinethio- carboxylate 1.12 Ethyl- 4.48 Wheat 45 20 piperidinethio- carboxylate 0.07 Ethyl- 4.48 Sorghum 75 20 piperidinethio- carboxylate131 0.28 Allyl-N- 4.48 Wheat 0 25 methyldi- thiocar- banilate 1.12 Allyl-N- 4.48 Wheat 45 25 methyldi- thiocar- banilate 0.07 Allyl-N- 4.48 Sorghum 15 35 methyldi- thiocar- banilate 0.28 Allyl-N- 4.48 Sorghum 25 65 methyldi- thiocar- banilate 1.12 Allyl-N- 4.48 Sorghum 40 60 methyldi- thiocar- banilate 4.48 Allyl-N- 4.48 Sorghum 50 50 methyldi- thiocar- banilate132 0.07 Allyldi- 4.48 Sorghum 25 25 thio-2-cyclo- hexene-1-car- bamate 0.28 Allyldi- 4.48 Sorghum 50 40 thio-2-cyclo- hexene-1-car- bamate 1.12 Allyldi- 4.48 Sorghum 80 20 thio-2-cyclo- hexene-1-car- bamate133 0.28 2-cyclo- 4.48 Wheat 10 15 hexen-1-yl diisopropyl- thiolcarbamate 1.12 2-cyclo- 4.48 Wheat 20 50 hexen-1-yl diisopropyl- thiolcarbamate134 0.07 Pentylhexa- 4.48 Sorghum 25 24 hydro(1H)- azepine-1-car- boxylate 0.28 Pentylhexa- 4.48 Sorghum 50 40 hydro(1H)- azepine-1-car- boxylate 1.12 Pentylhexa- 4.48 Sorghum 85 15 hydro(1H)- azepine-1-car- boxylate135 0.28 Isopropyl- 4.48 Wheat 0 25 hexahydroazocine- 1(2H)carbothionate 1.12 Isopropyl- 4.48 Wheat 25 45 hexahydroazocine- 1(2H)carbothionate 4.48 Isopropyl- 4.48 Wheat 75 15 hexahydroazocine- 1(2H)carbothionate136 0.28 Ethylocta- 4.48 Wheat 0 25 hydro(1H)azonine- thionocarboxylate 1.12 Ethylocta- 4.48 Wheat 30 40 hydro(1H)azonine- thionocarboxylate137 0.07 Methyl-N- 4.48 Sorghum 40 10 methyldithio- carbanilate 0.28 Methyl-N- 4.48 Sorghum 45 45 methyldithio- carbanilate 1.12 Methyl-N- 4.48 Sorghum 65 35 methyldithio- carbanilate138 0.28 3-chloro- 4.48 Wheat 0 25 2-butenyl- carbanilate 1.12 3-chloro- 4.48 Wheat 50 20 2-butenyl- carbanilate 0.07 3-chloro- 4.48 Sorghum 30 20 2-butenyl- carbanilate 0.28 3-chloro- 4.48 Sorghum 65 25 2-butenyl- carbanilate 1.12 3-chloro- 4.48 Sorghum 70 30 2-butenyl- carbanilate139 0.14 Allylthiol- 4.48 Wheat 30 18 carbamate 0.14 Allylthiol- 4.48 Sorghum 65 32 carbamate140 0.14 2-nitro-4- 4.48 Sorghum 50 47 trifluoromethyl- phenyl-N,N-di- methyldithiocar- bamate141 0.14 Allyl-N- 4.48 Wheat 15 33 cyclohexyl- thionocar- banilate 0.84 Allyl-N- 4.48 Wheat 55 20 cyclohexyl- thionocar- banilate 0.14 Allyl-N- 4.48 Sorghum 35 62 cyclohexyl- thionocar- banilate 0.84 Allyl-N- 4.48 Sorghum 65 33 cyclohexyl- thionocar- banilate142 0.14 Methyl-4- 4.48 Wheat 20 28 morpholino- carbodithioate143 0.14 Methyl-N- 4.48 Wheat 15 33 butylcar- banilate 0.84 Methyl-N- 4.48 Wheat 50 25 butylcar- banilate144 0.14 Allyl-N- 4.48 Wheat 15 33 methylthiol- carbamate 0.14 Allyl-N- 4.48 Sorghum 50 47 methylthiol- carbamate 0.84 Allyl-N- 4.48 Sorghum 75 23 methylthiol- carbamate145 0.28 2-chloro- 4.48 Sorghum 10 5 allyl-N-iso- butyldithio- carbanilate 0.56 2-chloro- 4.48 Sorghum 15 20 allyl-N-iso- butyldithio- carbanilate 1.12 2-chloro- 4.48 Sorghum 25 20 allyl-N-iso- butyldithio- carbanilate 2.24 2-chloro- 4.48 Sorghum 30 60 allyl-N-iso- butyldithio- carbanilate146 0.28 2-chloro- 4.48 Sorghum 10 5 allyl-p-chloro- dithiocarbanilate 0.56 2-chloro- 4.48 Sorghum 15 20 allyl-p-chloro- dithiocarbanilate 2.24 2-chloro- 4.48 Sorghum 55 35 allyl-p-chloro- dithiocarbanilate147 0.56 Methyl-p- 4.48 Sorghum 45 43 methyl-N-methyl- dithiocarbanilate 1.12 Methyl-p- 4.48 Sorghum 45 45 methyl-N-methyl- dithiocarbanilate 2.24 Methyl-p- 4.48 Sorghum 50 47 methyl-N-methyl- dithiocarbanilate 4.48 Methyl-p- 4.48 Sorghum 55 42 methyl-N-methyl- dithiocarbanilate__________________________________________________________________________ TABLE I (B)__________________________________________________________________________ Per- Safen- Acetan- Antag- cent ingEx. ilide Amount onistic Amount Inhibi- EffectNo. Herbicide (kg./ha.) Agent (kg./ha.) Crop tion (%)__________________________________________________________________________148 alachlor 4.48 Methyl-N- 4.48 Wheat 35 43 methyl-O- methyldithio- - carbanilate alachlor 4.48 Methyl-N- 4.48 Sorghum 75 20 methyl-O- methyldithio- carbanilate butachlor 4.48 Methyl-N- 4.48 Wheat 10 33 methyl-O- methyldithio- carbanilate butachlor 4.48 Methyl-N- 4.48 Sorghum 40 35 methyl-O- methyldithio- carbanilate149 butachlor 4.48 Methyl-N- 4.48 Wheat 20 23 ethyl-p-chloro- dithiocar- banilate butachlor 4.48 Methyl-N- 4.48 Sorghum 45 30 ethyl-p-chloro- dithiocar- banilate150 alachlor 0.56 2-cyclo- 4.48 Sorghum 50 33 hexen-1-yl-N- methyldithio- carbanilate alachlor 4.48 2-cyclo- 4.48 Sorghum 70 25 hexen-1-yl-N- methyldithio- carbanilate butachlor 4.48 2-cyclo- 4.48 Sorghum 50 25 hexen-1-yl-N- methyldithio- carbanilate151 butachlor 4.48 Ethyl-N- 4.48 Sorghum 65 20 isopropyl- carbanilate152 butachlor 0.56 Isopropyl-N- 4.48 Sorghum 15 25 isopropylcar- banilate butachlor 4.48 Isopropyl- 4.48 Sorghum 55 30 N-isopropyl- carbanilate153 butachlor 4.48 Methyl-N- 4.48 Sorghum 60 25 isopropyl- carbanilate154 butachlor 4.48 Butyl-N-iso- 4.48 Sorghum 70 15 propylthiol- carbanilate155 butachlor 4.48 o-fluoro- 4.48 Sorghum 60 25 benzyl-N- methyldithio- carbanilate156 butachlor 4.48 m-fluoro- 4.48 Sorghum 70 15 benzyl-N- methyldithio- carbanilate157 butachlor 4.48 m-trifluoro- 4.48 Wheat 10 35 methylbenzyl- N-methyldithio- carbanilate butachlor 0.56 m-trifluoro- 4.48 Sorghum 20 20 methylbenzyl- N-methyldithio- carbanilate butachlor 4.48 m-trifluoro- 4.48 Sorghum 60 25 methylbenzyl- N-methyldithio- carbanilate158 butachlor 0.56 Benzyl-N- 4.48 Wheat 0 15 butyldithio- carbanilate butachlor 0.56 Benzyl-N- 4.48 Sorghum 20 20 butyldithio- carbanilate159 butachlor 4.48 Methyl-N- 4.48 Wheat 20 25 propyldithio- carbanilate butachlor 4.48 Methyl-N- 4.48 Sorghum 45 40 propyldithio- carbanilate160 alachlor 0.28 Allyl-N- 4.48 Sorghum 35 20 propyldithio- carbanilate butachlor 0.56 Allyl-N- 4.48 Sorghum 30 10 propyldithio- carbanilate butachlor 4.48 Allyl-N- 4.48 Sorghum 45 40 propyldithio- carbanilate161 alachlor 0.28 Methyl-N- 4.48 Sorghum 45 10 propylthiol- carbanilate alachlor 2.24 Methyl-N- 4.48 Sorghum 75 10 propylthiol- carbanilate butachlor 0.56 Methyl-N- 4.48 Sorghum 25 15 propylthiol- carbanilate162 butachlor 4.48 Ethyl-N- 4.48 Sorghum 70 15 propylthiol- carbanilate163 butachlor 4.48 Propyl-N- 4.48 Sorghum 70 15 propylthiol- carbanilate164 butachlor 4.48 Propyl-N- 4.48 Wheat 25 20 propyldithio- carbanilate165 butachlor 4.48 Allylthiono- 4.48 Sorghum 55 40 carbanilate166 alachlor 2.24 Cyanoethyl- 4.48 Sorghum 45 25 N-methyl- dithio- carbanilate butachlor 4.48 Cyanoethyl- 4.48 Sorghum 60 35 N-methyl- dithio- carbanilate167 butachlor 4.48 Butyl-N- 4.48 Sorghum 50 45 isopropyl- dithio- carbanilate168 butachlor 0.56 Methyl-N- 4.48 Wheat 0 10 isopropyl- dithio- carbanilate butachlor 4.48 Methyl-N- 4.48 Wheat 20 25 isopropyl- dithio- carbanilate169 butachlor 4.48 Butyl-N- 4.48 Sorghum 70 25 isopropyl- carbanilate170 butachlor 4.48 Propyl-N- 4.48 Sorghum 70 25 isopropyl- carbanilate171 butachlor 4.48 Allyl-m- 4.48 Sorghum 65 23 chlorodithio- carbanilate172 butachlor 0.56 2-chloro- 4.48 Sorghum 20 20 allyldithio- carbanilate173 alachlor 0.28 Allylthiono- 4.48 Wheat 20 35 carbanilate butachlor 0.56 Allylthiono- 4.48 Sorghum 45 38 carbanilate butachlor 2.24 Allylthiono- 4.48 Sorghum 60 33 carbanilate butachlor 8.96 Allylthiono- 4.48 Sorghum 70 28 carbanilate174 butachlor 0.56 Isopropyl- 4.48 Sorghum 50 33 N-butyl- carbanilate butachlor 2.24 Isopropyl- 4.48 Sorghum 70 23 N-butyl- carbanilate175 alachlor 0.56 Allyl-N- 4.48 Sorghum 60 25 methyldithio- carbanilate alachlor 1.12 Allyl-N- 4.48 Sorghum 75 20 methyldithio- carbanilate butachlor 0.56 Allyl-N- 4.48 Sorghum 20 63 methyldithio- carbanilate butachlor 2.24 Allyl-N- 4.48 Sorghum 50 43 methyldithio- carbanilate butachlor 8.96 Allyl-N- 4.48 Sorghum 60 38 methyldithio- carbanilate176 alachlor 0.28 Methyl-N- 4.48 Wheat 0 55 ethyldithio- carbanilate alachlor 1.12 Methyl-N- 4.48 Wheat 45 48 ethyldithio- carbanilate alachlor 4.48 Methyl-N- 4.48 Wheat 70 30 ethyldithio- carbanilate alachlor 0.28 Methyl-N- 4.48 Sorghum 60 33 ethyldithio- carbanilate butachlor 0.56 Methyl-N- 4.48 Sorghum 50 33 ethyldithio- carbanilate butachlor 2.24 Methyl-N- 4.48 Sorghum 70 23 ethyldithio- carbanilate177 2'-t-butyl 4.48 Allylthiono- 4.48 Wheat 40 406'-methyl- carbanilate 2-bromo- acetanilide N-butoxy- 0.28 Allylthiono- 4.48 Wheat 40 33 methyl-2' carbanilatet-butyl- 6'-methyl- acetanilide178 2'-t-butyl 1.12 Isopropyl- 4.48 Wheat 35 256'-methyl- N-butyl- 2-bromo- carbanilate acetanilide 2'-t-butyl 0.28 Isopropyl- 4.48 Sorghum 30 676'-methyl- N-butyl 2-bromo- carbanilate acetanilide179 2'-t-butyl 0.28 Allyl-N- 4.48 Wheat 70 276'-methyl- methyldithio- 2-bromo- carbanilate acetanilide N-butoxy- 0.28 Allyl-N- 4.48 Wheat 40 33 methyl-2' methyldithio-t-butyl- carbanilate 6'-methyl- acetanilide N-butoxy- 0.28 Allyl-N- 4.48 Sorghum 35 63 methyl-2' methyldithio-t-butyl- carbanilate 6'-methyl- acetanilide180 2'-t-butyl 0.28 Methyl-N- 4.48 Wheat 0 106'-methyl- ethyldithio- 2-bromo- carbanilate acetanilide 2'-t-butyl 1.12 Methyl-N- 4.48 Wheat 30 306'-methyl- ethyldithio- 2-bromo- carbanilate acetanilide N-butoxy- 0.28 Methyl-N- 4.48 Wheat 40 33 methyl-2' ethyldithio-t-butyl- carbanilate 6'-methyl- acetanilide N-butoxy- 1.12 Methyl-N- 4.48 Wheat 65 28 methyl-2' ethyldithio-t-butyl- carbanilate 6'-methyl- acetanilide N-butoxy- 0.28 Methyl-N- 4.48 Sorghum 70 28 methyl-2' ethyldithio-t-butyl- carbanilate 6'-methyl- acetanilide__________________________________________________________________________

In the tables herein, the columns headed Percent Inhibition contain the observations of test pans of plants which quantify the response of plants to a combination treatment of acentanilide herbicide and safening agent. Likewise, the columns headed Safening Effect (%) contain the difference between the response of plants to treatment with acetanilide herbicide and the response of plants to a combination treatment of the same acetanilide herbicide and safening agent. Although in the foregoing examples the safening agent is applied to the soil before the acetanilide herbicide, equivalent results are obtainable when the safening agent is applied in mixture with the acetanilide herbicide or in sequence after the acetanilide herbicide is applied. This also is observed in post-emergent applications. The ability to be applied as mixtures and obtain safening of acetanilide herbicide with wheat and sorghum is confirmed in tank mix tests.

A key contribution of the present invention is that the safening or antagonistic agents when applied to seed reduce crop injury without reducing effective weed control by the acetanilide herbicides.

EXAMPLE 181

The procedure employed in Examples 1 through 180 is repeated except that neither the herbicide nor the antagonistic agents are incorporated into the soil, but rather the soil is placed over sorghum and weed seeds, the herbicide is sprayed on the surface of the soil, the antagonistic agent is then sprayed on the surface of the soil and then water from overhead is added to a depth of 6.3 mm. across the surface of each pan. Thereafter, until observation of results, water is added from below by subirrigation. All weeds are substantially controlled. The safening effect on sorghum is shown in Table II.

TABLE II______________________________________Amount of Per-alachlor Antago- centHerbicide nistic Amount Inhibi- Safening(kg./ha.) Agent (kg./ha.) tion Effect(%)______________________________________0.28 Isopropyl- 4.48 30 60 N-butylcar- banilate0.56 Isopropyl- 4.48 20 75 N-butylcar- banilate1.12 Isopropyl 4.48 85 12 N-butylcar- banilate2.24 Isopropyl 4.48 70 29 N-butylcar- banilate0.28 Methyl-N- 4.48 30 60 ethyldithio- carbanilate0.56 Methyl-N- 4.48 55 40 ethyldithio- carbanilate1.12 Methyl-N- 4.48 80 17 ethyldithio- carbanilate2.24 Methyl-N- 4.48 90 9 ethyldithio- carbanilate______________________________________

EXAMPLE 182

The primary use of acetanilideherbicides is for preemergent control of weeds by application of the herbicide to the soil before the plants emerge. This example illustrates the safening effect on alachlor herbicide when applied as a postemergent treatment on weeds in a crop of sorghum. Excellent weed control is shown with a substantial reduction in crop injury by the herbicide. The herbicide and antagonistic agent to be tested are applied in spray form to plants of a given age of several grasses and broadleaf species. In this test, one week after the plants are planted, each aluminum pan of plants is sprayed with a given volume of a solution of the desired percent concentration of the herbicide and antagonistic agent in sequence. The solution of safening agent is prepared by weighing the appropriate amount of agent in a suitable container, dissolving the safening agent in acetone and mixing the acetone solution with an approximately equal volume of water. The mixture of water and acetone solution is sprayed on the plants. The acetanilide herbicide along with a suitable emulsifying agent is dispersed in a suitable amount of water. The resulting water emulsion is then sprayed on the plants. The injuries to the plants are then observed approximately 21 days later and the results are recorded as percent inhibition of the plant. The results observed with respect to sorghum injury are presented in Table III.

EXAMPLE 183

The procedure of Example 182 is repeated except that the antagonistic agent is applied as a seed treatment rather than as a sequential spray before application of the herbicide. For seed treatment, the antagonistic agent is mixed with an inert carrier comprising a finely-divided clay and a high surface area calcium silicate in a range of weight percentages of active antagonistic agent to inert carrier. An excess of the antagonistic agent/inert carrier mixture is thoroughly mixed with the crop seed to be protected. With respect to sorghum seed, the following correlation of the composition of the mixture to the quantity of active ingredient per unit weight of sorghum seed is observed.

______________________________________Percent by weight Percent by weightof active antago- of active antago-nistic agent to nistic agent toinert carrier (% sorghum seed aftercomposition) treatment (% on seed)______________________________________ 1.25 0.125 2.5 0.25 5 0.510 1.0______________________________________

The results of applying antagonistic agents as a seed treatment of sorghum seed at various percentages and applying alachlor herbicide as a post-emergent herbicide at various application rates is shown in Table IV. Good control of weed species is observed.

TABLE III______________________________________Amount of Per-alachlor Antago- centHerbicide nistic Amount Inhibi- Safening(kg./ha.) Agent (kg./ha.) tion Effect (%)______________________________________2.24 Isopropyl-N- 0.28 15 30 butylcarbanilate2.24 Isopropyl-N- 1.12 25 20 butylcarbanilate2.24 Isopropyl-N- 4.48 20 25 butylcarbanilate2.24 Methyl-N-ethyl- 0.28 20 25 dithiocarbanilate______________________________________ TABLE IV______________________________________Amount of % On Seedalachlor Antago- Of Antago- PercentHerbicide nistic nistic Inhibi- Safening(kg./ha.) Agent Agent tion Effect (%)______________________________________1.12 Isopropyl-N- 0.25 28 45 butylcarbanilate2.24 Isopropyl-N- 0.25 43 37 butylcarbanilate4.48 Isopropyl-N- 0.25 50 20 butylcarbanilate1.12 Isopropyl-N- 1.00 58 15 butylcarbanilate2.24 Isopropyl-N- 1.00 58 22 butylcarbanilate4.48 Isopropyl-N- 1.00 60 10 butylcarbanilate1.12 Methyl-N-ethyl- 0.125 33 40 dithiocarbanilate2.24 Methyl-N-ethyl- 0.125 75 5 dithiocarbanilate1.12 Methyl-N-ethyl- 0.50 53 20 dithiocarbanilate2.24 Methyl-N-ethyl- 0.50 58 22 dithiocarbanilate0.56 Allyl-N-methyl- 0.25 15 38 dithiocarbanilate1.12 Allyl-N-methyl- 0.25 35 50 dithiocarbanilate2.24 Allyl-N-methyl- 0.25 63 30 dithiocarbanilate4.48 Allyl-N-methyl- 0.25 85 10 dithiocarbanilate0.56 Allyl-N-methyl- 1.00 10 43 dithiocarbanilate1.12 Allyl-N-methyl- 1.00 20 65 dithiocarbanilate2.24 Allyl-N-methyl- 1.00 40 53 dithiocarbanilate4.48 Allyl-N-methyl- 1.00 78 17 dithiocarbanilate______________________________________

EXAMPLES 184-202

These examples illustrate the application of the antagonistic agents of this invention as seed treatments to protect desired crops from herbicidal injury by acetanilide herbicides. In these examples the herbicide is applied to the soil as in Example 1-180. However, the antagonistic agent is applied to crop seed as in Example 183. The results are tabulated in Table V which show the safening effect of the antagonistic agents of this invention.

In order to counteract injury by the selective acetanilide herbicide, the crop seed need be treated with only a small amount of the antagonistic agent. For example, application rates of about 1100 g. to as low as about 1.5 g. of active agent per bushel of seed may be used. The presently preferred application rate is in the range of about 3 g. to 550 g. of agent per bushel. The seed is treated with an antagonistic agent by use of conventional seed treating apparatus well known to the art. The seed is thoroughly mixed with the antagonistic agent in the seed treating apparatus, thereby giving a seed which is coated with the agent.

Since only a very small amount of active antagonistic agent is required for the seed treatment, the compound preferably is formulated as a wettable powder or an emulsifiable concentrate which can be diluted with water by the seed treater for use in the seed treating apparatus. Of course, under certain conditions, it may be desirable to dissolve the antagonistic agent in an organic solvent for use as a seed treatment or the pure compound alone may be used under properly controlled conditions.

There are thus also provided by this invention novel seed treating compositions containing one or more of the described active antagonistic agents intimately dispersed in an inert carrier or diluent for the intended use. Such carriers may be either solids, such as talc, clay, diatomaceous earth, sawdust, calcium carbonate, and the like or liquids such as water, kerosene, acetone, benzene, toluene, xylene, and the like in which the active agent may be either dissolved or dispersed. Emulsifying agents are advisably used to achieve a suitable emulsion if two immiscible liquids are used as a carrier. Wetting agents may also be used to aid in dispersing the active antagonistic agent in liquids used as a carrier in which the agent is not completely soluble. Emulsifying agents and wetting agents, also known as "surface active agents," are sold under numerous tradenames and may be either pure compounds, mixtures of compounds of the same general groups, or they may be mixtures of compounds of different classes. Typical satisfactory surface active agents which may be used are alkali metal higher alkylarylsulfonates such as sodium dodecylbenzenesulfonate and the soldium salts of alkylnaphthalenesulfonic acids, fatty alcohol sulfates such as the sodium salts of monoesters of sulfuric acid with n-aliphatic alcohols containing 8-18 carbon atoms, long chain quaternary ammonium compounds, sodium salts of petroleum-derived alkylsulfonic acids, polyethylene sorbitan monooleate, alkylaryl polyether alcohols, water-soluble lignin sulfonate salts, alkali-casein compositions, long chain alcohols usually containing 10 to 18 carbon atoms, and condensation products of ethylene oxide with fatty acids, alkylphenols and mercaptans.

TABLE V__________________________________________________________________________ Amount of Per- alachlor Antago- Weight cent SafeningExample Herbicide nistic % on Inhibi- EffectNumber (kg./ha.) Agent Seed Crop tion (%)__________________________________________________________________________184 0.28 Isopropyl-N- 0.25 Sorghum 0 78 butylcarbani- late 0.28 Isopropyl-N- 0.50 Sorghum 0 78 butylcarbani- late 0.28 Isopropyl-N- 1.00 Sorghum 5 73 butylcarbani- late 0.56 Isopropyl-N- 0.25 Sorghum 0 75 butylcarbani- late 0.56 Isopropyl-N- 0.50 Sorghum 5 70 butylcarbani- late 0.56 Isopropyl-N- 1.00 Sorghum 10 65 butylcarbani- late 1.12 Isopropyl-N- 0.25 Sorghum 0 93 butylcarbani- late 1.12 Isopropyl-N- 0.50 Sorghum 0 93 butylcarbani- late 1.12 Isopropyl-N- 1.00 Sorghum 10 83 butylcarbani- late 2.24 Isopropyl-N- 0.25 Sorghum 25 75 butylcarbani- late 2.24 Isopropyl-N- 0.50 Sorghum 0 100 butylcarbani- late 2.24 Isopropyl-N- 1.00 Sorghum 0 100 butylcarbani- late185 0.28 Methyldiethyl- 0.25 Wheat 0 13 thionocar- bamate 0.28 Methyldiethyl- 0.50 Wheat 0 13 thionocar- bamate 0.28 Methyldiethyl- 0.25 Sorghum 55 23 thionocar- bamate 0.28 Methyldiethyl- 0.50 Sorghum 65 13 thionocar- bamate186 0.28 Methyl-N- 0.25 Wheat 0 13 ethyldithio- carbanilate 0.56 Methyl-N- 0.25 Wheat 5 10 ethyldithio- carbanilate 1.12 Methyl-N- 0.25 Wheat 0 15 ethyldithio- carbanilate 0.28 Methyl-N- 0.25 Sorghum 25 53 ethyldithio- carbanilate 0.28 Methyl-N- 0.50 Sorghum 30 48 ethyldithio- carbanilate 0.28 Methyl-N- 1.00 Sorghum 35 43 ethyldithio- carbanilate 0.56 Methyl-N- 0.25 Sorghum 25 50 ethyldithio- carbanilate 0.56 Methyl-N- 0.50 Sorghum 40 35 ethyldithio- carbanilate 0.56 Methyl-N- 1.00 Sorghum 40 35 ethyldithio- carbanilate 1.12 Methyl-N- 0.25 Sorghum 25 68 ethyldithio- carbanilate 1.12 Methyl-N- 0.50 Sorghum 25 68 ethyldithio- carbanilate 1.12 Methyl-N- 1.00 Sorghum 30 63 ethyldithio- carbanilate 2.24 Methyl-N- 0.25 Sorghum 40 60 ethyldithio- carbanilate 2.24 Methyl-N- 0.50 Sorghum 25 75 ethyldithio- carbanilate 2.24 Methyl-N- 1.00 Sorghum 50 50 ethyldithio- carbanilate187 0.28 Isopropyl-N- 0.016 Sorghum 45 30 butylcarbani- late 0.28 Isopropyl-N- 0.031 Sorghum 35 40 butylcarbani- late 0.28 Isopropyl-N- 0.063 Sorghum 35 40 butylcarbani- late 0.28 Isopropyl-N- 0.125 Sorghum 10 65 butylcarbani- late 0.28 Isopropyl-N- 0.25 Sorghum 15 60 butylcarbani- late 0.56 Isopropyl-N- 0.016 Sorghum 45 40 butylcarbani- late 0.56 Isopropyl-N- 0.031 Sorghum 50 35 butylcarbani- late 0.56 Isopropyl- 0.063 Sorghum 40 45 N-butylcar- banilate 0.56 Isopropyl- 0.125 Sorghum 15 70 N-butylcar- banilate 0.56 Isopropyl- 0.250 Sorghum 18 67 N-butylcar- banilate 1.12 Isopropyl- 0.016 Sorghum 65 27 N-butylcar- banilate 1.12 Isopropyl- 0.031 Sorghum 55 37 N-butylcar- banilate 1.12 Isopropyl- 0.063 Sorghum 50 42 N-butylcar- banilate 1.12 Isopropyl- 0.125 Sorghum 25 67 N-butylcar- banilate 1.12 Isopropyl- 0.250 Sorghum 40 52 N-butylcar- banilate 2.24 Isopropyl- 0.016 Sorghum 85 8 N-butylcar- banilate 2.24 Isopropyl- 0.031 Sorghum 85 8 N-butylcar- banilate 2.24 Isopropyl- 0.063 Sorghum 50 43 N-butylcar- banilate 2.24 Isopropyl- 0.125 Sorghum 40 53 N-butylcar- banilate 2.24 Isopropyl- 0.250 Sorghum 35 58 N-butylcar- banilate188 0.28 Methyl-N- 0.016 Sorghum 65 10 ethyldithio- carbanilate 0.28 Methyl-N- 0.031 Sorghum 50 25 ethyldithio- carbanilate 0.28 Methyl-N- 0.063 Sorghum 20 55 ethyldithio- carbanilate 0.28 Methyl-N- 0.125 Sorghum 15 60 ethyldithio- carbanilate 0.28 Methyl-N- 0.250 Sorghum 30 45 ethyldithio- carbanilate 0.56 Methyl-N- 0.016 Sorghum 65 20 ethyldithio- carbanilate 0.56 Methyl-N- 0.031 Sorghum 50 35 ethyldithio- carbanilate 0.56 Methyl-N- 0.063 Sorghum 25 60 ethyldithio- carbanilate 0.56 Methyl-N- 0.125 Sorghum 20 65 ethyldithio- carbanilate 0.56 Methyl-N- 0.250 Sorghum 35 50 ethyldithio- carbanilate 1.12 Methyl-N- 0.016 Sorghum 65 27 ethyldithio- carbanilate 1.12 Methyl-N- 0.031 Sorghum 70 22 ethyldithio- carbanilate 1.12 Methyl-N- 0.063 Sorghum 40 52 ethyldithio- carbanilate 1.12 Methyl-N- 0.125 Sorghum 35 57 ethyldithio- carbanilate 1.12 Methyl-N- 0.250 Sorghum 35 57 ethyldithio- carbanilate 2.24 Methyl-N- 0.016 Sorghum 80 13 ethyldithio- carbanilate 2.24 Methyl-N- 0.031 Sorghum 75 18 ethyldithio- carbanilate 2.24 Methyl-N- 0.063 Sorghum 60 33 ethyldithio- carbanilate 2.24 Methyl-N- 0.125 Sorghum 40 53 ethyldithio- carbanilate 2.24 Methyl-N- 0.250 Sorghum 35 58 ethyldithio- carbanilate189 0.14 Allylthio- 0.016 Sorghum 70 15 nocarbani- late 0.14 Allylthio- 0.063 Sorghum 45 40 nocarbani- late 0.28 Allylthio- 0.063 Sorghum 65 34 nocarbani- late190 0.14 Allyl-N- 0.016 Sorghum 75 20 methyldithio- carbanilate 0.14 Allyl-N- 0.063 Sorghum 20 75 methyldithio- carbanilate 0.14 Allyl-N- 0.250 Sorghum 25 70 methyldithio- carbanilate 0.14 Allyl-N- 1.00 Sorghum 10 85 methyldithio- carbanilate 0.28 Allyl-N- 0.063 Sorghum 40 45 methyldithio- carbanilate 0.28 Allyl-N- 0.250 Sorghum 25 60 methyldithio- carbanilate 0.28 Allyl-N- 1.00 Sorghum 25 60 methyldithio- carbanilate 0.56 Allyl-N- 0.063 Sorghum 40 58 methyldithio- carbanilate 0.56 Allyl-N- 0.250 Sorghum 25 73 methyldithio- carbanilate 0.56 Allyl-N- 1.00 Sorghum 20 78 methyldithio- carbanilate 1.12 Allyl-N- 0.063 Sorghum 50 50 methyldithio- carbanilate 1.12 Allyl-N- 0.250 Sorghum 45 55 methyldithio- carbanilate 1.12 Allyl-N- 1.00 Sorghum 45 55 methyldithio- carbanilate 2.24 Allyl-N- 0.063 Sorghum 65 35 methyldithio- carbanilate 2.24 Allyl-N- 0.250 Sorghum 60 40 methyldithio- carbanilate 2.24 Allyl-N- 1.00 Sorghum 55 45 methyldithio- carbanilate191 0.28 Allyl- 0.25 Wheat 30 13 thiono- carbanilate 0.56 Allyl- 0.25 Wheat 15 48 thiono- carbanilate 1.12 Allyl- 0.25 Wheat 40 33 thiono- carbanilate 2.24 Allyl- 0.25 Wheat 55 25 thiono- carbanilate 4.48 Allyl- 0.25 Wheat 60 33 thiono- carbanilate192 0.28 Allyl-N- 1.00 Wheat 20 23 methyldithio- carbanilate 0.56 Allyl-N- 1.00 Wheat 25 38 methyldithio- carbanilate 1.12 Allyl-N- 1.00 Wheat 55 28 methyldithio- carbanilate 2.24 Allyl-N- 1.00 Wheat 65 15 methyldithio- carbanilate 4.48 Allyl-N- 1.00 Wheat 65 28 methyldithio- carbanilate193 0.28 2-Chloroallyl- 1.00 Wheat 10 33 o-chloro-N-(2- chloroallyl)di- thiocarbanilate 0.56 2-Chloroallyl- 1.00 Wheat 15 48 o-chloro-N-(2- chloroallyl)di- thiocarbanilate 1.12 2-Chloroallyl- 1.00 Wheat 25 48 o-chloro-N-(2- chloroallyl)di- thiocarbanilate 2.24 2-Chloroallyl- 1.00 Wheat 45 35 o-chloro-N-(2- chloroallyl)di- thiocarbanilate 4.48 2-Chloroallyl- 1.00 Wheat 60 33 o-chloro-N-(2- chloroallyl)di- thiocarbanilate194 0.28 Allyl-N- 0.063 Wheat 15 35 methyldithio- carbanilate 0.28 Allyl-N- 0.25 Wheat 30 20 methyldithio- carbanilate 0.56 Allyl-N- 0.25 Wheat 60 10 methyldithio- carbanilate 1.12 Allyl-N- 0.25 Wheat 60 15 methyldithio- carbanilate 0.28 Allyl-N- 1.00 Wheat 30 20 methyldithio- carbanilate 0.56 Allyl-N- 1.00 Wheat 40 30 methyldithio- carbanilate 1.12 Allyl-N- 1.00 Wheat 60 15 methyldithio- carbanilate195 0.14 2-chloroallyl- 0.016 Wheat 0 25 o-chloro-N- (2-chloroallyl) dithiocarbanilate 0.56 2-chloroallyl- 0.016 Wheat 40 20 o-chloro-N- (2-chloroallyl) dithiocarbanilate 0.14 2-chloroallyl- 0.063 Wheat 0 25 o-chloro-N- (2-chloroallyl) dithiocarbanilate 0.14 2-chloroallyl- 0.25 Wheat 0 25 o-chloro-N- (2-chloroallyl) dithiocarbanilate 0.28 2-chloroallyl- 0.25 Wheat 20 30 o-chloro-N- (2-chloroallyl) dithiocarbanilate 1.12 2-chloroallyl- 0.25 Wheat 60 15 o-chloro-N- (2-chloroallyl) dithiocarbanilate196 0.07 Allyl-N- 1.0 Sorghum 5 75 methyldithio- carbanilate 0.14 Allyl-N- 1.0 Sorghum 0 90 methyldithio- carbanilate 0.28 Allyl-N- 1.0 Sorghum 10 85 methyldithio- carbanilate 0.56 Allyl-N- 1.0 Sorghum 15 85 methyldithio- carbanilate 1.12 Allyl-N- 1.0 Sorghum 25 75 methyldithio- carbanilate 2.24 Allyl-N- 1.0 Sorghum 40 60 methyldithio- carbanilate 0.07 Allyl-N- 2.0 Sorghum 0 80 methyldithio- carbanilate 0.14 Allyl-N- 2.0 Sorghum 0 90 methyldithio- carbanilate 0.28 Allyl-N- 2.0 Sorghum 10 85 methyldithio- carbanilate 0.56 Allyl-N- 2.0 Sorghum 15 85 methyldithio- carbanilate 1.12 Allyl-N- 2.0 Sorghum 15 85 methyldithio- carbanilate 2.24 Allyl-N- 2.0 Sorghum 40 60 methyldithio- carbanilate 0.07 Allyl-N- 4.0 Sorghum 5 75 methyldithio- carbanilate 0.14 Allyl-N- 4.0 Sorghum 0 90 methyldithio- carbanilate 0.28 Allyl-N- 4.0 Sorghum 10 85 methyldithio- carbanilate 0.56 Allyl-N- 4.0 Sorghum 20 80 methyldithio- carbanilate 1.12 Allyl-N- 4.0 Sorghum 20 80 methyldithio- carbanilate 2.24 Allyl-N- 4.0 Sorghum 40 60 methyldithio- carbanilate197 0.28 2-Cyclohex- 0.25 Wheat 40 20 en-1-yldiiso- propylthiolcar- bamate198 0.14 Isopropylhex- 0.063 Wheat 15 15 ahydroazocine-1 (2H)-carbothionate 0.28 Isopropylhex- 0.063 Wheat 20 30 ahydroazocine-1 (2H)-carbothionate 0.56 Isopropylhex- 0.063 Wheat 30 50 ahydroazocine-1 (2H)-carbothionate 1.12 Isopropylhex- 0.063 Wheat 35 40 ahydroazocine-1 (2H)-carbothionate 2.24 Isopropylhex- 0.063 Wheat 65 20 ahydroazocine-1 (2H)-carbothionate 0.14 Isopropylhex- 0.25 Wheat 15 15 ahydroazocine-1 (2H)-carbothionate 0.28 Isopropylhex- 0.25 Wheat 20 30 ahydroazocine-1 (2H)-carbothionate 0.56 Isopropylhex- 0.25 Wheat 20 60 ahydroazocine-1 (2H)-carbothionate 1.12 Isopropylhex- 0.25 Wheat 30 45 ahydroazocine-1 (2H)-carbothionate 2.24 Isopropylhex- 0.25 Wheat 40 45 ahydroazocine-1 (2H)-carbothionate199 0.14 Ethyloctahydro- 0.063 Wheat 0 15 (1H)azoninecar- bothionate 0.28 Ethyloctahydro- 0.063 Wheat 5 60 (1H)azoninecar- bothionate 0.56 Ethylocta- 0.063 Wheat 20 45 hydro(1H)azo- ninecarbothionate 1.12 Ethylocta- 0.063 Wheat 15 55 hydro(1H)azo- ninecarbothionate 2.24 Ethylocta- 0.063 Wheat 60 20 hydro(1H)azo- ninecarbothionate 0.14 Ethylocta- 0.25 Wheat 0 15 hydro(1H)azo- ninecarbothionate 0.28 Ethylocta- 0.25 Wheat 25 40 hydro(1H)azo- ninecarbothionate 0.56 Ethylocta- 0.25 Wheat 20 45 hydro(1H)azo- ninecarbothionate 1.12 Ethylocta- 0.25 Wheat 25 45 hydro(1H)azo- ninecarbothionate 2.24 Ethylocta- 0.25 Wheat 35 45 hydro(1H)azo- ninecarbothionate200 0.14 Benzyliso- 0.063 Wheat 10 15 butyldithio- carbamate 0.28 Benzyliso- 0.063 Wheat 20 45 butyldithio- carbamate 0.56 Benzyliso- 0.063 Wheat 30 45 butyldithio- carbamate 0.28 Benzyliso- 0.25 Wheat 15 50 butyldithio- carbamate 0.56 Benzyliso- 0.25 Wheat 15 60 butyldithio- carbamate 1.12 Benzyliso- 0.25 Wheat 30 40 butyldithio- carbamate 2.24 Benzyliso- 0.25 Wheat 50 30 butyldithio- carbamate201 0.14 Methyl-N- 0.063 Wheat 0 10 methyldithio- carbanilate 0.28 Methyl-N- 0.063 Wheat 0 55 methyldithio- carbanilate 0.56 Methyl-N- 0.063 Wheat 45 20 methyldithio- carbanilate 1.12 Methyl-N- 0.063 Wheat 55 35 methyldithio- carbanilate 2.24 Methyl-N- 0.063 Wheat 60 30 methyldithio- carbanilate 0.14 Methyl-N- 0.25 Wheat 0 10 methyldithio- carbanilate 0.28 Methyl-N- 0.25 Wheat 0 55 methyldithio- carbanilate 0.56 Methyl-N- 0.25 Wheat 0 65 methyldithio- carbanilate 1.12 Methyl-N- 0.25 Wheat 15 75 methyldithio- carbanilate 2.24 Methyl-N- 0.25 Wheat 25 65 methyldithio- carbanilate 0.28 Methyl-N- 1.0 Wheat 20 35 methyldithio- carbanilate 0.56 Methyl-N- 1.0 Wheat 15 50 methyldithio- carbanilate 1.12 Methyl-N- 1.0 Wheat 25 65 methyldithio- carbanilate 2.24 Methyl-N- 1.0 Wheat 25 65 methyldithio- carbanilate202 0.14 Phenyldi- 0.25 Sorghum 0 15 ethyldithio- carbanilate 0.28 Phenyldi- 0.25 Sorghum 0 35 ethyldithio- carbanilate 0.56 Phenyldi- 0.25 Sorghum 10 55 ethyldithio- carbanilate 1.12 Phenyldi- 0.25 Sorghum 15 75 ethyldithio- carbanilate 0.56 Phenyldi- 1.0 Sorghum 40 25 ethyldithio- carbanilate 1.12 Phenyldi- 1.0 Sorghum 50 40 ethyldithio- carbanilate__________________________________________________________________________

The safening results found in greenhouse tests are substantiated by field tests of a representative antagonistic agent, allyl-N-methyldithiocarbanilate. Good results are obtained when sorghum and wheat seed is treated with this antagonistic agent formulated with a variety of liquid carriers such as ketone solvents, for example acetone, chlorinated hydrocarbon solvents, for example dichloromethane, aromatic solvents, for example toluene and ester solvents, for example ethyl acetate, as well as a variety of solid diluents such as clays, silicates and combinations of clays and silicates. The preferred concentrations of solid formulations range from about 10 percent to about 50 percent by weight of active antagonistic agent to total formulation weight.

While this invention has been described with respect to certain embodiments, it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art to which this invention appertains can be made without departing from the spirit or scope thereof.

Claims

1. A method for reducing injury to crops by .alpha.-haloacetanilide herbicides which comprises applying to the soil, crop, or crop seed an effective safening amount of a compound of the formula ##STR10##wherein R is C.sub.1-6 alkyl, C.sub.2-8 alkenyl or haloalkenyl, phenyl, cyanomethyl, cyclohexyl, cyclohexenyl, benzyl or benzyl substituted with halo, nitro or trifluoromethyl groups; R.sup.1 is C.sub.1-8 alkyl, C.sub.2-8 alkenyl, phenyl or phenyl substituted with halo, nitro or lower alkyl groups and R.sup.2 is hydrogen, C.sub.1-8 alkyl or C.sub.2-8 alkenyl or haloalkenyl.

2. A method of claim 1 wherein the crops are wheat and sorghum.

3. A method of claim 1 wherein the acetanilide is .alpha.-chloroacetanilide.

4. A method of claim 1 wherein the compound is applied to the soil.

5. A method of claim 4 wherein the compound is applied to the soil and incorporated into the soil.

6. A method of claim 4 wherein the compound is applied to the soil dispersed in a liquid carrier.

7. A method of claim 4 wherein the compound is applied to the soil dispersed on a particulate solid carrier.

8. A method of claim 1 wherein the compound is applied to the seed.

9. A method of claim 8 wherein the compound is applied to the seed dispersed in a liquid carrier.

10. A method of claim 8 wherein the compound is applied to the seed dispersed on a particulate solid carrier.

11. A method of claim 1 wherein R.sup.1 is phenyl or phenyl substituted with halo, nitro or lower alkyl groups.

12. A method of claim 11 wherein R is C.sub.1-6 alkyl.

13. A method of claim 12 wherein R.sup.2 is hydrogen.

14. A method of claim 12 wherein R.sup.2 is C.sub.1-6 alkyl.

15. A method of claim 12 wherein R.sup.2 is C.sub.2-8 alkenyl.

16. A method of claim 12 wherein R.sup.2 is C.sub.2-8 haloalkenyl.

17. A method of claim 11 wherein R is C.sub.2-8 alkenyl.

18. A method of claim 17 wherein R.sup.2 is hydrogen.

19. A method of claim 17 wherein R.sup.2 is C.sub.1-6 alkyl.

20. A method of claim 17 wherein R.sup.2 is C.sub.2-8 alkenyl.

21. A method of claim 17 wherein R.sup.2 is C.sub.2-8 haloalkenyl.

22. A method of claim 11 wherein R is phenyl.

23. A method of claim 1 wherein R is cyclohexyl or cyclohexenyl.

24. A method of claim 11 wherein R is C.sub.2-8 haloalkenyl.

25. A method of claim 1 wherein R.sup.1 is C.sub.1-6 alkyl.

26. A method of claim 25 wherein R is C.sub.1-6 alkyl.

27. A method of claim 26 wherein R.sup.2 is C.sub.1-6 alklyl.

28. Method of claim 3 wherein said .alpha.-chloroacetanilide is alachlor.

29. Method of claim 19 wherein said compound is allyl N-methyldithiocarbanilate.

30. A method of claim 1 wherein R is benzyl or benzyl substituted with halogen or trifluoromethyl.