CA1097649A - N-(benzenesulfonyl) carbamates-herbicidal antidotes - Google Patents

Abstract

Abstract of the Disclosure N-(substituted benzenesulfonyl) carba-mates as new compositions of matter useful as active herbicidal antidotes to protect against and decrease crop injury when used with a thio-carbamate herbicide when applied in various methods; improved hervicidal compositions and utility of said compositions to protect against and decrease phytotoxic crop injury when employ-ing thiocarbamate herbicides and a two-part herbicide system comprising a first-part of one or more thiocarbamate herbicide and a second part of an effective antidote therefor compound said antidote compounds of the class N-benzene sulfonyl carbamates having the formula

Description

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Background of the Invention While many herbicides are immediately toxic to a large number of weed pests, it is known that the effect of many herbicides upon important plant cultivations is either non-selective or no-t adequately selective. Thus, many herbicides damage not only the weeds to be controlled but, to a greater or lesser extent, the desirable cultivated plants as well. This holds true for man~ her~icidal compounds which have been commercially successful and are commercially available. These herbicides include types such as triazines, urea derivatives, halogenated acetanilides, carbamates, thiocarbamates and the like. Some examples of these compounds are described in U.S.
Patents No. 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 2Q the crop plants sometimes result. This abnormal growth in the crop plants results in loss of crop yield. The search ; continues for good selective herbicides.
Previous attempts are described to overcome this problem. The treatment of t~e crop seed with certain "hormonal"
antagonistic agents prior to planting is described; see U.S.
Patents 3,13],509 and 3,564,768. The protective agents, as well as the herbicide, in these prior processes are largely specific ~'f~
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to certain cultivated plant species or in the nature of the antagoni.stic agents. The prior antagonistic agents have not been notably successful. The aforementioned patents specifically exemplify and describe the treatment oE seeds employing compounds of a different chemi.cal class, not suggestive of the present invention.
U.S. Patents 3,7~9,760 and 3r933~894~ and East German Patent DL 74982 disclose certain N-benzenesulonyl carbamate . compounds, disclosed herein. Also, in Berichte, Vol. 37 at 10 Page 699, certain compounds are specifically disclosed. None of these references anticipate or make obvious the utility of the compounds as herbicidal antidotes for thiocarbamate herbi-cides, in particular for S-n-propyl N,N-di-n-propylthiocarbamate.
None of the references anticipate or make obvious the improved r, herbicidal compositi.ons for use employing N-benzenesulfonyl carbamates and an active thiocarbamate herbicide, particularly S-n-propyl N,N-di-n-propylthiocarbamate.

. Descripti.on of the Invention ~ It has been di.scovered that cul~ivated crop plants, can :: ~ 20 be protected against injury ~y thiocar~amate-type herbicides, ,r~ and said injury can be decreased when the thiocarbamate-type . herbici.des r each alone or in mixtures or combination with other Y - compounds, are applied in a variety of ways. Further r as an ,~ ~ alternative effect, the tolerance of the plants, to these herbi cides, can be suhstantially- increased by adding to the soil an : antidote compound of the type N ~substituted benz~nesulfonyl) r~ . carbamates:, th.exe~ore~ the present inYention also includes a t~o-part h.erbi~cide system comp~ising a first part of one or more "

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:, , thiocarbamate herbicide and a second part of an effective anti-dote compound therefore, said anti`~dote compounds corresponding to the following formula ~f ~ ~ C OR

in which ~ is hydrogen, bromo, chloro, methoxy, trifluoromethyl, and methyl; n is an integer from 1 to 3 inclusive, provided that when X is bromo, trifluoromethyl, or methoxy, n is l; and R
is selected from alkyl having 1 to 4 carbon atoms, inclusive, haloalkenyl having 3 to 6 carbon atoms, inclusive and wherein halo is chloro from 1 to 4, inclusive, alkynyl having 3 to 6 carbon atoms, inclusive, trifluoracetamidomethyl, dialkylamino having a total of 2 to 8 carbon atoms, inclusive, cyanoalkylthio-alkyl having a total of 3 to 6 carbon atoms, inclusive, phos-phonomethyl, lower alkyl ~ubstituted phenyl said lower alkyl each having 1 to 4 carbon atoms, inclusive, 4-chlorophenylthio-methyl, alkoxyalkyl having ~ ~o ~ carbon atoms, inclusive, alkylthioalkyl having 2 to 6 carbon atoms, inclusive cyanoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkyl having 3 to 7 carbon atoms, inclusive, formamidoalkyl having 2 to 6 carbon atoms, inclùsive, alkoxycarbonylalkenyl havin~ 4 to 7 carbon atoms, inclusive, alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-methyl methy-lene, phenyl, chlorophenyl, benzyl, 4-chlorobenzyl, 4-methoxy-: benzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn~2-yl, ` methylthioacetimino, acetone amino and ~enzaldimino.
~ . Cer~ain compounds disclosed herein are considered new ~ composltions of matte.r and correspond to the following formula O ~ O
P~ C - OR

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in which X is hydrogen, b.romo, chloro~ methoxy, trifluoromethyl, and methyl; n is an integer from 1 to 3 inclusive, provided that when X is bromo, tri.fluoromethyl, or methoxy, n is l; and R is selected from haloalkyl having 2 to 6 carbon atoms, inclusive, wherein halo is ch.loro or fluoro from 1 to 6, inclusive, halo-alkenyl having 3 to 6 carbon atoms, inclusive and wherein halo i.s chloro from 1 to 4, inclusive, dialkylamino having a total of

2 to 8 carbon atoms, inclusive, cyanoalkylthioalkyl having a total of 3 to 6 carbon atoms, inclusive, phosphonomethyl, tri-fluoroacetamidomethyl, lower alkyl substituted phenyl said lower alkyl each having 1 to 4 carbon atoms, inclusive, 4-chloro-phenylthiomethyl, alkoxyalkyl having 2 to 6 carbon atoms, inclu-sive, alkylthioalkyl having 2 to 6 carbon atoms, inclusive cyanoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonyl-alkyl having 3 to 7 carbon atoms~ ï.nclusive, formamidoalkyl having 2 to ~ carbon atoms/ inclusive, alkoxycarbonylalkenyl ha~ing 4 to 7 carbon atoms, inclusive, alkylcarbonylalkyl having

3 to 6 carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-methyl methylene, chlorophenyl, 4-chlorobenzyl, 4-methoxyhenzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn-2-yl, methylthio-acetimino, acetone imino and benzaldimino.
~lso provided that when X is trifluoromethyl and n is 1, , then R can be alkyl having 1 to 4 carbon atoms inclusive, alkenyl having 3 to 6 carbon atoms, inclusive, and alkynyl having 3 to 6 carbon atoms, inclusi~e.
In the a~ove descriptions, the followïng embodiments are intended ~or the various substi.tuent groups: For R, haloalkyl preferahly includes those members which. contain from 1 to 6 car-~ bon atoms, i.nclusi.ve~ i.n ~oth straight chain and branched chain :.: 30 configurations and th.e term "halo" includes chloro, bromo and s;

`.' ~3 fluoro, as mono, _, tri, tetra7 or hexa substitutions that is from 1 to 6 halo substituents. As exemplary of the alkyl portion within the preferred embodiment are the following: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl and tert.-but~l. For R, alkynyl preferably includes those members which contain from 3 to 6 carbon atoms and at least one acety-lenic or triple bond such as in propargyl (propynyl), 2-butynyl, 3-butynyl, 1,1-dimethyl-3-butynyl, and the like. Chloroalkenyl preferably includes those members which contain from 3 to 6 carbon atoms, inclusive, and at least one olefinic double bond.
~ther substituent groups are as indïcated in carbon content in the above description.
As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate-type and other herbicides to render them selective in their action. The o~servation noted with the pres-ence of the herein described antidote i5 a decrease in phyto-toxuity with respect to various crops, otherwise observed when various thiocarbamate herbicides are used for weed control.
Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herhicidal effect of the thiocarbamate with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.
Therefore, the terms, "herbicide antidote" or "antidotal amount", is meant to describe that effect which tends to counter-act the normal injurious herbicidal response that the herbicide might otherwise prod~ce. ~hether it is to be termed a remedy, ,;lnterferant, protectan~, antagonist or the like, will depend !:~

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upon the exact mode of actlon. 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 Eor this purpose.
The compounds of this invention represented by the avove formulas can be prepared by several different procedures depending upon the starting materials.
One general method for preparing N-benzenesulfonyl alkynyl la carbamates is the reaction of an appropriate alkynol with ben-zenesulfonyl isocyanate. More particularly, the reaction is performed in the presence of a solvent such as benzene or chloro-form with catalytic amounts of triethylamine and dibutyl tin dilaurate. In some instances, a catalyst is not required. After the reaction is complete, the product is recovered by filtration or evaporation of the solvent. I~necessary, the product can be recrystallized from a suitable solvent.
A general method for preparing N-benzenesulfonyl alkyl carbamates is ~he reaction of an appropriate benzenesulfonamide with an alky~ chloroformate in th~ presence of a catalyst, such as potassium carbonate. A solvent is normally employed to facilitate the reaction and aid in the work-up of the product.
After filtration, extraction and dryin~, the product can be ; purified further by trituration with hexane or recrystallization from a suitable solvent. In mos-t instances, the structure was confirmed by infrared, nuclear magnetic resonance or mass spectroscopy.
The compounds of the presen~ invention and their prepar-ation are more particularly illustrated by the following examples.

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Following the examples of preparation is a table of compounds which are prepared according to the procedures described herein.
Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPI.E I

Preparation of 2-butyn-1-yl p~toluenesulfonyl carbamate.
To a solution o~ 2-butyn-1-ol, 1.75 g. (0.025 mole) in 25 ml~ chloroform was added slowly 4.9 gO ~0.025 mole) p-toluene-sulfonyl isocyanate. An exothermic reaction resulted. The product was removed by evaporating the solvent~ There was obtained a yield of 6.4 g. of the title compound, m.p. 85-90C.

EXAMPLE II

Preparation of 2-bromopropyl p-toluenesulfonyl carbamate.
In a similar procedure as described in Example 1, 2-bromo-1-propanol, 3.4 g~ (0.0~5 mole~ in 25 ml. chloroform and 4.9 g.
(0.025 mole) p-toluenesulfonylisocyanate were reacted. After a similar work-up to remove the solvent, there was obtained a yield of 8.4 g. of the title compound, n30 1.5375.

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EXAMPLE III

Prepara-tion of hexafluoroisopropyl p-toluenesulfonyl carbamate.
In a simllar procedure as described in Example 1, sym-hexafluoroisopropanol, 4.2 g. in 25 ml. chloroform and 4.9 g.
(0.025 mole) p toluenesulfonylisocyanate were reacted with 2 drops of triethylamine as catalyst. After a similar wor~ up to remove the solvent, there was obtained a yield of 8.9 g. of the title compound, m.pO 69-75C.

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EXAMPLE IV

Preparation of N-(p-chlorobenzenesul~onyl~-propargyl carbamate.
To a solution of 1.7 g. (0.03 mole) of propargyl alcohol in 20 ml. of benzene containing one drop of triethylamine and one drop o* dibutyl tin dilaurate was added a solution of 6.5 g. (0.03 mole) p chlorobenzenesulfonyl isocyanate in 25 ml.
benzene. The reaction was exothermic and the temperature was allowed to rise to 30C. The mixture was stirred several hours at room temperature and the precipitated solid was filtered and washed with a small amount of hexane and dried. There was obtained a yield of 8.0 g. ~98% of theory~ of the title compound, ` m.p. 106-108C. A pure sample melted at 120.5-121C. The ; structure was confirmed by infrared, nuclear magnetic resonance, and mass spectroscopy.

EXAMPLE V

Preparation of N-(p-chloro~enzenesulfonyl~-ethyl carbamateO
p-Chlorobenzenesulfonamide ~6.1 g., 0.032 mole), potas-sium carbonate (10.8 g., 0.078 molel, and ethyl chloroformate (3.7 g., 0.034 mole) in 40 ml. of acetone were stirred and re-fluxed for two hours. During the heating period the mixture~ecame thick and was diluted with another 30 ml. of acetone.
The cooled mixture was poured into 150 ml. of water and filtered through Celite. Th~ filtrate was acidi~ied with hydrochloric acid with cooling ~pH about 2~ and the product extracted with benzene. The extract was washed with water and dried over anhy-drous magnesium sulfate. Removal of the solvent left the title compound as a solid. There was obtained a yield of 5.5 g.
C65~ of theorv) of the title compound, m.p. 85-90C. Th~ struc-ture was confirmed by IR.

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EXAMPLE VI

Preparation of N-(p-methoxybenzenesulfonyl)-ethyl carbamate.
p-Methoxybenzenesulfonamide (5.0 g., 0.032 mole~
potassium carbonate (10.8 g., 0.078 mole), and ethyl chloroformate (3.7 g., 0.034 mole) in 40 ml. of acetone were refluxed for 2.5 hours. The product was worked up in a similar manner as in Example V. There was obtained a yield of 3.9 g. ~47% of theory) of the title compound, m.p. 110-116C.
The following is a table of the compounds which are pre-pared according to the aforementioned procedures. Compoundnumbers have been assigned to them and are used for identification throughout the balance of the specification.

TABLE I
X~ r--~ H
N C OR

m.p.C
COMPOUND or n NUMBER _ R D
1 4-CH3 CH(CH3~2 sticky*

3 4-Cl C2H5 85-90

4 4-CH3 CH(CF3)2 69-75 4-CH2 CH2CH2Br 1.5460 6 4-CH3 CH2CH2C1 1.5348 7 4-CH2 CH2CHBrCH3 1.5375 9 4-CH3 CH2cH(cl~cH2cl semi-solid*

4-CH3 CH2C(CH3)ClCH2C1 1.5640 TABLE I ~continued) m.p.C.
COMPOUND or n3 NUMBER X R D
11 4-Cl CH2CHC12 114-115 12 4-Cl CH2CF3 142-145 13 4-Cl CH~CF3~2 83-87 14 4-Br CH2CH2Cl semi-solid*
4-Cl CH2CH~Cl~CH2Cl semi-solid*
16 4-Cl CH2CH2B~ 92-98 18 4-Cl CH2C = CH 106-108 ~ 19 4-Cl OEI2CH2C _ CH 102-104 ,~ ~ 20 4-Cl C(CH3~2CH2C - CH 108-110 , . 21 4-Cl CH C - CCH 141~142 22 4~CH3 CH2CH2C = CH glass*

~ - - 3 H CH2CH~C - CH semi-solid*
26 H CH2CCl-CH2 semi-solid*
2Q 27 4-Br CH~C - CH 124-125 28 4-Br CH C - CCH 134-135 : 29 H CH2~F3 H CH2CH2Cl semi-solid*
..
3I E CH2CHC12 semi-solid*
. : 32 E CH3. 127~130 :

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TABLE I ( con tin ue d ) m.p. C.
COMPOUND o r n NUMBER_ X R D_ 33 H C2~I5 1.5003 34 H n C3H7 1.4942 H c C3 7 1.4952 38 H CH2CH=CH2 1O5175 39 4-CH3 CH2CC12CH2C1 1.5300 4-CH3 CH2CH=CH2 1.5375 41 4-CH3 CH2C(CH3) CH2 1.5300 42 4-CEI3 CH2C~Cl~=CEI2 1.5340 43 4-CH3 CH2~-~CH 1.5384 44 4-CH3 C(CH3)3C - CH glass*
4-CH3 C(CH3)2C - CCH3 glass*
46 4-CH3 CH(i-C3H7~ CH glass*
47 4-CH3 N(C2Hs)2 semi-solid*
48 4-CH3 CH2NHCCF3 sticky 49 4-CH3 CH2P(~)(o~I)2 semi-solid 4-CH3 C 2S ~ 1 65-70 51 4-Cl CH3 127-130 52 4-Cl n C3 7 1.5111 ~3 4-Cl C2 4 semi-solid ';

TABLE I ( continued ) m. p . C .
COl~IPOUND aE, n30 NUMBER_ X R D
54 4-Cl CH2CH=CH2 1.5262 4-Cl CH2C (Cl) =CH289--92 56 ~ 4--Cl CH2C (O) OC2H51.4783 57 4 -Cl phenyl 101- 104 58 4-Cl CH2~> 174-176 59 4-Cl CH2C C~ 109-111 64 3,4-diCl C2H5 100-102 - 66 3-Cl C2H5 1.5155 67 : 3--Cl CH2CF3 108--110 68 3-Cl CH2CH=CH2 58-61 69 3--Cl CH2C----CH 73-76 3--C l CH2 C_CCH 3 95 - 97 ; 71 2,4 ~ 6-CH3 C2H5 159~160 72 2,4,6-C~3 C-C3~7 112-114 2,4,6-C~3 CH2CF3 159-162 74 2,4,6-CH3 CH2CC13 139-141 ,.

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:, TABLE I (continued~

m.p.C.

NUMBER X R or nD
2,4,6-CH3 CH C CH 150-151 76 2,4,6-CH3 4-Cl-phenyl 131-132 77 2,4,6-CH3 -N=CH ~ 120-122 dec.
78 4-CH3 C2H4F 1.5022 79 4-CH3 C2H4SC2H4CN 1.5482 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-Cl C2H4F 1.5192 ~ 84 4-Cl CH2CF2CF2H 82.85 !' 85 4-C1 C~CH3)(C2H5)C - CH 122-124 86 4-Cl C2H4OC2H5 semi-solid*
87 4-Cl C2H4SC2H5 1.5360 88 4~Cl C~CH3~2CN 68-71 89 4-Cl C2H4C(o~cH3 94-98 4-Cl CH2 ~ ~ viscous semi-/ ~ o solid*

; 91 4-?Cl CH~CH3)C(O)OC2H5 1.4950 92 4-Cl C2H4NHC (O)H 154-157 dec.
`~ 23 4-Cl C(CH3)=CHC(O)OC2H5 1.5100 94 4-C1 4-Cl-phenyl 159-160 4-C1 2-Cl-phenyl 77-80 .;
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TABLE I (continued~

m.p.C.
COMPOUND n NUMBER X R D
96 4-C1 3,4-diCH3-phenyl 100-103 97 4-C1 3,4,5-tri-CH3-phenyl 1.5473 98 4-C1 2-i-C3H7-Phen~l 1.5471 99 4-C1 3,5-di-1-C3H7-phenyl 1.5415 100 4-C1 3-t-C4Hg-phenyl oil*
101 4-Cl benzyl 98-101 102 4-C1 4-C1-benzyl 138-139 103 4 Cl 4-CH30-benzyl 119-122 104 4-Cl phenoxy-CH2CH2 98-99 105 4-Cl -N-C(CH3~2 161-162 106 4-Cl -N=c(cH3lscH3 125-128 107 4-Cl -N=CH-phenyl 120-124 dec.

*Structure confirmed ~y either infrared or nuclear magnetic resonance spectroscopy.

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The herbicides indicated in the tables and elsewhere are used at rates which produce effective control of undesir-able vegetation. The range of 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 characterized as 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 re~dily may be made. Within the present invention, the prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by thïs method is not intended to be limited by the specific crops employed in the examples.
The herbicidal compound employed in the utility of this invention is an active thiocarbamat~ herbicide of a general type. That is, it is a mem~er o~ the class of herbicidally active compounds effective agains-t a wide range of plant species with no discrimination bet~een desira~le and undesirable species.
The method of controlling vegetation comprises applying an herhicidally effective amount of the herein described her~icidal compound to the area or plant locus where control is desired.
'30 The compositions as set forth in this invention include those ; -16-:

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wherei.n the antidote i.s as described above and the preferred active herbicial compound is selected from the class of thio-carbamate herbicides and includes the following as representative members, S-ethyl dipropyl thiocarbamate, S-ethyl dilsobutyl thiocarbamate, S-propyl di-n-propyl thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, S-ethyl hexahydro-lH-azeplne-l carbothioate, ~,3,3-trichloroallyl N,N-diisopropyl thiocarbamate, S-isopropyl l-(5-ethyl-2-methylpiperidine~ carbothioate; alone and with various combinations thereof and with such other classes of herbicidal compounds, as triazines, for example, 2-chloro-4-ethylamino-6-isopropylamino-s-triaz.ine, 2-chloro-~,6-bis(ethyl-amino)-3-triazine, 2(4-chloro-6-ethylamine-s-triazine-2-yl amino~-2-methylpropionitrlle, 2-chloro-4-cyclopropylamino-6-; isopropylamino-s-triazine.
As an embodiment within the scope of the present invention is a two part or package herbicide sys-tem comprising a first part of one or more thiocarbamate herbicide and a second part of an antldote compound therefore it is understood that the antidote compound is used in an effectlve amount to render the two-part herbicide system selecti.ve i.n decreasing phytotoxic effects to desi.red or bene~icial crops and yet phytotoxic to the undesirable or un~anted vegetation. Thus the soil treated by such a system becomes extremely useful and desirable, allow-ing previously injured crops to be planted ln said treated soil, otherwise injured by the herbi.cï.de when used alone. Hence, soil treated ~ith herbicide and antidote ;.s described herein ;s ~enefi.cial, desirable and useful.
An herbicide as used h.erein means a compound ~hich controls or modifies the growth of vegeta~ion or plants. Such ., 7~

controlling or modifying effects include all deviations from natural de~elopment; for example, killing, retardation, defolia-tion, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants", it is meant germinant seeds, emerging seedlings and established vegetation including the roots and above-ground portions.

Evaluation Procedures 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. Her~icide - S-n-propyl N,N-di-n-propyl thiocarbamate - BERNAM ~ 6E - 1560 mg. of VERNAM 6E was diluted in 250 ml. of water so that 5 ml. applied to a flat is equiva-lent to 6 lb/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 l~
Tween 20 ~ (polyoxyethylene sorbitan mono-laurate~ so that 5 ml. when applied by pre-plant incorporation technique (PPI) is equal to 5 lb/A per flat.
The herbicide and antidotes were applied to the soil together as a tank mix employing pre-plant incorporation tech-nique. To prepare the com~ined tank mix, 5 ml. of the VERNAM
were admixed, followed by incorporation into the soil from the flats during incorpora-tion in a rotary mixer.

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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 between 70-90F. The soil was watered by sprinkling to assure 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 of this invention.

TABLE II

Application Method : Pre-plant Incorporation - PPI (Tank Mix2 20 Crop Species : Soybeans (Glycine max) ' Weed Species : Foxtail (Setaria vlridis~
Watergrass (Echinochloa crusgalli) * = ~ injury *~ = % protection , ~

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-PPI (6 lb/A) (Tank Mix~
COMPOUND
NUMBERSoybeans Watergrass Foxtail VERNAM 6 lb/A40* 100* 100*

1** 75 0 0 4 37.5 0 0 ~5 0 0 6 25 Q o 16 5Q a o 19 lQ0 0 5 21 1~0 0 5 23a lQ0 Q
24a 75 0 0 , 1 a Q o o i 30 j -20-, ~

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TABLE II (continued) PPI (~6 lb/A~ (Tank Mix) COMPOUND
NUMBER o~beans Watergrass Foxtail 26a 75 0 0 27a 100 0 0 28a 100 0 0 29a 75 0 0 30a 67.5 0 0 = Pre-plant incorporation of VE~NAM ~ and antidote applied separately prior to ;ncorporation.

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. Five ml. of stock solution was applied to the soil in a volumetric pipet. Five ml. of stock solution contained an equivalence of herbicide which equals six (6) pounds per acre when applied to the soil in the flats. After the her~icide 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 up the seeds. The soil ~as leveled and rows one-half inch deep were made for planting seeds. Alternating rows of - treated and untreated crop seeds were sown. In each tes~, , -~76~

soybean (Glycine maxl seeds were planted in each row. Rows ~ere approximately 1-1/2 inches apart in the flat. Seeds were treated by preparïng 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. Antldote compounds can also be applied as liquid slurries and powders or dusts. In some cases, acetone is used to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.
~fter 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 where temp~ratures ranging from 70-79~F. Flats were watered by sprinkling as needed to assure 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 phytoxicity. 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 thiocarbamate, Compound No. 17 exhibited ; 5a% 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 No. 17, compared to ~; untreated seed grown in soil containing the thiocarbamate ;' herbicide.

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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 thiocarbamate herbicide and antidote; application by an in-furrow treatment of the seeds and surrounding soil in ~hich the herbicide had been applied previously to the ~oil; and treatment of the crop seeds with an antidote candidate prior to planting in herbicïde treated soil.
Stock solutions of other representative thiocarbamate herbicides and antidote candidates were prepared as follows:

Herbicides C. S-ethyl di-n-propyl thiocarbamate - EPTC
EPTAM ~ 6E - 260 mgO dissolved in 200 ml.
~ater such that 4 ml. applied to the soil from a planting fl~t is equivalent to 1 l~/A
applïed in 80 gal. of ~ater per acre and 3 ml. is équivalent to 0.75 l~/A.

D. S-isopropyl 1-(5-ethyl-2-methyl-piperidine~
carhothioate ~R-12001i, 390 mg. dissolved in 200 ml. of a etone with 1% Tween 20 ~ , or 975 mg. in 250 ml. of acetone, such that

5 ml. of solution applied to a planting flat is equivalent of 2 l~/A pre-plane incorporated and 6 ml. is equivalent to 6 lb/A respectively.

3Q E. 5-eth~l di~ïso~utyl thiocarbamate - SUTAN ~
6E or 5-ethyl cyclohexy-l ethyl thiocarbamate -RONEET ~ 6E - 52~ ~g. dlssolved in 20Q ml.
~ater such that 4 ml. applied to the soil from a plantïng flat is equïvalent to 2 lb/A, applied ïn 80 gal. of water per acre. For 6 lb/A or .~

12 lh/A, 13Q0 m~. or 26 m~. ~as dissolved in 25a ml. water, such that 6 ml. was equivalent to the desired amount, respectively.

F. 2,3,3-trïchloroallyl N~N-diisopropyl thio-carbc~mate - AVADE~ BW ~ 4E - 1219 mg.
dissolved in 3Q0 ml. dïstilled water, such that 6 ml. is equivalent to 3 lb/A when applied to the soil from a planting flat pre-plant incorporated.

G. S-ethyl~hexahydro-l~-azepine-l-carbothioate -ORDRAM 8E - 857 mg. dissolved in 250 ml.
water such that 5 ml. is equivalent to 4 lb/A
and 2.5 ml. is equivalent to 2 lb/A when applied to the soil from a planting flat pre-plant incorporated.

Antidotes H. For each candidate compound employed, 250 mg.
active ingredient was diss~lved in 2.5 ml.
acetone, with 1% Tween 20 ~ (polyoxy-ethylene ~orbitan monolaurate) such that 0.5 ml. of solution per 10 gm. of seeds is egual to 1/2% w/w. For seed treatment of 1/4%, 0.25 ml. was diluted with 0O25 ml. o~ acetone, such that 0.5 ml. of solution for 10 gm. of seeds is equal to 1/4% w/w. This solution was used for the seed treatment procedure in varying amounts and dilutions for example for 0.10~, 0.1 ml. is diluted with 0.4 ml. of acetone.

r. For each candidate compound employed in the 'lin-furrow" method of application, 95 mg. of active ingredient was dissolved in 15 ml. of acetone with 1% Tween 20 ~ such ~hat 1.5 ml.
applied to the seed and~soil in the furrow, in one-half of the flat was equivalent to 5 lb/A.
- When 1.0 lb/A is desired 0.3 ml. is diluted with 1.2 ml~ of acetone.
., ., `; J. For each candidate compound employed in the tank mi~ pre-plant incorporation test, 39 . 4Q m~ o.~ actl~e in~redient ~as dissolved in 10 s ~ ~1. of acetone ~ith 1% Tween 2Q ~ , such that 5~ml. when applied to t~e soil of a ;~ flat was- eguivalent to 5 l~/A.
~!
. .

~ 24-.
!
~;
J

~7~

In-furrow application of the antidote employed the ahove stock solutions. As a preparatory step, a one pint sample of soil was removed from eac~ flat to be retained and used later to cover the seeds after treatment with the stock solutions. The soil was leveled before planting. The herbicide stock solution was applied respectively to separate flats and pre-plant incorporated in the soil from the planting flat at the equivalent rate of 1 lb/A active ingredient or the indicated rate.
- 10 Rows 1/4-inch deep were made lengthwise in each treated flat, preparatory to seeding. After seeding, the flats were sectioned into t~o equal portions using a wooden barrier and 1-1/2 ml. of 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 o~serve any lateral movement o 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. Five milliliters ~5 ml.) of herbicide stock solukions A or C were each mixed wi~h five millilit~rs (5 ml.) of ~ antidote candidate stock solution J such that the equivalent of ; 1 lb/A and 5 lbs/A of her~icide and antidote, respectivelyr were applied and incorporated into the soil of each flat. For pre-plant incorporation, the mixed stock solutions weEe injected into the soïl during incorporatiGn in a 5-gallon rotary mixer.
~ Other stoc~ solutions ere employed at indicated rates in the 1 30 tank mix procedure.

,, -25-.. ..

,,.
,~.

~7~

For seed treatment, lQ grams of seed in a suitable container was shaken with a. 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. 5haking 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 l lb/A active ingredient.
All fla-ts were placed on greenhouse benches where temperatures were maintained between 70-90F. The soil was watered by sprinkling to assure good plant growth. Injury ratings were taken 2 and 4 weeks after the applications were made. Individual control flats treated with the herbicide alone ~ere 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 ACTIV_TY

Application Method: Seed Treatment - ST
In-Furrow - IF

Pre-Plant Incorporation - PPI (Tank Mix) Crop Species: Barley - ~A ~Hordeum vulgare (L.~]
; Corn -~ CN ~Zea maize~
Cotton - CT I~ y~ hirsutum]

TABLE III (con~inued~

Crop Species: Grain Sorghum - GS ~So~hum ~ ]
Rice - R ~)ry:a S`t.;.~.]
Soybeans - SB [Glycine max]
Wheat - WT [ Tri ticum ae s tivum ]

Weed Species: Watergra5~ - WG [Echinochloa crusgalli]
Green :Fox~ail ~ FT ~Setaria viridLs]
Wild Oats - WO [Avena fatua (L- ? ]
Shattercane ~- SC [ ~ bicolor]

Result - Percent injury with antidote presen~/percent injury of herbicidF alone.

COMPOUNDMET~IOD OF
NUMBERHERBICIDE APPLICATION 'RATE CROP RESULT
1 ORDR~M PPI . 6~5 CN 60/90 RONEET PPI 6~5 CN 85/95 RONEET: PPI 2~5 ~.S 40/50 .
ORD~AM PPI 4~5 SB 70/80 RONEETPPI ' 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 7BA 30/60 ~ ~ ST 2~.25 BA 30190 " VERNAM ST 1~.10 BA 40/60 OR'~RAM PPI 6+5 CN 50l90 . '~ONEET PPI 6~5 CN 30/95 : PPI 6tO.5 CN 30/50 i~
,s, .
,.; ~

~ ~ 7 TABLE III (continued) COMæOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
3 cont. VERNAM PPI 6~5 CN 60¦75 EPTAM PPI 0.75~5 GS 60/100 ORDRAM PPI 2+5 GS 45/82 ST 2f.l25 GS 55/75 RONEET PPI 3~5 GS 40/75 ST 3-~.125 GS 50/70 R-12001 ~PI 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 - ORDRAM PPI 4+1 SB 40~80 RONEET PPI 2~ SB 10/70 SUTAN PPI 5+1 SB 45/65 VERNAM IF 6~1 SB ~ 0/40 ST 6~.062 SB 10/45 ORDR~M ST 4~.125 WT 10¦20 RONEET IF 2+1 WT 75/90 R-12001 PPI 2~1 WT 60l95 R-12001 ST 2~.062 WT 40/70 VERN~M 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 ~ ' .

~ ~ 7 TABLE III (continued) COMPOUND MEI~IOD OF
NUMBERHERBICIDEAPPLICATION RATECROP RESULT
ORDRAM PPI 6~5 CN 80/90 RONEET PPI 6~5 CN 80/95 RONEET PPI 2+5 GS 40/50

6 0RDRAM 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 VERN~M 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 70f90 RONEET PPI 6~5 CN 70/95 VERN~M IF 5+5 CN 50/75 VERNAM IF 1~5 R 40/60 VERNAM IF 1~5 ~T 60/87 ORDRAM PPI 6~5 CN 80/90 RONEET PPI 6~5 CN 75~95 VERNAM IF 5-~5 CT 70/80 ORDRA~ PPI 2+5 GS 50/85 RONEET PPI 2~5 GS 40/50 ~29 TABLE III ~continued) __ COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
. ., _ . ~ . ~ .
11 ORDRAM PPI 6 +5 CN 70/90 RONEET PPI 6+5 CN 75/95 VERNAM IF 6+5 CN 0/70 ORDRAM PP~ 2~5 GS 75/85 ROMEET PPI 2+5 SB 50/70 ; VF.RNAM IF 6+1 SB 20/40 :
. 12 ORDRAM PPI 6~ CN 70/90 RONEET PPI 6+5 CN 75/95 i 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-~ SB 10/40 ;
,~ 13 RONEET PPI" 6+5 CN 75/95 VERNAM IF 5~5 CT 60/80 ORDRAM PPX 4~5 SB 70/80 RONEET PPI 2~5 SB ~0/70 - 14 VERNAM IF 5~5 BA 50/82 , ', ~ VERNAMIF 5+5 CN 50/70 ~: VERNAM IF 1~5 WT 60/75 ; 15ORDRAMPPI 6+5 CN 75/90 VERNAM IF 5~5 CN 40/50 :: ORDRAM PPI 2+5 GS 70/85 ,"

, ~a76 TABLE III (continued) COMl?OUND ~El~lOD OF
NU~ER HERBICIDE APPLICATION RATE CP~OP RESULT
15 cont. VERN~MIF 1+5 GS60/100 EPTAMPPI 5+5 SB 35/65 ORDRAMPPI 4-.'5 SB 50/80 RONEETPPI 2~5 SB50 /7 0 SUTANPPI 5~5 SB 30/65 VERNAMIF 6~1 SB 20/50 16 ORDRAMPPI 6+5 CN 80/90 ORDR~MPPI 2~5 GS 60/85 RONEETPPI 2~5 GS 40/50 VERNAMIF 1~5 GS60/100 ORDRAMppT 4~5 SB 60/80 17 ORDRAMST . 4 tO "5 BA 10/30 RONEETST 2 t0.25 13A10/80 R-12001PPI 2~5 BA 40/60 R-12001ST 3~0.25 BA 25/90 SUTAN ST 2~0 . 25 BA 0/75 VERNAMIF 1~5 BA30/100 ORDRAMPPï 2~5 GS 10/82 ORD~AMST 2~0.25 GS 40175 ~-RONEETPPI 3~5 GS 50/75 RO~EETST 2~.2$ GS 10/70 R-12001PPI 2~5 GS 68/92 R-12001ST 2~0.25 GS 25/85 SUTAN ST 2-0 . 25 GS 10/95 VERNAMIF 1~5 GS40/100 VERN~MST 1~0.25 GS 30/-95 7 ~
TABIE III (continued) CO~IPOUND METHOD OF
NUMBER HERBICIDEAPPLICATION RATE CROPRESULT
17 cont. 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-~ .10 BA 20/80 R-12001 PPI 2~5 ~A 10/60 R-12001 ST 3~Q.10 BA 30/90 SUTAN ST 2-0.10 BA 0/75 VERNAM IF 1~5 BA 30/95 PPI 1~5 BA ~0/95 ST 1~0.10 BA10 /60 ORDRAM PPI 6~5 CW 30/90 RONEET PP~ 6+~ C~ 70/95 R-12001 PPI 6tO.5 CN 20/50 VERNAM PPI 6~5 CN 50/75 VERNAM IF 5~5 CN 40/90 EPTAM PPI .75+5 GS50/100 ORDRAM PPI 2+5 GS 30/82 ORD~AM ST 2~0.125 GS 50/75 RONEET PPI 2~5 GS 20/75 RONEET ST ~+0.125 GS 2Q/70 R 12001 ST 2~0.1?5GS 50/85 SUTAN PPI 2+5 GS 75/95 7~
TABLE III (continued) COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
18 cont, SUTAN ST 2~0.125 GS 60/95 VERNAMPPI 1-~5 GS60/100 IF 1-~5 GS40/100 ST l~O.125 GS 60/95 R-12001PPI 2~5 R 60/70 VERNAMIF 1~5 R 80/100 EPTAMPPI 5~5 SB 20/65 ORDRA~PPI 4~5 SB 40/80 RONEETPPI 2~5 SB 30/70 SUTANPPI 5~5 SB 20/65 VERN~MIF 6~1 SB 13/50 ST 6~0.125 SB 15/25 . ORDRAMST 4~0.125 WT 5/30 RONEETST 1~n.25 WT 70/95 R-12001PPI 2~5 WT 75/95 ST 2f~o63 WT 40/70 VERNAMIF 1~5 WT70/100 . 19 R-12aOlPPI 2~5 BA 30160 `. VERNl~PPI 1~5 BA 40/95 VERN~ IF 1~5 BA 20/96 ORDRAMPPI 6 ~5 CN6 0 / 90 , RONEETPPI 6~5 CN 50/95 VERNAM IF 5~5 CN 50/90 . EPTAMPPI 0.75.~5 GS60/100 ORDRAMPPI 2~5 GS S2/82 , RONEETPPI ~5 GS 20/75 R ï2001PPI 2~5 GS 62/92 " .

s' TAB~ III (c ontinued) COMPOUND METHOD OF
NU~ER ~ERBICIDEAPPLICATIONRATE CROP RESULT

19 cont. SUTAN PPI 2~5 GS 70/95 VERNAM PPI 1-~5 GS 6 0/100 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 ~-12001 PPI 2~1 WT 50/95 VERNAM IF 1~5 W~T 80/100 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 60/8() VERNAM IF 1~5 R 85 / ~ 00 VERNAM IF 6~1 SB 20 /40 21 R lZOOl PPI 2~5 BA 30/60 VE~N~M PPI 1-~5 BA 60/95 VERNAM IP 1~5 BA 30/95 OR~RAM PPX 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/lOO
O~DRAM PPI 2~5 GS 25~82 RONEET PPI 2~5 GS 40/75 R-12001 PPI 2~5 GS 45/92 :~3 TABIE III (continued) COMPOUND ~ETHOD OF
NU~El~ HER13XCIDEAPPLICATION RATE CROP RESULT

21 cont, SUTAN PPI 2-~5 BA 30/95 VERN~M PPI 1+5 GS 60 /100 VERNAM IF ~ 5 GS 40/100 R-12001 PPI 2~5 GS 40/70 RONEET PPI 2+5 SB 50/70 VER~AM 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 C~ 85/95 . O~DRAM PPI 4~5 SB 70/80 RO~EET PPI 2+5 SB 60/70 VERNAM IF 6~1 SB 30/40 23 VERNAM IF 1+5 BA 20/90 ~:RNAM IF 5+5 - CN 20/90 EPTAM PPI 0.75~5 GS 70/100 ORD3~ PPI 2~ GS 60/80 . RONE:ETPPI: 3~5 GS 50/75 RONEET IF 3-~5 GS 30/75 ~: R-12001 PPI 2~5 GS 50/90 24 VERNAM IF 1~5 BA 10/90 ,.:
VER~;M IF 5~5 CN 50/90 EPTAM PPI 0 . 75~5 GS 40/100 ORI3RA~ PPI 2+5 GS 40/80 .
~.,.
~j; RONEET PPI 3~5 GS 20/75 ,~j : -35-,;''' ~Q76`~

TABLE III (continued) CO~OUND METHOD OF
NI~ER HERBICIDE APPLICATION RATE CROP RE~ULT

24 con~. RONEET IF 2+5 GS 30/65 R-12001 PPI 2~5 GS 30/90 SUTAN PPI 2~5 GS 40/95 VERNAM IF l~S GS 20/96 VE~NAM IF 1-~5 ~A 20/70 VERNAM IF 5~5 CN 20/90 RONEET IF 2t~ GS 30/65 VERNAM IF 1~5 GS 30/96 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 2~0c25 BA 0/75 VER~AM IF 1~5 BA 10/70 . VERMAM ST 1~0 ~ 10 BA 20/60 . VERN~M IF 5t~ CN 40/90 : EPTA~ PPI 0.75~5 CT50/100 ORDRAM PPI 2~5 CT 50/80 ORDRAM ST 2~00125 CT 40/75 RONEET PPI 3~5 CT 30/75 RONEET IF 3~ CT 40/65 .

.

~7 TAB I (continued) COMPOUND METHOD OF
NUMBER ~ERBICIDEAPPLICATION TE CROP RESULT

27 cont . RQNEET ST 3-~0.125CT 20/70 R-12001 PPI 2-.'5 CT 50/92 R-12001 ST 2tO .125 CT 30/85 SUTAN ST. 2-~0.125CT 30/95 EPT~M PPI 0.75+5 GS 50/100 ORDRA~ PPI 2~5 , GS 50/80 ORDRAM ST 2~0.125GS 40/75 RONEET PPI 3~5 GS 30t75 IF 3~1 ~S 40/65 ST 3~0.125GS 20/70 R~12001 ST 2~0.125GS 30/85 SUTAN ST 2~0.125GS 30/95 VERNAM IF 1~5 GS 30/96 ORDRAM ST 6t0.125WT 10/30 R~12001 ST 2~0.062WT 40/70 28 VERNAM IF 1~5 BA 20/70 VERNAM IF 5~5 CN 50/90 ORDRAM ST 2~0.125GS 45/75 RONEET IF 2~5 GS 40/65 RONEET ST 3t0.125GS 30/70 R-12001 PPI 2+5 GS 50/95 ; . R-12G01 ST 2~0.125GS 30/85 SUTAN ST 2~0.125GS 40/95 VERNAM IF 1~5 &S 20/96 VERNAM ST 1~0.125GS 40/95 ORDRAM ST 6~0L 125 WT 0/40 /

., ~ 9 TABLE III (c ontinued ~

COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT

28 cont. R-12001 PPI 2+5 WT 50/95 R-12001 ST 2+.125WT 30/70 29 ORDRAM ST 4~0.125 BA 10/30 R-12001 PPI 2+1 BA 40/60 VERNAM ST 1-~0.50BA 50t95 EPTAM PPI 5~5 CN 20/85 R-12001 PPI 5+0.5 CN 20/50 ~PTAM 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 &S 30/75 RONEET IF 3+2 GS 40/65 RONEET ST 3*0.125 &S 20/70 - SUTAN PPI 2~5 GS 30/95 VERNAM IF 1+5 GS 40/100 VERNAM PPI' 6+5 SB 15/40 31 EPTAM PPI 5+5 CN 30/85 VERN~M IF 5+5 S8 10/40 32 VER~AM IF 1~5 ~A 60/70 ; VERNAM IF 1~5 CT 40 /60 : VERNAM IF 1+5 GS 70/100 VERN~M IF 1~5 SB 0/42 , 33 VERNAM IF 1~5 BA 60/70 f. VERNAM IF 1~5 GS 50/100 VERNAM IF 1~5 R 70/95 :, . .

COMPQUND ME lHOD OF
NU~ER HERBICIDEAPPI.ICATI ON RATE CROP ~ESULT

33 cont. 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 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 VERNA~ IF 1~5 BA 30/60 VERNAM IF 1+5 CN 50/95 VERN~M IF 1~5 GS 50/100 37 VERNAM IF lf5 BA 20/60 VERNAM IF 6~5 CN 60/95 VERN~M IF 1+5 CT 20/5û
VERNAM IF 1~5 GS 40/100 VERNAM I~. 1t5 WT 6û/90 38 VERNAM IF 1~5 BA 20/60 VERNAM IF . 6~ CN 10/95 VERNAM l~ ^ 6+5 SB 20/50 - 39 RONEET PPI 6~5 C~ 75/95 VERNA~ 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 , COMPOUND ~ETHOD OF
NUMBERHERBICIDE APPLICATION RATE CROP RESULT

42 VERNAM IF 1-~5 BA 30/50 RONEET PPI 2 +5 GS 40 / 75 43 ORDRAM PPI 6~5 CN 70/90 RONEET PPI 2+5 &S 40/50 ORDRAM PPI 4~5 SB 50/80 VERNAM IF 1~5 ~T 60/90 44 VERNAM -IF 6~5 GN 50/70 yERNAM IF 1~5 CT 40/70 RONEET PPI 3~5 ~S 60/75 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 30195 47 VERNAM PPI 6+1 SB 10/40 ~ERN~M IF 6~5 SB 60/80 VERNAM IF 1~5 WT 50/75 48 ORDRAM :PPL 2~5 GS 60/85 VER~M PPI 6~5 SB 30/40 49 VERNAM IF 5~5 CN 40/70 . RONEET PPI 2-~5 SB 50/70 VER~AM PPI 6+5 SB 30/40 VERNAM IF 1~5 BA 60/90 VERNAM IF 1~5 R 50/90 ORDRAM PPI 4+5 SB 50/80 ~

TAB (continued) COMPOUN~ METHOD OF
NUMBER . HERBICIDE APPLIC~TION RATE CROP RESULT
.
50 cont. VERNAM IF 6+1 SB 30/40 51 VERNAM IF 1~5 BA 30/83 EPTAM PPI O.75~5 GS 50/100 ORDRAM ST 2~00125 GS 50/75 : RONEET ST 3~0.125 &S 30/70 VERNAM IF 1~5 GS 60/100 VERN~M 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 3~1 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 ORD~AM PPI 6~5 CN 50/90 . "
ORDRAM PPI 2~5 GS 60/85 ,: VER~AMi IF lt~ R 50/95 54 ~ERNAM IF 1~5 BA 10/60 . VERNAM IF 6~5 CN 40/70 . EPTAM PPI 0~75~5 GS 30/100 ORDRAMi PPI 2~5 GS 40/80 ' RONEET PPI 3+5 GS 20/75 .'. RONEET IF 3-~5 GS 10/75 . ~-12001 PPI 2~5 GS 20/90 '. SUTAN PPI 2~5 GS 30/95 ., , ,;

TABLE III (continued) , .

COMPOUND METHOD OF
NUMBERHERBICIDE APPT.TCATION RATE CROP RESULT

54 cont. 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 C~ 70/90 VERNAM IF 1+5 GS 75/100 VERNAM PPI 6+5 SB 10/40 ~ERNAM 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 P~I 6~Q.5 SB 20/40 VERNA~ IF 6~5 SB 40/60 58 VERNAM PPI 6~1 SB 10/40 VERNAM IF 1~5 WT 50/78 59 VERMAM IF 1~5 GS 70/100 VERN~M PPI 6~5 SB 30/50 VERNAM IF 6~5 SB 10/30 VERNAM IF 1~5 BA 30155 VEP~NAM IF 1+S GS 60/85 61 VERNAM IF 6~5 CN 80/90 VE~NAM IF 1+5 CT 40/50 62 VERNAM IF 1+5 BA 30/55 VERN~M IF 6~5 CN 70/90 7~
TABLE III (continued) -COMPOUND METHOD OF
ERHERBICIDE APPLICATION RATE CROP RESULT

63 VERNAM IF 1+5 BA 20/55 VERNAM IF 6~5 CN 50/90 VF,RNAM IF 6~5 SB 30/55 64 VERNAM IF 1+5 CT 40/60 VERNAM IF 1~5 GS 40/100 VERNAM -IF 1+5 BA 40/60 yERN~M IF 1+5 CN 30/95 . VERNAM IF 1~5 GS 40/95 VERNAM IF 6+5 SB 0/60 , 66 VERN~M IF 1~5 BA 30t55 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 70/9O
VERNAM IF 1~5 GS 60/85 VERNAM IF 1~5 WT 60/70 68 VERN~M IF 1~5 BA 30l55 , VERNAM IF 6~5 C~ 30/90 VERNA~ IF 1~5 GS 40/85 VERNAM IF 6~5 SB 30/55 ~. VERNAM IF 1~5 WT 50/70 .~ 69 VERMAM IF 1~5 BA 20/55 ~: VERNAM IF 6~5 CN 30/90 .~; VERNAM IF 1+5 GS 40/85 ~,.

,,;

~Q~ ~9 TABLE III (c on~inued) CGMæOUND ~THOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT

VERM~M 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 VERN~M IF 1~5 BA 40/50 VERN~M IF 5~5 SB 10/40 72 VERNAM IF 1~5 WT 40/75 73 VERN~M 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 ~ERNAM IF . 1~5 ~T 50/75 77 VERMA~ IF 1+5 BA 30/60 VERNAM IF 6~1 SB 10/40 78 R~12001 IF 6~5 CT 50/65 VERNAM XF 1+5 CT 10/50 VERNAM IF 6~5 SB 40/60 79 VERNAM IF 6~5 SB 30/60 VERN~M IF 1~5 BA 40/70 VERNAM IF 1~5 GT 40/60 VERNAM IF 1~5 R 60/95 VERNAM IF 6~5 SB 40/60 . -44 -TABLE III (continued) COMPOUND METHOD OF
NUMBER HERBICIDE APPLICATION RATE CROP RESULT
.

81 VERNAM IF 1~5 CT 40/50 82 VERNAM IF 1~5 GS60/100 VERNAM PPI 6tO.5 SB 20/40 83 VE~NAM IF 6+5 CN 50/95 VERNAM IF 1+5 CT 30/50 VERNAM -IF 1+5 GS80/100 yERNAM IF 6+1 SB 10/50 84 VERNAM IF l+S GS 70/95 VERNAM IF 6~1 SB 0/40 RONEET IF 3+5 GS 30/75 VERNAM IF 1~5 GS50/100 VERNAM PPI 6+5 SB 10/SO
86 VERNAM IF 1~ RA 70/83 VERN~M IF 6+5 CN 60/90 - VERNAM IF 1~5 GS70/100 VERNAM PPI 6+1 SB 20/40 87 ~RN~ IF 6-~5 CN 80/90 ~ERNAM IF 1~5 GS60/100 VERNAM IF 6~5 SB 40/60 88 VERNAM IF 6+5 CN 80/00 VERNAM IF 1~5 GS80/100 VERNAM IF 6+1 SB 10/42 89 VERN~M IF 1~5 CT lO/50 VERN~ IF 6~5 SB 30/60 :
~ " : - ~

7~

TABLE III (c ontinued) COMPOUND METHOD OF
NU~ER HERBICIDE APPLICATION RATE CROP RESULT

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 VERN~M IF 1~5 CT 30/50 VER~AM IF 6~5 SB 20/50 93 V~RNAM 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/~5 : 95 VE~N~M IF 6+5 CN 80/90 VERNAM IF 1~5 R 20/70 6 VERNAM IF 1~5 BA 40/70 VER~AM IF lt~ CT 40 /60 VERN~M IF 1~5 R 60/95 . V~RN~ IF 6~5 SB 30/60 - 97 ~ERN~M IF 1+5 BA 40/55 98 VERNAM IF 6~5 SB 30/55 99 VERNhM IF 1~5 BA 30/55 . VERNAM IF 1~5 R 20/70 ;::
; 100 VE~NAM IF 1~5 BA 30/55 . VERMAM IF 1~5 R 60/70 ;,:, 1, .

. ~46 -,,:

~7 TAl~J~. III (continued~

NIJMBERHE:R ICIDEAPPLICA ON RATE CROPRESULT

101 VERNAM IF 1~5 BA40/55 VERNAM IF 6~5 SB20/50 VERNAM IF 1t~5 WT6 0/85 102 VERNAM IF' 1~5 BA30/55 VERNAM IF 1+5 CT40/50 VERNAM IF 6+5 SB 0/50 103 R-12001 IF 6~5 CT50/65 VERNAM IF 1~5 CT30/50 VERNAM ` IF 6~5 SB 0/60 VER~AM IF 1~5 WT60/85 104 VERNAM IF 1~5 BA40/55 VERN~M IF 6~5 SB30/60 VERN~I IF 1~5 WT60/70 105 VERNAM IF 1~5. BA40l55 VERMAM IF,. 6~5 SB 0/60 VERNaM IF 1~5 WT60/85 106 YERNAM IF 1t-5 BA30~60 VERN~M IF 6t-5 CN70/95 VERNAM IF 6+5 S1330¦60 107 VE~RN~M IF 6~5 SB 0/60 VERNAM IF 1~5 WT60/85 ' -47- , ~ ~ 7 ~ ~
In side~by-side tests with various weed species and crops, it was ~ound that weed control was maintained while at the same ~ime the crop species were protec~ed or iniury de-creased, when compared to a check or control flat. The control ~lat contained no antidote compound candida~e. The following table further exemplifies those results.

TABLE IV .
~`~
HERBICIDE RATE GS SC WG
RONEET ~ 3 lb/A- 50 50 lO0 (PPI) COMPOUND
NDMBER RATE (IF~ GS SC WG
2 l lb/A 40 lO0 lO0 33 l lb/A 30 lO0 lO0 l lb/a 30 lO0 lO0 36 l lblk lO 100 lO0 37 l lb/A 25 lO0 lO0 38 l lb/A 1. 30 lO0 lO0 lO0 lO0 l lb/A 15 lO0 lO0 68 l lb/A 40 lO0 lO0 69 l lb/A 40 lO0 lO0 l lb/A 15 lO0 lO0 93 1 lb/A 40 lO0 lO0 g3 5 :Lb/A 30 lO0 lO0 106 l lb/A 40 lO0 lO0 ,, . -48~

~7 ~9 Perc ent Inj ury HERBICIDE RATE RC w'r WG WO
ORDRAM~) 8 lb/A 25 30 100 100 (PPI ) _ COMPOUND
NLTMBER ~ RC WT WG WO
3 1 lb/A 50 20 100 100 5 lb/A O 60 0 O
17 1 lb/A 50 10 100 100 5 lb/A 20 0 100 100 18 5 lb/A 20 10 100 100 19 1 lb/A 60 20 100 100 S lb/A O 60 100 100 1 lb/A 40 10 100 100 5 lb/A 10 10 10(~ lOû
27 1 lb/A 60 10 100 100 5 lb/A 10 50 lQO lOQ
29 5 lb/A 20 LO lQO 100 47 5 lb/A 20 2Q 100 100 51 5 lb/A 40 20 100 100 94 5 :Lb/A 40 10 100 100 96 5 lb/A 60 lO 100 100 /

': -4g-s , .

TABLE IV (continued~

ORDRAM ~ 8 lb/A PPI

COMPOUND
NUMBER RATE ~F) R WT WG WO
32 1 lb/A 40 20 100 100 5 lb/A O 10 80 100 35. 1 lb/A 10 10 100 100 37 l lb/A 40 10 100 100 - 38 5 lb/A 30 10 100 100 e ~
HERBICI~E KATE C. WG FT
SUTAN ~ 12 lb/A 50 100100 COMPOUND RATE ~PPI
NUMBER . TANK MIX C WG FT
; 3 5 lb/A 20 100 100 1~ 5 1~/~ " 4~ 100 100 19 5 lbiA 40 100 100 21 5 lb/A ~0 100 100 : 23 5 lb/A 40 100 100 24 5 lb/A : 30 100 130 29 5 lb/A 20 100 100 51 5 lb/A ?~ 100 100 The compounds and compositions of this invention were employed in efective herbicidal compositions comprising the antidote and a thiocarbamate herbicide as described herein-above-. The herbicidal compositions were tested in the above -5~-, ~ ~ 7 manner.
A preferred herbicidal composition comprises a thio-carbamate herbicide and an antidotally effective amount of an antidote compound therefor corresponding to the formula in ~ N- ~ OR

. which ~ is hydrogen, methyl, methox~, chloro or bromo; and R is alkyl having 1 to 4 carbon a~oms~ inclusive, haloalkyl having 2 to 6 carbon atoms~ inclusive, wherein halo is chloro, bromo or fluoro from 1 to 6, inclusi~e; alkenyl having 3 to 6 carbon atoms, inclusive, chloroalkenyl having 3 to 6 carbon atoms, in clusive, or alkynyl having 3 to 6 carbon atoms, incluslve, di-alkylamino, having 2 to 6 carbon atoms, inclusive~ trifluor-acetamidomethyl, 4-chlorophenylthiomethyl, phenyl, 3-phenyl~
propyn-2~yl, 3-pyridylmethyl and phosphonomethyl.
The compositions of the present în~rention for the pro-tectio~ of cul~ivated crop plants ~-omprise the active herbicidal compound and an antidote therefor selected from the above-de-scribed compounds. The compositions of herbicide and antidote , can be prepared by conven~ional me~hods through ~he thorough .~ mixing and grinding of the ac ~ive herbicide agents and the anti-dote with suitable carriers and/or other distributiol media, possibly with the addition of dispe~sion agents or solvents.
,;
The antidote compounds and composi~ions of the present inventio~ can be used in any co~venient form. A solvent or inert carrier is not necessary in view of low volume spray tech-nology which permits ~he use of nea~ ~echnical grade materials . as sprays Thus, the antidote compounds and composition wi~h .. the thiocarbamate herbicide can be formulated into emulsifiable -. .

, . , :,, , , , "

~ ~ 7 ~ ~9 liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form. In its preferred form, a non-phytotoxic quantity of an herbicidal 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 can be incorporated into the soil and thereafter ~he antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated wlth a non-phytotoxic quantity of the compound and planted into the soil which has been treated with .
herbicide, or un~reated with the herbicide and subsequently treated with the herbicide. The addition of the antidote com-pound does not aff~ct the herbicidal activity of the herbicide.
The alternative methods o~ application have been exemplified in the above examples.
The amount of antidote compound present ~an range be~ween about 0.001 to about 30 parts by weight of antidote compound described herein per eaoh part by weight of herbicide.
The exact amount o antidote compound will usually be determined on econ~mic ratios or the most éfective amou~ usable~ It is understood that a non~phytotoxic, bu~ effective quantity of a~tidote compound will be employed in the herbicidal composi~ions and methods described herein.
Ater treatment with the antidote and herbicide there ~s obtain as a resultant thereo~ soil which is novel in compo-sition. Said 50il iS improved in its capabi~ity to grow crops and to ofer weed con~rol. Fur~her said soil trea~ed with herbi- -cide and an~idote has the particular utility for allowing seed ', ., ~ -52~

"

... .

of crops oth~rwise injured by the herbicide to be planted and grown. The herbicide has its utility in controlling undesir-able vegetation; the antidote compound decrease the injury from the herbicide upon the crop species, and the soil ~reated with herbicide and antidote compound provides an improved media to grow the crop in the presence of an othe~ise injurious herbicide.

In the utility of the present antidote compounds and impro~ed herbicide system the thiocarbamate can be applied to the soil. Application of the herbicide to the soil can take place by preplant incorporation. In conjunction with the prior application of the herbicide employing the present invention crop seeds aré planted. Seed planting is followed by applica-tion of the antidote as a preemergence surface application. This sequen~e of application of herbicide, seed plan~ing and anti-dote is unusual and fully e~fective in decreaslng injury to the plant crop, otherwise injured by the thiocarbama~e.
~e~
Variou~ antidote compounds described herein have been ~: fouad capable of decreasing in~ury ~o the class of cxops known as legumes~ By legumes is meant those plants that have a sym-biotic relationship with nitrogen fixing organisms. For example, so~beans, varieties of Phaeseolus vulgaris (L. ~, peanuts, alfalfa, c lover and ~he like .
The following test was performed to determine the efficac~ as decreased injury of the 1~ ume crops by a representa-tive thiocarbamate herbicide, EPTAM ~ (EPTC), S-ethyl di~n-propyl thiocarbamate with compounds described hereinabove.
' ~ ~ r ~

Various edible bean and pea varieties were tested. The anti-dotes were applied at 1 and 2 lb/A preplant incorporated, tank mixed with EPTC at 6 lb/A preplant incorporated.
Stock Solutions:
.. . . . .
Antidote: For each candidate compound employed .
39 mg. dissolved in 25 ml. aceton~; 2.5 ~1. equivalent to 1 lb/A preplant lncorporated.
Herb : EPTAM ~ 6E: 1560 mg. dis301ved in 250 ml. watex; 5 ml. equivalent ~o 6 lb/A preplant incorporated.
- The crops tested were Navy bean - NB, Kidney bean - KB, Pinto bean - ~B (various varieties of Phaeseolus vulgaris L.) and peas (Pisum sati~um L~) The weed species included in the tests were wa~ergras~ - wg and foxtail ~.

TABLE V

Perce~t InlurY
~71 ~I--a~--~e~lr7rla¦~
NB PB WG FT
EPTC 6 lb/A65 , 50 100 100 C~MPOUND
NUMBER RATE~ NB PB~ WG FT
3 1 lb/A30 20 100 100 2 lb/A20 20 100 100 17 1 1~l~30 50 100 100 2 lb/A50 40 18 1 lbA25 30 100 2 lb/A50 40 ': .

", ' -54-:

TABLE V (continued~

COMPOUND
NUMBER R~TE NB PB WG Fl~
28 1 lb/A 50 40 2 lb/A 50 30 100 100 29 1 lb/A 0 40 100 lO0 2 lb/A 30 20 100 100 33 1 lb/A 40 40 100 100 2 lb/A 50 40 100 100 51 l lb/A 40 20 100 100 2 lb/A 50 30 100 100 54 1 lb/A 30 40 100 100 2 lb/A 50 0 100 100 57 l lb/A 50 30 100 100 2 lb/A 50 40 lO0 ïO0 1 lb/A 50 40 100 100 2 l~/A 50 10 100 100 A~ two pounds :~or a~re compound number 3 also exhibi-ted comple~e protection (100%) of kidney leave~. Compound number 28 exhib~-ke~ S0 percent protection of kidney b ans at two po~mds per acre. I~1ury to pea~ was decrea~d 37.5 percent with compound number 28 at two pounds per acre.

Claims (10)

FOR FOREIGN FILING

WHAT IS CLAIMED IS:

1. Compounds according to the formula in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl, and methyl;
n is an integer from 1 to 3 inclusive, pro-vided that when X is bromo, trifluoromethyl, or methoxy, n is 1;
and R is selected from haloalkyl having 2 to 6 carbon atoms, inclusive, wherein halo is chloro or fluoro from 1 to 6, inclusive, halo-alkenyl having 3 to 6 carbon atoms, inclusive, and wherein halo is chloro from 1 to 4 inclu-sive, dialkylamino having a total of 2 to 8 carbon atoms, inclusive, cyanoalkylthioalkyl having a total of 3 to 6 carbon atoms, inclu-sive, phosphonomethyl, trifluoroacetamidomethyl, lower alkyl substituted phenyl said lower alkyl each having 1 to 4 caxbon atoms, inclusive, 4-chlorophenylthiomethyl, alkoxyalkyl having 2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2 to 6 carbon atoms, inclusive, cyanoalkyl havang 2 to 6 carbon atoms, inclusive, alkoxy-carbonylalkyl having 3 to 7 carbon atoms, inclu-sive, formamidoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkenyl having 4 to 7 carbon atoms, inclusive, alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-methyl methylene, chlorophenyl, 4-chlorobenzyl, 4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenyl-propyn-2-yl, methylthioacetimino, acetone imino and benzaldimino;
also provided that when X is trifluoromethyl and n is 1, then R can be alkyl having 1 to 4 carbon atoms, inclusive, alkenyl having 3 to 6 carbon atoms, inclusive, and alkynyl having 3 to 6 carbon atoms, inclusive.

2. The compound according to Claim 1, in which X is hydrogen and R is haloalkyl.

3. The compound according to Claim 2 in which R is 2,2,2-trifluoroethyl.

4. The compound according to Claim 2 in which R is is 2-chloroethyl.

5. The compound according to Claim 2 in which R
is 2,2-dichloroethyl.

6. The method of decreasing injury to crops, said injury due to a thiocarbamate herbicide, comprising applying into the seed furrow to the seed and adjacent soil in the open furrow prior to covering to achieve a planted state, a non-phytotoxic antidotally effective amount of a compound corresponding to the formula in which X is hydrogen, bromo, chloro, methoxy, trifluoro-methyl, and methyl; n is an integer from 1 to 3 inclusive, provided that when X is bromo, trifluoromethyl, or methoxy, n is 1; and R is selected from haloalkyl having 2 to 6 carbon atoms, inclusive, wherein halo is chloro or fluoro from 1 to 6, inclusive, haloalkenyl having 3 to 6 carbon atoms, inclusive and wherein halo is chloro from 1 to 4, inclusive, dialkylamino having a total of 2 to 8 carbon atoms, inclusive, cyanoalkylthio alkyl having a total of 3 to 6 carbon atoms, inclusive, phos-phonomethyl, trifluoroacetamidomethyl, lower alkyl substituted phenyl said lower alkyl each having 1 to 4 carbon atoms, inclusive, 4-chlorophenylthiomethyl, alkoxyalkyl having 2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2 to 6 carbon atoms, inclusive, cyanoalkyl having 2 to 6 carbon atoms, in-clusive, alkoxycarbonylalkyl having 3 to 7 carbon atoms, in-clusive, formamidoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkenyl having 4 to 7 carbon atoms, inclusive, alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-methyl methylene, chlorophenyl, 4-chloro-benzyl, 4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn-2-yl, methylthioacetimino, acetone imino and benzaldimino, also provided that when X is trifluoromethyl and n is 1, then R can be alkyl having 1 to 4 carbon atoms, inclusive, alkenyl having 3 to 6 carbon atoms, inclusive, and alkynyl having 3 to 6 carbon atoms, inclusive.

7. The method according to Claim 6 in which X is 3-trifluoromethyl and R is haloalkyl.

8. The method according to Claim 6 in which X is 3-chloro and R is haloalkyl.

9. A two-part composition comprising (1) an active thiocarbamate herbicide and (2) a compound having the formula in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl, and methyl; n is an integer from 1 to 3 inclusive, provided that when X is bromo, trifluoromethyl, or methoxy, n is 1; and R is selected from haloalkyl having 2 to 6 carbon atoms, inclusive, wherein halo is chloro or fluoro from 1 to 6, inclusive, haloalkenyl having 3 to 6 carbon atoms, inclusive and wherein halo is chloro from 1 to 4, inclusive, dialkyl-amino having a total of 2 to 8 carbon atoms, inclusive cyanoalkylthioalkyl having a total of 3 to 6 carbon atoms, inclusive, phosphonomethyl, trifluoroacetamidomethyl, lower alkyl substituted phenyl said lower alkyl each having 1 to 4 carbon atoms, inclusive, 4-chlorophenylthiomethyl, alkoxyalkyl having 2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2 to 6 carbon atoms, inclusive, cyanoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkyl having 3 to 7 carbon atoms, inclusive, formamidoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkenyl having 4 to 7 carbon atoms, inclusive, alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-methyl methylene, chloro-phenyl, 4-chlorobenzyl, 4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn-2-yl, methylthioacetimino, acetone imino and benzaldimino also provided that when X is trifluoro-methyl and n is 1, then R can be alkyl having 1 to 4 carbon atoms, inclusive, alkenyl having 3 to 6 carbon atoms, inclusive, and alkynyl having 3 to 6 carbon atoms, inclusive.

10. A two-part herbicide system comprising a first part of one or more thiocarbamate herbicides and a second part of a compound being antidotally active with said carbamate herbicide said compound of the second part having the formula:

in which X is hydrogen, bromo, chloro, methoxy, trifluoromethyl, and methyl; n is an integer from 1 to 3 inclusive, provided that when X is bromo, trifluoromethyl, or methoxy, n is 1; and is selected from haloalkyl having 2 to 6 carbon atoms, inclusive, wherein halo is chloro or fluoro from 1 to 6, inclusive, haloalkenyl having 3 to 6 carbon atoms, inclusive and wherein halo is chloro from l to 4, inclusive, dialkylamino having a total of 2 to 8 carbon atoms, inclusive, cyanoalkyl-thioalkyl having a total of 3 to 6 carbon atoms, inclusive, phosphonomethyl, trifluoroacetamidomethyl, lower alkyl substituted phenyl said lower alkyl each having 1 to 4 carbon atoms, inclusive, 4-chlorophenylthiomethyl, alkoxyalkyl having 2 to 6 carbon atoms, inclusive, alkylthioalkyl having 2 to 6 carbon atoms, inclusive, cyanoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkyl having 3 to 7 carbon atoms, inclusive, formamidoalkyl having 2 to 6 carbon atoms, inclusive, alkoxycarbonylalkenyl having 4 to 7 carbon atoms, inclusive, alkylcarbonylalkyl having 3 to 6 carbon atoms, inclusive, 1,3-dioxacyclohexane-5,5-mekhyl methylene, chloro-phenyl, 4-chlorobenzyl, 4-methoxybenzyl, 3-pyridylmethyl, phenoxyethyl, 3-phenylpropyn-2-yl, methylthioacetimino, acetone imino and benzaldimino also pxovided that when X is trifluoromethyl and n is 1, then R can be alkyl having 1 to 4 caxbon atoms, inclusive, alkenyl having 3 to 6 carbon atoms, inclusive, and alkynyl having 3 to 6 carbon atoms, inclusive.