GB1571904A

GB1571904A - Use of n-arylsulphonyl carbamates as herbicide antidotes

Info

Publication number: GB1571904A
Application number: GB40797/76A
Authority: GB
Original assignee: Stauffer Chemical Co
Current assignee: Stauffer Chemical Co
Priority date: 1975-10-02
Filing date: 1976-10-01
Publication date: 1980-07-23
Also published as: CH629081A5; AU509009B2; MX5392E; FR2326414B1; GB1571905A; FR2326414A1; IL50595A; YU241876A; DE2644504A1; AU1832876A; YU130682A; GR65992B; DD127619A5; DK442876A; NL7610893A; IL50595A0; NZ182204A; JPS5919533B2; CA1097649A; ES452285A1

Abstract

Compounds of the formula <IMAGE> in which n denotes a number from 1 to 3 and X and R have the meaning given in Patent Claim 1 are used as antidotes for reducing crop plant damage by thiocarbamate herbicides.

Description

(54) USE OF N-ARYL SULPHONYL CARBAMATES AS HERBICIDE ANTIDOTES (71) We, STAUFFER CHEMICAL COMPANY, a corporation organised under the laws of the State of Delaware, United States of America, of Westport, Connecticut 06880, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to the use of N-arylsulphonyl carbamates as herbicide antidotes.

While many herbicides are immediately toxic to a larger number of weed pests, it is known that the effect of many herbicides upon important plant cultivations is either non-selective or not adequately selective. Thus, many herbicides damage not only the weeds to be controlled, but also, to a greater or lesser extent, the desirable cultivated plants. This holds true for many herbicidal compounds which have been commercially successful and are commercially available. These herbicides include various types, such as triazines, urea derivatives, halogenated acetanilides, carbamates and thiolcarbamates. Some examples of these compounds are described in U.S. Patent Nos. 2,913,327; 3,037,853; 3,175,897; 3,185,720; 3,198,786 and 3,582,314.

The side effect of injury to a cultivated crop by various herbicides is particularly inconvenient and unfortunate. When used in the recommended amounts in the soil to control broadleaf weeds and grasses, serious malformation or stunting of the crop plants sometimes result. This abnormal growth in the crop plants results in loss of crop yield. The search continues for good selective herbicides.

Previous attempts have been described to overcome this problem. The treatment of the crop seed with certain 'hormonal' antagonistic agents prior to planting has been described; see U.S. Patent Nos.3,131,509 and 3,564,768. The protective agents, as well as the herbicide, in these prior references are largely specific to certain cultivated plant species or in the nature of the antagonistic agents. The prior antagonistic agents have not been notably successful. The aforementioned references specifically exemplify and describe the treatment of seeds employing compounds of a different chemical class, not suggestive of the present invention.

U.S. Patent Nos. 3,799,760 and 3,933,894 and East German Patent No. DL 74982 disclose certain N-benzenesulphonyl carbamate compounds. Also, in Berichte Vol. 37 at page 699, certain compounds are specifically disclosed. None of these references relate to the use of the compounds as herbicide antidotes, in particular for thiolcarbamate herbicides, more partlcularly for S-n-propyl, N,N-di-n-propyl-thiolcarbamate. None of the references relate to herbicidal compositions employing N-benzenesulphonyl carbamate antidoes and an active thiolcarbamate herbicide, particularly S-n-propyl N,N-di-n-propylthiolcarbamate N,N-di-n-propylthiolcarbamate.

In general terms, it has now been discovered that cultivatd crop plants may be protected against injury by herbicides, in particular by thiolcarbamate-type herbicides, and that the injury may be decreased when the herbicides, either alone or in the form of mixtures with other compounds, are applied in a variety of ways. Furthermore, as an alternative effect, the tolerance of the plants to the herbicides may be substantially increased, for example, by adding to the soil directly or indirectly an N-(substituted benzenesulphonyl) carbamate antidote compound.

As an alternative mode of action, the compounds used according to the present invention may interfere with the normal herbicidal action of the thiolcarbamate-type and other herbicides to render them selective in the action thereof. The observation noted with the presence of the antidote is a decrease in phytotoxicity with respect to various crops, otherwise observed when various thiolcarbamate herbicides are used for weed control. Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiolcarbamate with the accompanying decreased herbicidal effect on desired crop species.

Therefore, the term 'herbicidal antidote' or 'antidotal amount' or equivalents are meant to refer to that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed, for example, a remedy, interferant, protectant or antagonist, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the seed, soil or furrow in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpose.

In general terms, the present invention is concerned with the use of certain N-arylsulphonyl carbamates as herbicide antidotes.

The term 'herbicide' as used herein, means one or more thiolcarbamates alone or one or more thiolcarbamates together with one or more other herbicidal compounds.

In a first embodiment, the present invention relates generally to the use of a compound corresponding to the following general formula:

wherein n represents 0, 1,2 or 3; X represents methyl, chloro, bromo, methoxy or trifluoromethyl; Provided that, when X represents bromo, methoxy or trifluoromethyl, n represents 1; and R represents C1-C4 alkyl, C3-C6 alkenyl which may optionally be substituted up to four times by chloro. C3-Cs alkynyl, mono- to hexa- fluoro-, chloro- or bromo- C2-Ce alkyl, C2-C8 dialkylamino, C3-C6 cyanoalkylthioalkyl, phenyl which may optionally be substituted by C1-G alkyl or chloro, benzyl which may optionally be substituted in the 4-position by chloro or methoxy, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 cyanoalkyl, C3-C7 alkoxycarbonylalkyl, C2-Ce formamidoalkyl, C4-C7 alkoxycarbonylalkenyl, C3-C6 alkylcarbonylalkyl, phosphonomethyl, trifluoroacetamidomethyl, 4chlorophenylthiomethyl, 1,3-dioxacyclohexane-5,5-methyl methylene, 3-pyridylmethyl, phenoxyethyl, cyclopropyl, 3-phenyl-propyn-2-yl, methylthioacetimino, acetoneimino or benzaldimino; Provided that, when R represents C3-C6 alkenyl or C3-C6 alkynyl, the phenyl ring is other than methoxy-substituted; and provided that, when R represents C1-C4 alkyl or C3-C6 alkenyl, the phenyl ring is other than bromo-substituted.

In a second embodiment, the present invention relates generally to the use of a compound corresponding to the following general formula:

wherein X represents hydrogen, methoxy, chloro or bromo; and R represents mono- to hexa- fluoro-, chloro- or bromo- C2 - C6 alkyl or C3 - C6 alkenyl substituted by chloro; provided that, when R represents 2-chloroethyl, X represents other than chloro.

Certain of these compounds are considered to be novel and are the subject of U.K. Patent No. (application No. 7921016) Serial No. 1571905.

In a first embodiment, the above-mentioned reference discloses and claims a compound corresponding to the following general formula:

wherein n represents 0, 1,2 or 3; X represents methyl, chloro, bromo, methoxy or trifluoromethyl; provided that, when X represents bromo, methoxy or trifluoromethyl, n represents 1; and R represents C1-C4 alkyl, C3-C6 alkenyl which may optionally be substituted up to four times by chloro, C3-C6 alkynyl, mono- to hexa- fluoro-, chloro- or bromo- C2-C6 alkyl, C2-Cs dialkylamino, C3-Cs cyanoalkylthioalkyl, phenyl which may optionally be substituted by C1-C4 alkyl or chloro, benzyl which may optionally be substituted in the 4-position by chloro or methoxy, C2-C6 alkoxyalkyl, C2-Ce alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 cyanoalkyl, C3-C7 alkoxycarbonylalkyl, C2-C6 formamidoalkyl, C4-C7 alkoxycarbonylalkenyl, C2-Ce alkylcarbonylalkyl phosphonomethyl, trifluoroacetamidomethyl, 4-chlorophenylthiomethyl, 1,3-dioxacyclohexane-5,5-methyl methylene, 3-pyridylmethyl, phenoxyethyl, cyclopropyl, 3-phenyl-propyn-2-yl, methylthioacetimino, acetoneimino or benzaldimino; provided that, when R represents C3-Cs alkenyl or C3-C6 alkynyl, the phenyl ring is other than methoxysubstituted, provided that, when R represents C3-C6 alkenyl, the phenyl ring is other than bromo-substituted; provided that, when R represents C2-C4 alkyl, the phenyl ring is trifluoromethyl-substituted; provided that, when R represents C2 alkyl, the phenyl ring is other than 4-triuoromethyl-substituted; and provided that, when R represents C3, C4, or C6 alkoxyalkyl, the phenyl ring is bromo- or trifluoromethyl-substituted.

In a second embodiment, the above-mentioned reference discloses and claims a compound corresponding to the following general formula:

wherein X represents hydrogen, methoxy, chloro or bromo; and R represents mono- to hexa- fluoro-, chloro- or bromo C2-C6 alkyl or C3-C6 alkenyl substituted by chloro; provided that, when R represents 2-chloroethyl, X represents other than chloro.

These compounds may be prepared by various known processes. For example, such compounds may be prepared by reacting appropriate benzenesulphonyl isocyanates with appropriate hydroxylamines or oximes or by reacting appropriate aliphatic alcohols with appropriate benzenesulphonyl isocyanates or by reacting appropriate benzenesulphonamides with appropriate chloroformates.

Reference may be made to the above-mentioned reference for further details in this connection.

The following is a Table of compounds which may be prepared by the above processes and used in accordance with the present invention. Compound numbers have been assigned and are used for identification throughout the remainder of the specification.

Table I

Compound X R m.p. so0C Number or nD 1 4-CH3 CH(CH3)2 sticky* 2 4-OCH3 C2Hs 110-116 3 4-C1 C2He 85-90 4 4-CH3 CH(CF3)2 69-75 Compound X R m.p.30 C Number or nD 5 4-CH CH2CH2Br 1.5460 6 4-CH3 CH2CH2C1 1.5348 7 4-CH CH2CHB4CH3 1.5375 8 4-CH3 CH2CF3 120-125 9 4-CH3 CH2CH(Cl)CH2Cl semi-solid* 10 4-CH3 CH2C(CH3)C1CH2C1 1.5640 I1 4-C1 CH2CHC12 114-115 12 4-C1 CH2CF3 142-145 13 4-C1 CH(CF3)2 83-87 14 4-Br CH2CH2C1 semi-solid* 15 4-C1 CH2CH(Cl)CH2Cl semi-solid* 16 4-C1 CH2CH2Br 92-98 17 4-CH3 CH2C=CCH3 85-90 18 4-C1 CH2C=CH 106-108 19 4-C1 CH2CH2C#CH 102-104 20 4-C1 C(CH3)2CH2CCH 108-110 21 4-C1 CH2C#CCH3 141-142 22 4-CH3 CH2CH2C#CH glass* 23 H CH2CCH 78-80 24 H CH2C#CHCH3 114-116 25 H CH2CH2C=-CH Semi-solid* 26 H CH2CC1=CH2 Semi-solid* 27 4-Br CH2CCH 124-125 28 4-Br CH2C#CCH3 134-135 29 H CH2CF3 93-95 30 H CH2CH2C1 semi-solid* 31 H CH2CHC12 semi-solid* 32 H CH3 127-130 33 H C2H5 1.5003 34 H n-C3H7 1.4942 35 H cyclo-C3H7 1.4952 36 H CH2CC13 121-122 37 H CH2CF2CF2H 94-97 38 H CH2CH=CH2 1.5175 39 4-CH3 CH2CCl2CH2Cl 1.5300 40 4-CH3 CH2CH=CH2 1.5375 41 4-CH3 CH2C(CH3)=CH2 1.5300 42 4-CH3 CH2C(C1)=CH2 1.5340 43 4-CH3 CH2CCH 1.5384 44 4-CH3 C(CH3)2C#CH glass* 45 4-CH3 C(CH3)2CCCH3 glass* 46 4-CH3 CH(i-C3H7)CCH glass* 47 4-CH3 N(C2Hs)2 semi-solid* 0 48 4-CH3 CH2NHCCF3 sticky 49 4-CH3 CH2P(O)(OH)2 semi-solid

50 4-CH3 cH2 S+CI 65-70 CH2 SC 51 4-C1 CH3 127-130 52 4-C1 n-C3H7 1.5111 53 4-C1 C2H4C1 semi-solid 54 4-C1 CH2CH=CH2 1.5262 55 4-C1 CH2C(C1)=CH2 89-92 56 4-C1 CH2C(O)OC2H5 1.4783 57 4-C1 phenyl 101-104

58 4-C1 cm24 174-176

59 4-C1 CH2 C C 109-111 60 3-CF3 C2H5 59-63 61 3-CF3 CH2CF3 91-96 62 3-CF3 CH2CH=CH2 66-70 63 3-CF3 CH2C3CH 76-77 64 3,4-C1 C2Hs 100-102 65 2-CF3 C2H5 129-131 66 3-C1 C2H5 1.5155 67 3-C1 CH2CF3 108-110 68 3-C1 CH2CH=CH2 58-61 69 3-C1 CH2C=CH 73-76 70 3-C1 CH2C#CCH3 95-97 71 2,4,6-CH3 C2Hs 159-160 72 2,4,6-CH3 cyclo-C3H7 112-114 73 2,4,6-CH3 CH2CF3 150-162 74 2,4,6-CH3 CH2CC13 139-141 75 2,4,6-CH3 CH2CCH 150.151 76 2,4,6-CH3 4-Cl-phenyl 131-132

77 2,4,6-CH3 -N=CH 4 120-122 dec.

78 4-CH3 C2H4F 1.5022 79 4-CH3 C2H4SC2H4CN 1.5482 80 4-CH3 3,4-di-CH3-phenyl 80-82 81 4-CH3 -N=C(CH3)SCH3 145-147 82 4-CH3 t-C4H9 119-122 83 4-C1 C2H4F 1.5192 84 4-C1 CH2CF2CF2H 82.85 85 4-C1 C(CH3)(C2Hs)C#CH 122-124 86 4-C1 C2H4OC2Hs semi-solid* 87 4-C1 C2H4SC2Hs 1.5360 88 4-C1 C(CH3)2CN 68-71 89 4-C1 C2H4C(O)CH3 94-98

90 4-Cl viscous semi-solid* 91 4-C1 CH(CH3)C(O)OC2Hs 1.4950 92 4-C1 C2H4NHC (O) H 154-157dec.

93 4-C1 C(CH3)=CHC(O)OC2Hs 1.5100 94 4-C1 4-Cl-phenyl 159-160 95 4-C1 2-Cl-phenyl 77-80 96 4-C1 3,4-di-CH3-phenyl 100-103 97 4-C1 3,4,5-tri-CH3-phenyl 1.5473 98 4-C1 2-i-C3H7-phenyl 1.5471 99 4-C1 3,5-di-i-C3H7-phenyl 1.5415 100 4-C1 3-t-C4H9-phenyl oil* 101 4-C1 benzyl 98-101 102 4-C1 4-Cl-benzyl 138-139 103 4-C1 4-CH30-benzyl 119-122 104 4-C1 phenoxy-CH2CH2 98-99 105 4-C1 -N=C(CH3)2 161-162 106 4-C1 -N=C(CH3)SCH3 125-128 107 4-C1 -N=CH-phenyl 120-124 dec.

*Structure confirmed by either infra-red or nuclear magnetic resonance spectroscopy.

(Except for the compounds numbered 1, 2, 3, 32, 33, 34, 51, 52, 64, 66, 71, 82 and 86, the above compounds are considered to be novel).

The present invention is particularly concerned with compositions which comprise herbicides, in particular thiolcarbamates alone, more particularly S-n-propyl-N ,N-di-n-propyl thiolcarbamate, and antidotes therefor of the type used according to the present invention.

A preferred herbicidal composition comprises a thiolcarbamate herbicide and an antidotally effective amount of an antidote therefor corresponding to the following general formula:

wherein X represents hydrogen, methyl, methoxy, chloro or bromo; and R represents Cl-C4 alkyl, mono- to hexa- fluoro-, chloro- or bromo- C2-C6 alkyl, C3-Cs alkenyl which may be substituted by chloro, C3-C6 alkynyl, C2-C6 dialkylamino, trifluoroacetamidomethyl, 4-chlorophenylthiomethyl, phenyl, 3-phenyl-propyn-2-yl 3pyridylmethyl or phosphonomethyl; subject, of course, to the above provisos.

In addition, the present invention encompasses two-component systems which comprise first components comprising herbicides, in particular thiolcarbamates alone, and second components comprising antidotes therefor of the type used according to the present invention.

The above-mentioned compositions may comprise inert carriers or diluents.

In general terms, these compositions may be used to control vegetation by the application thereof to the locus where the control is desired.

As indicated above, the antidote compounds may be used in a variety of ways to afford crops the desired protection against injury due to herbicides. Of course, when the antidote is 'applied' the herbicide may already be present and/or may be applied simultaneously and/or may be applied subsequently.

For example, the present invention particularly relates to methods of protecting plant crops in particular soybeans, from injury due to herbicides, in particular thiolcarbamates, more particularly S-n-propyl-N,N-di-n-propyl-thiolcarbamate, which comprise applying to the crop seed prior to planting or introducing into the seed furrow during the sowing procedure or applying to and/or incorporating in the soil, before or after planting, nonphytotoxic antidotally effective amounts of the antidotes.

Furthermore, the present invention relates to crop seed, in particular soybeans, having applied thereto a non-phytotoxic antidotally effective amount of antidote.

Moreover, the present invention relates to soil having applied thereto and/or incorporated therein a non-phytotoxic antidotally effective amount of antidote.

The herbicides indicated in the Tables below and elsewhere are used at rates which produce effective control of undesirable vegetation (i.e. weeds). The rates employed herein produce representative results within the recommended amounts set forth by the supplier. Therefore, the weed control in each instance is commercially acceptable within the desired or recommended amount.

It is clear that the class of herbicidal agent described and illustrated herein is characterised as an effective herbicide exhibiting such activity. The degree of this herbicidal activity varies among specific compounds and among combinations of specific compounds within the class.

Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus, selection of a specific herbicidal compound or combination to control undesirable plant species may readily be made. According to the present invention, the reduction or prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved.

In general terms, the herbicidal compound employed in the utility of the present invention is, in particular, an active thiolcarbamate herbicide of a general type. That is, it is a member of the class of herbicidally active compounds effective against a wide range of plant species with no discrimination between desirable and undesirable species. As mentioned above, the general method of controlling vegetation comprises applying a herbicidally effective amount of the herbicidal compound to the area or plant locus where control is desired.

Examples of suitable herbicides include: S-ethyl dipropyl thiolcarbamate, S-ethyl diisobutyl thiolcarbamate, S-propyl di-n-propyl thiolcarbamate, S-ethyl cyclohexyl ethylthiolcarbamate and 2,3,3-trichloroallyl N,N-diisopropyl thiolcarbamate, S-ethyl hexahydro-IH-azepine-1 carbothioate or S-isopropyl-1-(5-ethyl-2-methylpiperidine) carbothioate; either singly or as mixtures optionally with other types of herbicidal compounds, such as triazines, for example 2-chloro-4-ethylamino-6-isopropylamino-striazine, 2-chloro-4,6-bis(ethylamino)-3-triazine and 2-chloro-4-cyclopropyl-amino-6 isopropylamino-s-triazine or on 2(4-chloro-6-ethylamino-2-triazine-2-yl amino)-2- methylpropionitrile.

As mentioned above, one embodiment of the present invention relates to a two-part or package herbicide system comprising a first part of one or more herbicides, in particular thiolcarbamate herbicides, and a second part of one or more antidote compounds therefor, it being understood that the antitode is used in an effective amount to render the two-part herbicide system selective in decreasing phytotoxic effects to desired or beneficial crops and yet phytotoxic to the undesirable or unwanted vegetation. Thus, as indicated above, the soil treated with an antidote and optionally a herbicide, for example, by such a system, becomes extremely useful and desirable, allowing previously injured crops to be planted in the treated soil. otherwise injured by the herbicide when used alone. Hence, soil treated with antidote and optionally herbicide as described herein is beneficial, desirable and useful.

Subject to the foregoing definition, the term 'herbicide' as used herein, means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, simulation and dwarfing. By the term plants', is meant germinant seeds, emerging seedlings and established vegetation including the roots and above-ground portions.

Evaluation Procedurres Flats to be used for growing the crops and weed species were filled with loamy sand soil.

Stock solutions of the herbicide and each candidate antidote were prepared as follows: A. Herbicide - S-n-propyl N,N-di-n-propyl thiolcarbamate - VERNAM 6E -1560 mg.

of VERNAM 6E was diluted in 250 ml. of water so that 5 ml. applied to a flat is equivalent to 6 Ib/A per flat (based on the surface area of a flat).

B. Antidote -- of each candidate, 78 mg. was dissolved in 20 ml. of acetone with 1%, by weight, Tween (Registered Trade Mark) 20 (polyoxyethylene sorbitan monolaurate) so that 5 ml. when applied by preplant incorporation technique (PPI) is equal to 5 Ib/A per flat.

The herbicide and antidotes were applied to the soil together as a tank mix employing a re-lant incorporation technique. To prepare the combined tank mix, 5 ml. of the EAM were admixed, followed by incorporation into the soil from the flats during incorporation in a rotary mixer.

One row each of the following weeds and crop was seeded into the treated soil in the flats: watergrass (Echinochloa crusgalli), foxtail (Setaria viridis) and soybeans (Glycine max).

The flats were placed on greenhouse benches where temperature were maintained at from 70 to 90IF. The soil was watered by sprinkling to ensure good plant growth Injury ratings were taken 2 and 4 weeks after the applications were made. Individual flats treated with the herbicide alone were included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes.

The following Table includes results as per cent protection for the crop according to the procedure discussed above. The per cent protection is determined by a comparison with flats not treated with the candidate antidotes used according to the present invention.

Table II Application Method: Pre-plant Incorporation - PPI (Tank Mix) Crop Species: Soybeans (Glycine max) Weed species: Foxtail (Setaria viridis) Watergrass (Echinochloa crusgalli) *i = % injury ** = % protection Compound PPI (6 i-b/A) (Tank Mix) Number Soybeans Watergrass Foxtail Vernam 6 Ib/A 40- 100* 100* 1** 75 0 0 2 75 0 0 3 100 0 5 4 37.5 0 0 5 25 0 0 6 25 0 0 7 25 0 0 8 75 0 0 9 75 0 0 10 50 0 0 11 75 0 0 12 100 0 0 13 50 0 0 14 25 0 0 15 75 0 0 16 50 0 0 17 100 0 5 18 100 0 5 19 100 0 5 20 75 0 0 21 100 0 5 22 75 0 0 23a 100 0 0 24a 75 0 0 25a 100 0 0 26a 75 0 0 27a 100 0 0 28a 100 0 0 29a 75 0 0 30a 67.5 0 0 a = Pre-plant incorporation of VERNAM and antidote applied separately prior to incorporation.

Seed Treatment Test Small flats were filled with Felton loamy sand soil. Soil incorporated herbicides were applied at this time. The soil from each flat was placed into a five-gallon cement mixer where the soil was mixed as the herbicides were applied using a pre-determined amount of a stock solution containing 780 mg. of approximately 75% active ingredient to 125 ml. of water. 5 ml.

of stock solution was applied to the soil ina volumetric pipette. 5 ml. of stock solution contained an equivalence of herbicide which equals 6 pounds per acre when applied to the soil in the flats. After the herbicide incorporation, the soil was placed back into the flats.

Flats of the herbicide-treated and untreated soil were then ready to be planted. A pint sample of soil was removed from each flat and placed next to each flat for later use in covering the seeds. The soil was levelled and rows one-half inch deep were made for planting seeds.

Alternating rows of treated and untreated crop seeds were sown. In each test, soybeans (Glycine max) seeds were planted in each row. Rows were approximately 11/2 inches apart in the flat. Seeds were treated by preparing a stock solution by dissolving 250 mg. of the antidote compound in 2.5 ml. of acetone, then using 0.5 ml. of the stock solution to treat 10 g. of soybean seed equivalent to 0.5% w/w. Antidote compounds may also be applied as liquid slurries and powders or dusts. In some cases, acetone is used to dissolve powdered or solid compounds, as they could be more effectively applied to the seeds.

After the flats were seeded, they were covered with the one pint of soil which had been removed just prior to planting. Flats were placed on greenhouse benches at temperatures ranging from 70 to 79IF. Flats were watered by sprinkling as needed to ensure good plant growth. Per cent control ratings were taken four weeks after the treatments were applied.

In each test, the herbicide was applied alone, in combination with the seed protectant and the seed protectant was applied alone to check for phytotoxicity. The untreated adjacent row was employed to observe any beneficial lateral movement of the antidote compound through the soil. The degree of the effect was noted by comparison with the control.

In this seed treatment test with the herbicide S-n-propyl N,N-di-n-propyl thiolcarbamate, Compound No. 17 exhibited 50% protection to the treated soybean seeds. That is, the injury was reduced by at least 50% to the emerging soybean plants grown from seed treated with Compound 17, compared to untreated seed grown in soil containing the thiolcarbamate herbicide.

Evaluation Procedure and Method Flats to be used for growing the crops and weed species were filled with loamy sand soil.

Various methods of application were employed, such as pre-plant incorporation of (1) the herbicide and antidote separately and (2) as a tank mix with the herbicide and antidote together. The application was by incorporation, whereinafter the seeds were planted in soil treated with an effective herbicidal composition of thiolcarbamate herbicide and antidote; application by an in-furrow treatment of the seeds and surrounding soil in which the herbicide had been applied previously to the soil; and treatment of the crop seeds with an antidote candidate prior to planting in herbicide treated soil.

Stock solutions of other representative herbicides and antidote candidates were prepared as follows: Herbicides C. S-ethyl di-n-propyl thiolcarbamate - EPTC - EPTAM (Registered Trade Mark) 6E-260 mg. dissolved in 200 ml. water such that 4 ml. applied to the soil from a planting flat is equivalent to 1 lb/A applied in 80 gal. of water per acre and 3 ml. is equivalent to 0.75 lb/A.

D. S-isopropyl 1-(5-ethyl-2-methyl-piperidine) carbothioate (R-12001), 390 mg.

dissolved in 200 ml. of acetone with 1% by weight, Tween 20 or 975 mg. in 250 ml. of acetone, such that 5 ml. of solution applied to a planting flat is equivalent to 2 lb/A pre-plant incorporated and 6 ml is equivalent to 6 Ib/A respectively.

E. S-ethyl di-isobutyl thiolcarbamate - SUTAN 6E or S-ethyl cyclohexyl ethyl thiolcarbamate - RONEET 6E -520 mg. dissolved in 200 ml. water such that 4 ml. applied to the soil from a planting flat is equivalent to 2 Ib/A, applied in 80 gal. of water per acre. For 6 Ib/A or 12 Ib/A, 1300 mg. or 26 mg. was dissolved in 250 ml. water such that 6 ml. was equivalent to the desired amount, respectively.

F. 2,3,3-trichloroallyl N,N-diisopropyl thiolcarbamate - AVADEX (Registered Trade Mark) 4E - 1219 mg. dissolved in 300 ml. distilled water, such that 6 ml. is equivalent to 3 Ib/A when applied to the soil from a planting flat pre-plant incorporated.

G. S-ethyl hexahydro-IH-azepine-1-carbothioate - ORDRAM 3E -857 mg. dissolved in 250 ml. water such that 5 ml. is equivalent to 4 Ib/A and 2.5 ml. is equivalent to 2 lb/A when</RT additive stock solution I was atomized directly onto the exposed seed and soil in the open furrow in one-half of the flat. The untreated section of the flat served as an herbicide check and also made it possible to observe any lateral movement of the antidote through the soil.

The seeds were covered with the one pint sample of untreated soil which had been removed earlier.

For tank mixes to be applied as a pre-plant incorporated application, the following solutions and procedure were employed. 5 ml. of herbicide stock solutions A or Cwere each mixedwtih 5 ml. of antidote candidate stock solution J such that the equivalent of 1 lb/A and 5 lbs/A of herbicide and antidote, respectively, were applied and incorporated into the soil of each flat.

For pre-plant incorporation, the mixed stock solutions were injected into the soil during incorporation in a 5-gallon rotary mixer. Other stock solutions were employed at indicated rates in the tank mix procedure.

For seed treatment, 10 grams of seed in a suitable container was shaken with 0.5 ml. of antidote stock solution H, or other stock solution as indicated, such that the seed treatment was equivalent to 0.5% w/w, 0.25% w/w, 0.125% w/w or 0.1% w/w.

Shaking was continued until the seeds were uniformly covered. The antidote compounds may be applied as liquid slurries and powder or dust treatments. The treated seeds were planted in soil in which herbicide stock solution had been pre-plant incorporated into the soil at a rate equivalent to 1 lb/A active ingredient.

All flats were placed on greenhouse benches where temperatures were maintained at from 70 to 90IF. The soil was watered by sprinkling to ensure good plant growth. Injury ratings were taken 2 and 4 weeks after the applications were made. Individual control flats treated with the herbicide alone were included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The results of these tests are tabulated in Table III.

Table III ANTIDOTE ACTIVITY Application Method: Seed Treatment- ST In-Furrow - IF Pre-Plant Incorporation - PPI (Tank Mix) Crop Species: Barley - BA [Hordeum vulgare (L)j Corn - CN [Zea maize] Cotton - CT [Gossypium hirsutum] Grain Sorghum - GS [Sorghum vulgare] Rice - R [Dryma sativa] Soybeans - SB [Glycine mar] Wheat - WT [Triticum aestivum] Weed Species: Watergrass - WG [Echinochloa crusgalli] Green Foxtail FT [Setaria viridis] Wild Oats - WO [Avenafatua (L.)] Shattercane - SC [Sorghum bicolor] Result = Percent injury with antidote present/percent injury of herbicide alone.

Compound Herbicide Method of Rate Crop Result Number Application 1 ORDRAM PPI 6+5 CN 60/90 RONEET PPI 6+5 CN 85/95 RONEET PPI 2+5 GS 40/50 ORDRAM PPI 4+5 SB 70/80 RONEET PPI 2+5 SB 60/70 VERNAM PPI 6+5 SB 10/40 IF 6+5 SB 20/40 3 ORDRAM ST 4+.125 BA 10/30 RONEET ST 2+. 10 BA 50/80 R-12001 PPI 2 + 1 BA 30/60 ST 2+.25 BA 30/90 VERNAM ST 1+.10 BA 40/60 3 ORDRAM PPI 6+5 CN 50/90 RONEET PPI 6+5 CN 30/95 PPI 6+0.5 CN 30/50 VERNAM PPI 6+5 CN 60/75 EPTAM PPI 0.75+5 GS 60/100 ORDRAM PPI 2+5 GS 45/82 ST 2+.125 GS 55/75 RONEET PPI 3+5 GS 40/75 ST 3+.125 GS 50/70 R-12001 PPI 2+5 GS 58/92 ST 2+.125 GS 45/85 SUTAN PPI 2+5 GS 50/95 ST 2+.125 GS 70/95 VERNAM ST 1+.125 GS 65/95 EPTAM PPI 5+1 SB 30/65 ORDRAM PPI 4+1 SB 40/80 RONEET PPI 2+5 SB 10/70 SUTAN PPI 5+1 SB 45/65 VERNAM IF 6+1 SB 0/40 ST 6+.062 SB 10/45 ORDRAM ST 4+.125 WT 10/20 RONEET IF 2+1 WT 75/90 R-12001 PPI 2+1 WT 60/95 R-12001 ST 2+.062 WT 40/70 VERNAM IF 1+5 WT 60/90 4 ORDRAM PPI 6+5 CN 80/90 RONEET PPI 6+5 CN 75/95 RONEET PPI 2+5 SB 60/70 VERNAM PPI 6+5 25/40 5 ORDRAM PPI 6+5 CN 80/90 RONEET PPI 6+5 CN 80/90 Compound Herbicide Method of Rate Crop Result Number Application 5 RONEET PPI 2+5 GS 40/50 6 ORDRAM PPI 6+5 CN 80/90 RONEET PPI 6+5 CN 80/95 RONEET PPI 2+5 GS 40/50 ORDRAM PPI 4+5 SB 50/80 7 ORDRAM PPI 6+5 CN 70/90 RONEET PPI 6+5 70/95 ORDRAM PPI 4+5 SB 70/80 8 ORDRAM PPI 6+5 CN 80/90 RONEET PPI 6+5 CN 80/95 VERNAM IF 5+5 CT 30/60 RONEET PPI 3+5 GS 50/75 VERNAM IF 6+5 SB 20/40 9 ORDRAM PPI 6+5 CN 70/90 RONEET PPI 6+5 CN 70/95 VERNAM IF 5+5 CN 50/75 VERNAM IF 1+5 R 40/60 VERNAM IF 1+5 WT 60/87 10 ORDRAM PPI 6+5 CN 80/90 RONEET PPI 6+5 CN 75/95 VERNAM IF 5+5 CT 70/80 ORDRAM PPI 2+5 GS 50/85 RONEET PPI 2+5 GS 40/50 11 ORDRAM PPI 6+5 CN 70/90 RONEET PPI 6+5 CN 75/95 VERNAM IF 6+5 CN 0/70 ORDRAM PPI 2+5 GS 75/85 RONEET PPI 2+5 SB 50/70 VERNAM IF 6+1 SB 20/40 12 ORDRAM PPI 6+5 CN 70/90 RONEET PPI 6+5 CN 75/95 ORDRAM PPI 2+5 GS 62/82 RONEET PPI 3+5 GS 50/75 R-12001 PPI 2+5 GS 50/90 VERNAM IF 1+5 GS 50/100 ORDRAM PPI 4+5 SB 20/80 RONEET PPI 2+5 SB 40/70 VERNAM IF 6+1 SB 10/40 13 RONEET PPI 6+5 CN 75/95 VERNAM IF 5+5 CT 60/80 ORDRAM PPI 4+5 SB 70/80 RONEET PPI 2+5 SB 60/70 14 VERNAM IF 5+5 BA 50/82 VERNAM IF 5+5 CN 50/70 VERNAM IF 1+5 WT 60/75 15 ORDRAM PPI 6+5 CN 75/90 VERNAM IF 5+5 CN 40/50 ORDRAM PPI 2+5 GS 70/85 VERNAM IF 1+5 GS 60/100 EPTAM PPI 5+5 SB 35/65 ORDRAM PPI 4+5 SB 50/80 RONEET PPI 2+5 SB 50/70 SUTAN PPI 5+5 SB 30/65 VERNAM IF 6+1 SB 20/50 16 ORDRAM PPI 6+5 CN 80/90 ORDRAM PPI 2+5 GS 60/85 RONEET PPI 2+5 GS 40/50 VERNAM IF 1+5 GS 60/100 ORDRAM PPI 4+5 SB 60/80 17 ORDRAM ST 4+0.5 BA 10/30 RONEET ST 2+0.25 BA 10/80 R-12001 PPI 2+5 BA 40/60 Compound Herbicide Method of Rate Crop Result Number Application 17 R-12001 ST 3+0.25 BA 25/90 SUTAN ST 2+0.25 BA 0/75 VERNAM IF 1+5 BA 30/100 ORDRAM PPI 2+5 GS 10/82 ORDRAM ST 2+0.25 GS 40/75 RONEET PPI 3+5 GS 50/75 RONEET ST 2+.25 GS 10/70 R-12001 PPI 2+5 GS 68/92 R-12001 ST 2+0.25 GS 25/85 SUTAN ST 2+0.25 GS 10/95 VERNAM IF 1+5 GS 40/100 VERNAM ST 1+0.25 GS 30/95 EPTAM PPI 5+5 SB 40/57 EPTAM ST 5+0.5 SB 0/50 SUTAN PPI 5+5 SB 30/65 VERNAM IF 6+5 SB 10/50 ORDRAM ST 6+0.125 WT 10/30 R-12001 PPI 2+5 WT 80/95 18 ORDRAM ST 4+0.125 BA 10/30 RONEET ST 2+0.10 BA 20/80 R-12001 PPI 2+5 BA 10/60 R-12001 ST 3+0.10 BA 30/90 SUTAN ST 2-0.10 BA 0/75 VERNAM IF 1+5 BA 30/95 PPI 1+5 BA 40/95 ST 1+0.10 BA 10/60 ORDRAM PPI 6+5 CN 30/90 RONEET PPI 6+5 CN 70/95 R-12001 PPI 6+0.5 CN 20/50 VERNAM PPI 6+5 CN 50/75 VERNAM IF 5+5 CN 40/90 EPTAM PPI .75+5 GS 50/100 ORDRAM PPI 2+5 GS 30/82 ORDRAM ST 2+0.125 GS 50/75 RONEET PPI 2+5 GS 20/75 RONEET ST 2+0.125 GS 20/75 R-12001 ST 2+0.125 GS 50/85 SUTAN PPI 2+5 GS 75/95 SUTAN ST 2+0.125 GS 60/95 VERNAM PPI 1+5 GS 60/100 IF 1+5 GS 40/100 ST 1+0.125 GS 60/95 R-12001 PPI 2+5 R 60/70 VERNAM I IF 1 1+5 R 80/100 EPTAM PPI 5+5 SB 20/65 ORDRAM PPI 4+5 SB 40/80 RONEET PPI 2+5 SB 30/70 SUTAN PPI 5+5 SB 20/65 VERNAM IF 6+1 SB 13/50 ST 6+0.125 SB 15/25 ORDRAM ST 4+0.125 WT 5/30 RONEET ST 1+0.25 WT 70/95 R-12001 PPI 2+5 WT 75/95 ST 2+0.63 WT 40/70 VERNAM IF 1+5 WT 70/100 19 R-12001 PPI 2+5 BA 30/60 VERNAM PPI 1+5 BA 40/95 VERNAM IF 1+5 BA 20/96 ORDRAM PPI 6+5 CN 60/90 RONEET PPI 6+5 CN 50/95 VERNAM IF 5+5 CN 50/90 EPTAM PPI 0.75+5 GS 60/100 Compound Herbicide Method of Rate Crop Result Number Application 19 ORDRAM PPI 2+5 GS 52/82 RONEET PPI 2+5 GS 20/75 R-12001 PPI 2+5 GS 62/92 SUTAN PPI 2+5 GS 70/95 VERNAM PPI 1+5 GS 60/100 VERNAM IF 1+5 GS 50/100 R-12001 PPI 2+5 R 50/70 VERNAM IF 1+5 R 80/100 RONEET PPI 2+5 SB 40/70 VERNAM IF 6+1 SB 10/40 R-12001 PPI 2+1 WT 50/95 VERNAM IF 1+5 WT 80/100 20 VERNAM IF 1+5 BA 50/95 ORDRAM PPI 6+5 CN 70/90 RONEET PPI 6+5 CN 70/95 VERNAM IF 5+5 CN 70/90 VERNAM IF 5+5 CT 60/80 VERNAM IF 1+5 R 85/100 VERNAM IF 6+5 SB 20/40 21 R-12001 PPI 2+5 BA 30/60 VERNAM PPI 1+5 BA 60/95 VERNAM IP 1+5 BA 30/95 ORDRAM PPI 6+5 CN 60/90 RONEET PPI 6+5 CN 70/95 VERNAM IF 5+5 CN 60/90 EPTAM PPI 0.75+5 GS 40/100 ORDRAM PPI 2+5 GS 40/75 RONEET PPI 2+5 GS 40/75 R-12001 PPI 2+5 GS 45/92 SUTAN PPI 2+5 BA 30/95 VERNAM PPI 1+5 GS 60/100 VERNAM IF 1+5 GS 40/100 R-12001 PPI 2+5 GS 40/70 RONEET PPI 2+5 SB 50/70 VERNAM IF 6+1 SB 25/50 R-12001 PPI 2+5 WT 50/95 VERNAM IF 1+5 WT 80/100 22 ORDRAM PPI 6+5 CN 60/90 RONEET PPI 6+5 CN 85/95 ORDRAM PPI 4+5 SB 70/80 RONEET PPI 2+5 -SB 60/70 VERNAM IF 6+1 SB 30/40 23 VERNAM IF 1+5 BA 20/90 VERNAM IF 5+5 CN 20/90 EPTAM PPI 0.75+5 GS 70/100 ORDRAM PPI 2+5 GS 60/80 RONEET PPI 3+5 GS 50/75 RONEET IF 3+5 GS 30/75 R-12001 PPI 2+5 GS 50/95 24 VERNAM IF 1+5 BA 10/90 VERNAM IF 5+5 CN 50/90 EPTAM PPI 0.75+5 GS 40/100 ORDRAM PPI 2+5 GS 40/80 RONEET PPI 3+5 GS 20/75 RONEET IF 2+5 GS 30/65 R-12001 PPI 2+5 GS 30/90 SUTAN PPI 2+5 GS 40/95 VERNAM IF 1+5 GS 20/95 25 VERNAM IF 1+5 BA 20/70 VERNAM IF 5+5 CN 20/90 RONEET IF 2+5 GS 30/65 VERNAM IF 1+5 GS 30/96 Compound Herbicide Method of Rate Crop Result Number Application 25 VERNAM IF 1+5 R 50/100 26 VERNAM IF 5+5 CN 60/90 VERNAM IF 1+5 GS 60/96 27 ORDRAM ST 4+0.125 BA 0/30 RONEET ST 2+0.25 BA 10/80 R-12001 PPI 2+5 BA 10/60 R-12001 ST 3+0.125 BA 0/70 SUTAN ST 2+0.25 BA 0/75 VERNAM IF 1+5 BA 10/70 VERNAM ST 1+0.10 BA 20/60 VERNAM IF 5+5 CN 40/90 EPTAM PPI 0.75+5 CT 50/100 ORDRAM PPI 2+5 CT 50/80 ORDRAM ST 2+0.125 CT 40/75 RONEET PPI 3+5 CT 30/75 RONEET IF 3+1 CT 40/65 RONEET ST 3+0.125 CT 20/70 R-12001 PPI 2+5 CT 50/92 R-12001 ST 2+0.125 CT 30/85 SUTAN ST 2+0.125 CT 30/95 EPTAM PPI 0.75+5 GS 50/100 ORDRAM PPI 2+5 GS 50/80 ORDRAM ST 2+0.125 GS 40/75 RONEET PPI 3+5 GS 30/75 IF 3+1 GS 40/65 ST 3+0.125 GS 20/75 R-12001 ST 2+0.125 GS 30/85 SUTAN ST 2+0.125 GS 30/95 VERNAM IF 1+5 GS 30/96 ORDRAM ST 6+0.125 WT 10/30 R-12001 ST 2+0.062 WT 40/70 28 VERNAM IF 1+5 BA 20/70 VERNAM IF 5+5 CN 50/90 ORDRAM ST 2+0.125 GS 45/75 RONEET IF 2+5 GS 40/65 RONEET ST 3+0.125 GS 30/70 R-12001 PPI 2+5 GS 50/95 R-12001 ST 2+0.125 GS 30/85 SUTAN ST 2+0.125 GS 40/95 VERNAM IF 1+5 GS 20/96 VERNAM ST 1+0.125 GS 40/95 ORDRAM ST 6+0.125 WT 0/40 R-12001 PPI 2+5 WT 50/95 R-12001 ST 2+. 125 WT 30/70 29 ORDRAM ST 4+0.125 BA 10/30 R-12001 PPI 2+1 BA 40/60 VERNAM ST 1+0.50 BA 50/95 EPTAM PPI 5+5 CN 20/85 R-12001 PPI 5+0.5 CN 20/50 EPTAM PPI 0.75+5 GS 40/100 ORDRAM PPI 2+5 GS 30/80 ORDRAM ST 2+0.125 GS 40/75 RONEET PPI 3+5 GS 30/75 RONEET IF 3+2 GS 40/65 RONEET ST 3+0.125 GS 20/70 SUTAN PPI 2+5 GS 30/95 VERNAM IF 1+5 GS 40/100 30 VERNAM PPI 6+5 SB 15/40 31 EPTAM PPI 5+5 CN 30/85 VERNAM IF 5+5 SB 10/40 32 VERNAM IF 1+5 BA 60/70 VERNAM IF 1+5 CT 40/60 Compound Herbicide Method of Rate Crop Result Number Application 32 VERNAM IF 1+5 GS 70/100 VERNAM IF 1+5 SB 0/42 33 VERNAM IF 1+5 BA 60/70 VERNAM IF 1+5 GS 50/100 VERNAM IF 1+5 R 70/95 VERNAM IF 1+5 SB 30/60 34 VERNAM IF 1+5 BA 50/70 VERNAM IF 1+5 CN 70/90 VERNAM IF 1+5 GS 60/100 VERNAM IF 6+1 SB 10/42 35 VERNAM IF 1+5 BA 60/70 VERNAM IF 1+5 CT 40/60 VERNAM IF 1+5 GS 50/100 VERNAM IF 6+5 SB 20/42 36 VERNAM IF 1+5 BA 30/60 VERNAM IF 1+5 CN 50/95 VERNAM IF 1+5 GS 50/100 37 VERNAM IF 1+5 BA 20/60 VERNAM IF 6+5 CN 60/95 VERNAM IF 1+5 CT 20/50 VERNAM IF 1+5 GS 40/100 VERNAM IF 1+5 WT 60/90 38 VERNAM IF 1+5 BA 20/60 VERNAM IF 6+5 CN 10/95 VERNAM IF 6+5 SB 20/50 39 RONEET PPI 6+5 CN 75/95 40 VERNAM IF 1+5 BA 60/100 ORDRAM PPI 6+5 CN 70/90 VERNAM IF 1+5 GS 60/100 VERNAM PPI 6+5 SB 10/40 41 VERNAM IF 1+5 BA 40/50 ORDRAM PPI 2+5 GS 60/80 42 VERNAM IF 1+5 BA 30/50 RONEET PPI 2+5 GS 40/75 VERNAM PPI SB 40/60 45 ORDRAM PPI 6+5 CN 70/90 RONEET PPI 2+5 GS 40/50 ORDRAM PPI 4+5 SB 50/80 VERNAM IF 1+5 WT 60/90 44 VERNAM IF 6+5 CN 50/70 VERNAM IF 1+5 CT 40/70 RONEET PPI 3+5 GS 60/75 45 VERNAM IF 1+5 R 40/95 VERNAM PPI 4+5 SB 40/50 46 VERNAM IF 1+5 BA 30/50 RONEET PPI 3+5 GS 50/75 VERNAM IF 1+5 R 30/95 47 VERNAM PPI 6+5 SB 10/40 VERNAM IF 6+5 SB 60/80 VERNAM IF 1+5 WT 50/75 48 ORDRAM PPI 2+5 GS 60/85 VERNAM PPI 6+5 SB 30/40 49 VERNAM IF 5+5 CN 40/70 RONEET PPI 2+5 SB 50/70 VERNAM PPI 6+5 SB 30/40 50 VERNAM IF 1+5 BA 60/90 VERNAM IF 1+5 R 50/90 ORDRAM PPI 4+5 SB 50/80 VERNAM IF 6+1 SB 30/40 51 VERNAM IF 1+5 BA 30/83 EPTAM PPI 0.75+5 GS 50/100 ORDRAM ST 2+0.125 GS 50/75 Compound Herbicide Method of Rate Crop Result Number Application 51 RONEET ST 3+0.125 GS 30/70 VERNAM IF 1+5 GS 60/100 VERNAM IF 6+0.5 SB 10/40 52 EPTAM PPI 0.75+5 GS 50/100 RONEET PPI 3+5 GS 20/75 RONEET IF 2+1 GS 40/75 SUTAN PPI 2+5 GS 40/95 VERNAM IF 1+5 GS 40/100 VERNAM PPI 6+5 SB 10/50 IF 6+5 SB 10/30 53 ORDRAM PPI 6+5 CN 50/90 ORDRAM PPI 2+5 GS 60/85 VERNAM IF 1+5 R 50/95 54 VERNAM IF 1+5 BA 10/60 VERNAM IF 6+5 CN 40/70 EPTAM PPI 0.75+5 GS 30/100 ORDRAM PPI 2+5 GS 40/80 RONEET PPI 3+5 GS 20/75 RONEET IF 3+5 GS 10/75 R-12001 PPI 2+5 GS 20/90 SUTAN PPI 2+5 GS 30/95 VERNAM IF 1+5 GS 30/100 VERNAM PPI 6+5 SB 0/50 VERNAM IF 1+5 WT 60/90 55 ORDRAM PPI 6+5 CN 70/90 VERNAM IF 6+5 CN 70/90 VERNAM IF 1+5 GS 75/100 VERNAM PPI 6+5 SB 10/40 VERNAM IF 6+1 SB 20/40 56 ORDRAM PPI 6+5 CN 70/90 RONEET PPI 2+5 GS 40/50 VERNAM PPI 6+5 SB 10/40 VERNAM IF 6+1 SB 20/40 57 VERNAM PPI 6+0.5 SB 20/40 VERNAM IF 6+5 SB 40/60 58 VERNAM PPI 6+1 SB 10/40 VERNAM IF 1+5 WT 50/78 59 VERNAM IF 1+5 GS 70/100 VERNAM PPI 6+5 SB 30/50 VERNAM IF 6+5 SB 10/30 60 VERNAM IF 1+5 BA 30/55 VERNAM IF 1+5 GS 60/85 61 VERNAM IF 6+5 CN 80/90 VERNAM IF 1+5 CT 40/50 62 VERNAM IF 1+5 BA 30/55 VERNAM IF 6+5 CN 70/90 63 VERNAM IF 1+5 BA 20/55 VERNAM IF 6+5 CN 50/90 VERNAM IF 6+5 SB 30/55 64 VERNAM IF 1+5 CT 40/60 VERNAM IF 1+5 GS 40/100 65 VERNAM IF 1+5 BA 40/60 VERNAM IF 1+5 CN 30/95 VERNAM IF 1+5 GS 40/95 VERNAM IF 6+5 SB 0/60 66 VERNAM IF 1+5 BA 30/55 VERNAM IF 6+5 CN 30/90 VERNAM IF 1+5 GS 40/85 67 VERNAM IF 1+5 BA 40/55 VERNAM IF 6+5 CN 70/90 VERNAM IF 1+5 GS 60/85 VERNAM IF 1+5 WT 60/70 Compound Herbicide Method of Rate Crop Result Number Application 68 VERNAM IF 1+5 BA 30/55 VERNAM IF 6+5 CN 30/90 VERNAM IF 1+5 GS 40/95 VERNAM IF 6+5 SB 30/55 VERNAM IF 1+5 WT 50/70 69 VERNAM IF 1+5 BA 20/55 VERNAM IF 6+5 CN 30/90 VERNAM IF 1+5 GS 40/85 70 VERNAM IF 1+5 BA 30/55 VERNAM IF 6+5 CN 40/90 VERNAM IF 1+5 GS 30/85 VERNAM IF 6+5 SB 30/55 71 VERNAM IF 1+5 BA 40/50 VERNAM IF 5+5 SB 10/40 72 VERNAM IF 1+5 WT 40/75 73 VERNAM IF 6+5 SB 30/60 74 VERNAM IF 1+5 WT 50/75 75 VERNAM IF 1+5 BA 30/50 VERNAM IF 1+5 WT 40/75 76 VERNAM IF 1+5 CT 55/70 VERNAM IF 1+5 WT 50/75 77 VERNAM IF 1+5 BA 30/60 VERNAM IF 6+1 SB 10/40 78 R-12001 IF 6+5 CT 50/65 VERNAM IF 1+5 CT 10/50 VERNAM IF 6+5 SB 40/60 79 VERNAM IF 6+5 SB 30/60 80 VERNAM IF 1+5 BA 40/70 VERNAM IF 1+5 CT 40/60 VERNAM IF 1+5 R 60/95 VERNAM IF 6+5 SB 40/60 81 VERNAM IF 1+5 CT 40/50 82 VERNAM IF 1+5 GS 60/100 VERNAM PPI 6+0.5 SB 20/40 83 VERNAM IF 6+5 CN 50/95 VERNAM IF 1+5 CT 30/50 VERNAM IF 1+5 GS 80/100 VERNAM IF 6+1 SB 10/50 84 VERNAM IF 1+5 GS 70/95 VERNAM IF 6+1 SB 0/40 85 RONEET IF 3+5 GS 30/75 VERNAM IF 1+5 GS 50/100 VERNAM PPI 6+5 SB 10/50 86 VERNAM IF 1+5 BA 70/83 VERNAM IF 6+5 CN 60/90 VERNAM IF 1+5 GS 70/100 VERNAM PPI 6+1 SB 20/40 87 VERNAM IF 6+5 CN 80/90 VERNAM IF 1+5 GS 60/100 VERNAM IF 6+5 SB 40/60 88 VERNAM IF 6+5 CN 80/100 VERNAM IF 1+5 GS 80/100 VERNAM IF 6+1 SB 10/42 89 VERNAM IF 1+5 CT 10/50 VERNAM IF 6+5 SB 30/60 90 VERNAM IF 1+5 BA 30/55 VERNAM IF 6+1 SB 0/50 VERNAM IF 1+5 WT 60/85 91 VERNAM IF 1+5 CT 20/50 VERNAM IF 6+5 SB 30/55 92 VERNAM IF 1+5 BA 20/55 VERNAM IF 1+5 CT 30/50 Com ound Herbicide Method of Rate Crop Result Number Application 92 VERNAM IF 6+5 SB 20/50 93 VERNAM IF 1+5 GS 60/95 VERNAM IF 6+5 SB 40/60 94 VERNAM IF 1+5 GS 80/100 VERNAM IF 6+5 SB 30/50 VERNAM IF 1+5 WT 70/85 95 VERNAM IF 6+5 CN 80/90 VERNAM IF 1+5 R 20/70 96 VERNAM IF 1+5 BA 40/70 VERNAM IF 1+5 CT 40/60 VERNAM IF 1+5 R 60/95 VERNAM IF 6+5 SB 30/60 97 VERNAM IF 1+5 BA 40/55 98 VERNAM IF 6+5 SB 30/55 99 VERNAM IF 1+5 BA 30/55 VERNAM IF 1+5 R 20/70 100 VERNAM IF 1+5 BA 30/55 VERNAM IF 1+5 R 60/70 101 VERNAM IF 1+5 BA 40/55 VERNAM IF 6+5 SB 20/50 VERNAM IF 1+5 WT 60/85 102 VERNAM IF 1+5 BA 30/55 VERNAM IF 1+5 CT 40/50 VERNAM IF 6+5 SB 0/50 103 R-12001 IF 6+5 CT 50/65 VERNAM IF 1+5 CT 30/50 VERNAM IF 6+5 SB 0/60 VERNAM IF 1+5 WT 60/85 104 VERNAM IF 1+5 BA 40/55 VERNAM IF 6+5 SB 30/60 VERNAM IF 1+5 WT 60/70 105 VERNAM IF 1+5 BA 40/55 VERNAM IF 6+5 SB 0/60 VERNAM IF 1+5 WT 60/85 106 VERNAM IF 1+5 BA 3-/60 VERNAM IF 6+5 CN 70/95 VERNAM IF 6+5 SB 30/60 107 VERNAM IF 6+5 SB 0/60 VERNAM IF 1+5 WT 60/85 In side-by-side tests with various weed species and crops, it was found that weed control was maintained while at the same time the crop species were protected or injury thereto reduced, when compared to a check or control flat. The control flat contained no antidote compound.

The following Table further exemplifies those results.

Table IV Percent Injury HERBICIDE RATE GS SC WG RONEET 31b/A 50 50 100 (PPI) Compound Rate (IF) GS SC WG Number 2 11b/A 40 100 100 33 1 Ib/A 30 100 100 35 llb/A 30 100 100 36 1 Ib/A 10 100 100 37 1 Ib/A 25 100 100 38 llb/A 30 100 100 64 1 Ib/A 30 100 100 65 1 Ib/A 15 100 100 68 1 Ib/A 40 100 100 69 1 lb/A 40 100 100 70 1 Ib/A 15 100 100 93 1 Ib/A 40 100 100 Compound Rate (IF) GS SC WG Number 93 5 Ib/A 30 100 100 106 1 lb/A 40 100 100 Percent Injury HERBICIDE RATE RC WT WG WO ODRAM 8ib/A 25 30 100 100 (PPI) Compound Rate (IF) RC WT WG WO Number 3 1 lb/A 50 20 100 100 51b/A 0 60 0 0 17 1 Ib/A 50 10 100 100 5 Ib/A 20 0 100 100 18 5 Ib/A 20 10 100 100 19 11b/A 60 20 100 100 5 Ib/A 0 60 100 100 25 1 Ib/A 40 10 100 100 5 Ib/A 10 10 100 100 27 1 Ib/A 60 10 100 100 5 Ib/A 10 60 100 100 29 5 Ib/A 20 10 100 100 47 5 Ib/A 20 20 100 100 51 5 Ib/A 40 20 100 100 94 5 Ib/A 40 10 100 100 96 5 Ib/A 60 10 100 100 32 1 Ib/A 40 20 100 100 5 Ib/A 0 10 80 100 35 1 Ib/A 10 10 100 100 37 1 Ib/A 40 10 100 100 38 5 Ib/A 30 10 100 100 Percent Injury HERBICIDE RATE C WG FIT SUTAN 12/lb/A 50 100 100 Compound Rate (PPI) C WG FT Number Tank Mix 3 5 lb/A 20 100 100 18 5 lb/A 40 100 100 19 5 lb/A 40 100 100 21 5 lb/A 40 100 100 23 5 lb/A 40 100 100 24 5 lb/A 30 100 100 29 5 Ib/A 20 100 100 51 5 lb/A 20 100 100 The compounds used according to the present invention may be employed in effective herbicidal compositions comprising the antidote and a thiolcarbamate herbicide as described above. The herbicidal compositions maybe tested in the above manner.

The compositions according to the present invention for the protection of cultivated crop plants comprise the active herbicidal compound and an antidote therefor selected from the above-described compounds. The compositions of herbicide and antidote may be prepared by conventional methods by the thorough mixing and grinding of the active herbicide agents and the antidote optionally with suitable carriers and/or other distribution media, possibly with the addition of dispersion agents or solvents.

The antidote compounds and compositions may be used in any convenient form. A solvent or inert carrier is not necessary in view of low volume spray technology which permits the use of neat technical grade materials as sprays. Thus, the antidote compounds and compositions with thiolcarbamate herbicides maybe formulated into, for example, emulsifiable liquids, emulsifiable concentrates, liquid, wettable powder, powders or granulates. In its preferred form, a non-phytotoxic quantity of an antidote compound is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the herbicide may be incorporated into the soil and thereafter the antidote compound may be incorporated into the soil. Moreover, the crop seed itself may be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicide, or it may be planted in untreated soil which is subsequently treated with the herbicide. The addition of the antidote compound does not affect the herbicidal activity of the herbicide towards weeds.

The amount of antidote compound present may range from 0.001 to 30 parts, by weight, of antidote compound per part, by weight, of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. It is to be understood that a non-phytotoxic, but antidotally effective quantity of antidote compound will be employed.

After treatment with the antidote and herbicide there is obtained soil which is novel in composition. The soil is improved in its capability to grow crops and to offer weed control.

Furthermore, the treated soil has the particular utility for allowing seed of crops otherwise injured by herbicide to be planted and grown. The herbicide has its utility in controlling undesirable vegetation; the antidote compound decreases the injury caused by the herbicide to the crop species, and the soil treated with herbicides and antidote compound provides an improved media to grow the crop in the presence of an otherwise injurious herbicide.

In the utility of the present antidote compounds and improved herbicide system, a thiocarbamate may be applied to the soil. Application of the herbicide to the soil may take place by pre-plant incorporation. Following application of the herbicide to the soil, crop seeds may be planted. Seed planting may be followed by application of the antidote as a preemergence surface application. This sequence of application of herbicide, seed planting and antidote is unusual and fully effective in decreasing injury to the plant crop, otherwise injured by the thiolcarbamate.

Legume Evaluation Test Various antidote compounds described herein have been found capable of decreasing injury to the class of crops known as legumes. By the term 'legumes' is meant those plants that have a symbiotic relationship with nitrogen fixing organisms. For example, soybeans, varieties of Phaeseolus vulgaris (L.), peanuts, alfalfa and clover.

The following test was performed to determine the efficacy as decreased injury of the legume crops by a representative thiolcarbamate herbicide, EPTAM (EPTC), S-ethyl-di-npropyl thiolcarbamate with compounds described above. Various edible bean and pea vaneties were tested. The antidotes were applied at 1 and 2 Ib/A pre-plant incorporated, tank mixed with EPTC at 6 Ib/A pre-plant incorporated.

Stock Solutions: Antidote: For each candidate compound employed 39 mg. dissolved in 25 ml. acetone; 2.5 ml. equivalent to 1 Ib/A preplant incorporated.

Herbicide: EPTAM 6E: 1560 mg. dissolved in 250 ml. water; 5 ml. equivalent to 6 Ib/A preplant incorporated.

The crops tested were Navy bean - NB, Kidney bean - KB, Pinto bean - PB (various varieties of Phaeseolus vulgaris L.) and peas (Pisum sativum L.) The weed species included in the tests were watergrass - WG and foxtail - FT.

Table V Percent Injury PPI (Tank Mix) 4 Week Data NB PB WG FT EPTC 6 Ib/A 65 50 100 100 Compound Rate NB -B WG FT Number 3 1 Ib/A 30 20 100 100 2 Ib/A 20 20 100 100 17 1 Ib/A 30 50 100 100 2 lb/A 50 40 18 1 Ib/A 25 30 100 2 Ib/A 50 40 28 11b/A 50 40 2 Ib/A 50 30 100 100 29 1 Ib/A 0 40 100 100 2 Ib/A 30 20 100 100 33 1 Ib/A 40 40 100 100 2 Ib/A 50 40 100 100 51 1 Ib/A 40 20 100 100 2 Ib/A 50 30 100 100 54 1 Ib/A 30 40 100 100 54 2 Ib/A 50 0 100 100 57 1 Ib/A 50 30 100 100 2 Ib/A 50 40 100 100 90 1 Ib/A 50 40 100 100 2 Ib/A 50 10 100 100 At 2 pounds per acre, compound number 3 also exhibited complete protection (100%) of kidney beans. Compound number 28 exhibited 50 percent protection of kidney beans at 2 pounds per acre. Injury to peas was decreased 37.5 percent using compound number 28 at 2 pounds per acre.

WHAT WE CLAIM IS: 1. A composition which comprises a herbicide (as hereinbefore defined) and an antidote therefor whichis a compound corresponding to the following general formula:

wherein n represents 0, 1, 2 or 3; X represents methyl, chloro, bromo, methoxy or trifluoromethyl; provided that, when X represents bromo, methoxy or trifluoromethyl, n represents 1; and R represents C1-C4 alkyl, C3-C6 alkenyl which may optionally be substituted up to four times

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

varieties of Phaeseolus vulgaris (L.), peanuts, alfalfa and clover.

The following test was performed to determine the efficacy as decreased injury of the legume crops by a representative thiolcarbamate herbicide, EPTAM (EPTC), S-ethyl-di-npropyl thiolcarbamate with compounds described above. Various edible bean and pea vaneties were tested. The antidotes were applied at 1 and 2 Ib/A pre-plant incorporated, tank mixed with EPTC at 6 Ib/A pre-plant incorporated.

Stock Solutions: Antidote: For each candidate compound employed 39 mg. dissolved in 25 ml. acetone; 2.5 ml. equivalent to 1 Ib/A preplant incorporated.

Herbicide: EPTAM 6E: 1560 mg. dissolved in 250 ml. water; 5 ml. equivalent to 6 Ib/A preplant incorporated.

The crops tested were Navy bean - NB, Kidney bean - KB, Pinto bean - PB (various varieties of Phaeseolus vulgaris L.) and peas (Pisum sativum L.) The weed species included in the tests were watergrass - WG and foxtail - FT.

Table V Percent Injury PPI (Tank Mix) 4 Week Data NB PB WG FT EPTC 6 Ib/A 65 50 100 100 Compound Rate NB -B WG FT Number

3 1 Ib/A 30 20 100 100

2 Ib/A 20 20 100 100

17 1 Ib/A 30 50 100 100 2 lb/A 50 40

18 1 Ib/A 25 30 100

2 Ib/A 50 40

28 11b/A 50 40

2 Ib/A 50 30 100 100

29 1 Ib/A 0 40 100 100

2 Ib/A 30 20 100 100

33 1 Ib/A 40 40 100 100

2 Ib/A 50 40 100 100

51 1 Ib/A 40 20 100 100

2 Ib/A 50 30 100 100

54 1 Ib/A 30 40 100 100

54 2 Ib/A 50 0 100 100

57 1 Ib/A 50 30 100 100

2 Ib/A 50 40 100 100

90 1 Ib/A 50 40 100 100

2 Ib/A 50 10 100 100 At 2 pounds per acre, compound number 3 also exhibited complete protection (100%) of kidney beans. Compound number 28 exhibited 50 percent protection of kidney beans at 2 pounds per acre. Injury to peas was decreased 37.5 percent using compound number 28 at 2 pounds per acre.

WHAT WE CLAIM IS: 1. A composition which comprises a herbicide (as hereinbefore defined) and an antidote therefor whichis a compound corresponding to the following general formula:

wherein n represents 0, 1, 2 or 3; X represents methyl, chloro, bromo, methoxy or trifluoromethyl; provided that, when X represents bromo, methoxy or trifluoromethyl, n represents 1; and R represents C1-C4 alkyl, C3-C6 alkenyl which may optionally be substituted up to four times

by chloro, C3-C6 alkynyl, mono- to hexa- fluoro-, chloro- or bromo- C2-C6 alkyl, C2-C8 dialkylamino, C3-C6 cyanoalkylthioalkyl, phenyl which may optionally be substituted by C1-C4 alkyl or chloro, benzyl which may optionally be substituted in the 4-position by chloro or methoxy, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 cyanoalkyl, C3-C7 alkoxycarbonylalkyl, C2-C6 formamidoalkyl, C4-C7 alkoxycarbonylalkenyl, Ca-Ce alkylcarbonylalkyl, phosphonomethyl, trifluoroacetamidomethyl, 4-chlorophenylthiomethyl, 1 ,3-dioxacycohexane-5,5-methyl methylene, 3-pyridylmethyl, phenoxyethyl, cyclopropyl, 3-phenylpropyn-2-yl, methylthioacetimino, acetoneimino or benzaldimino; provided that, when R represents C3-C6 alkenyl or C3-C6 alkynyl, the phenyl ring is other than methoxy substituted; and provided that, when R represents C1-C4 alkyl or Ca-Ce alkenyl, the phenyl ring is other than bromo-substituted.

2. A composition which comprises a thiolcarbamate herbicide and an antidote therefor which is a compound corresponding to the following general formula:

wherein X represents hydrogen, methoxy, chloro, or bromo; and R represents mono- to hexa- fluoro, chloro or bromo- C2-C6 alkyl or C2-C6 alkenyl substituted by chloro; provided that, when R represents 2-chloroethyl, X represents other than chloro.

3. A composition as claimed in claim 1 comprising a herbicide which is a thiolcarbamate herbicide.

4. A composition as claimed in claim 2 comprising a thiolcarbamate herbicide which is S-n-propyl-N,N-di-n-propyi-thiolcarbamat 5. A composition as claimed in any of claims 1 to 4 comprising an inert carrier or diluent.

6. A composition as claimed in any of claims 1 to 5 substantially as herein described.

7. A composition as claimed in any of claims 1 to 5 substantially as herein described with reference to the testing procedures.

8. A two-component system which comprises a first component comprising a herbicide (as hereinbefore defined) and a second component comprising an antidote therefor which is a compound corresponding to the general formula defined in claim 1.

9. A two-component system as claimed in claim 8 comprising a first component comprising a herbicide which is a thiolcarbamate herbicide.

10. A two-component system as claimed in claim 8 or claim 9 substantially as herein described.

11. A method of controlling vegetation which comprises applying to the locus where the control is desired a composition as claimed in claim 1 or claim 3.

12. A method of controlling vegetation which comprises applying to the locus where the control is desired a composition as claimed in claim 2 or claim 4.

13. A method as claimed in claim 11 or claim 12 substantially as herein described.

14. A method as claimed in claim 11 or claim 12 substantially as herein described with reference to the testing procedures.

15. A method of protecting a plant crop from injury due to a herbicide (as hereinbefore defined) which comprises applying to and/or incorporating in the soil in which the crop is to be planted, prior to planting, a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 1.

16. A method of protecting a plant crop from injury due to a herbicide (as hereinbefore defined) which comprises applying to and/or incorporating in the soil in which the crop has been planted, subsequent to planting, a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 1.

1.A method of protecting a plant crop from injury due to a herbicide (as hereinbefore defined) which comprises applying to the crop seed, prior to planting, a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 1.

18. A method of protecting a plant crop from injury due to a herbicide (as hereinbefore defined) which comprises introducing a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 1, into the seed furrow during the sowing procedure.

19. A method as claimed in any of claims 15 to 18 in which the herbicide is a thiolcarbamate herbicide.

20. A method as claimed in any of claims 15 to 19 substantially as herein described.

21. A method as claimed in any of claims 15 to 19 substantially as herein described with reference to the testing procedures.

22. A method of protecting a plant crop from injury due to a thiolcarbamate herbicide which comprises applying to and/or incorporating in the soil in which the crop seed is to be planted, prior to planting, a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 2.

23. A method of protecting a plant crop from injury due to a thiolcarbamate herbicide which comprises applying to and/or incorporating in the soil in which the crop has been planted, subsequent to planting, a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 2.

24. A method of protecting a plant crop from injury due to a thiolcarbamate herbicide which comprises applying to the crop seed, prior to planting, a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 2.

25. A method as claimed in any of claims 22 to 24 in which the thiolcarbamate herbicide is S-n-propyl-N,N-di-n-propyl-thiolcarbamate.

26. A method as claimed in any of claims 22 to 25 in which the plant crop is soybeans.

27. A method as claimed in any of claims 22 to 26 substantially as herein described.

28. A method as claimed in any of claims 22 to 26 substantially as herein described with reference to the testing procedures.

29. Crop seed having applied thereto a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 1.

30. Soybeans having applied thereto a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 2.

31. Crop seed or soybeans as claimed in claim 29 or claim 30 substantially as herein described.

32. Crop seed or soybeans as claimed in claim 29 or claim 30 substantially as herein described with reference to the testing procedures.

33. Soil having applied thereto and/or incorporated therein a non-phytotoxic antidotally effective amount of a compound corresponding to the general formula defined in claim 1 or claim 2.

34. Soil as claimed in claim 33 substantially as herein described.

35. Soil as claimed in claim 33 substantially as herein described with reference to the testing procedures.