CA1075925A - Haloacyl and thiohaloacyl aryl-substituted oxazolidines and thiazolidines-herbicidal antidotes - Google Patents

Abstract

HALOACYL AND THIOHALOACYL ARYL-SUBSTITUTED

OXAZOLIDINES AND THIAZOLIDINES - HERBICIDAL ANTIDOTES

Abstract of the Disclosure Haloacyl and thiohaloacyl aryl-substituted oxazolidines and thiazolidines useful as active antidotes against crop injury when used with various herbicides; herbicidal compositions and utility of various herbicides and aryl substituted oxazolidines and thiazolidines having the formula

Description

1~75925 Back~round 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 not 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 many herbicidal compounds which have been commercially successful and are commercially available. These herbicides include types such as triazines, urea derivatives, ; halogenated acetanilides, carbamates, thiocarbamates and thelike. 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 ~arious 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 som~times result. This abnormal growth in the crop plants results in loss of crop yield. The search con-tinues for good selective herbicides.

previous attempts are described to overcome this pro-blem. The treatment of the crop seed with certain "hormonal"
antagonistic agents prior to planting is described; see U.S.
Patents 3,131,509 and 3,564,768. The protective agents, as well as the herbicide, in ~hese prior processes are largely specific to certain cultivated plant species. The antagonistic agents ( 1C1 759~S

have not been notably successful. The aforementioned patents specifically exemplify and describe the treatment of seeds employing compounds of a different chemical class, not sugges-tive of the present invention.

Descri~tion of the Invention - It has been discovered that cultivated crop plants can be protected against injury by thiocarbamate-type herbicides and by halogenated acetanilide herbicides, each alone or in mix-tures or combination with other compounds. Further, as an alter-native effect, the tolerance of the plants to these herbicides can be substantially increased by adding to the soil an antidote compound corresponding to the following formula Y ~ R
R-C-N
~~X

wherein X and Y are independently oxygen or sulfur; R is halo-alkyl or chloro alkenyl; Rl is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are mono-fluoro, mono- or di- chloro, nitro, methyl, methoxy or hydroxyl;
R2 is hydrogen or lower alkyl; R4 is hydrogen or lower alkyl; R3 is hydrogen, lower alkyl, hydroxymethyl, N-methyl carbamoyloxy-methyl or dichloroacetoxymethyl; R5 is hydrogen, lower alkyl or phenyl; and R6 is hydrogen; provided that at least one of Rl or R5 is phenyl, substituted phenyl or naphthyl.

Certain of the compounds disclosed herein are considered new compositions and correspond to the following formula ~ - \

10759'~s R3 R4 ¦5 y .~--R6 R-C-N
. ~ ~ ~ .
Rl R2 in which X and Y are independently o~ygen or sulfur; R is halo-alkyl or chloroalkenyl; Rl is hydrogen, lower alkyl or phenyl;
R2 is hydrogen or lower alkyl; R3 is hydrogen or`lower alkyl;
R4 is hydrogen or lower alkyl; R5 is phenyl and ~ is hydrogen.

~ 5 In the above description, the following embodiments ; are intended for the various substituent groups: For R, halo-` alkyl preferably includes those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain configurations and the term halo includes chloro and bromo . 10 as mono, di, tri and tetra substitutions. As e~emplary of the ' alkyl portion within the preferred embodiment are the following:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-` dimethylbutyl, amyl, isoamyl, n-hexyl and isohe~yl. For R, chloro alkenyl preferably includes those members which contain from 2 to 4 carbon atoms and at least one olefinic double bond and the chloro substituents are present as mono-, di-, tri-, or tetra- substitutions, such as trichlorovinyl. For Rl, R2, R39 R4 and R5, lower alkyl in each instance preferably includes those members which contain from 1 to 4 carbon atoms, inclusive, ;.
~0 in both straight chain and branched chain configurations, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl and the like.
.
As an alternative mode of action, the compounds of ; this invention may interfere with the normal herbicidal action 1C~759Z5 of the thiocarbamate-type and other herbicides to render them selective in their action. Whichever mode of action is present, the corresponding beneficial and desirable effect is the con-tinued herbicidal effect of the thiocarbamate ~ith the accom-panying 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 night other~7is~e produce. Whether it is to be termed a remedy, interferant, protectant, or the like, ~7ill depend upon the exa_t mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soil in ~hich a crop is planted. Hitherto, there have been no systems t~hich have been satisfactory for this purpose.

The compounds of this invention represented by the above formula can be prepared by several difLerent procedures depending upon~the starting materials.

The oxazolidine and thiazolidine intermediates were prepared by the condensation of the amino alcohol or mercaptan with a suitable aldehyde or ketone in boiling benzene with the continuous separation of l~ater. This method is described by Ber~mann et al., JA5S 75 358 (1953). usually, the o~azolidines and thiazolidines intermediates were pure enough to be used directly without further ?urification. Aliquots of these solu-tions were then used to pre?are the compounds of this invention.

Compounds having a 3- thi~cylsubstitution may be pre-pared from the corresponding o:ygen analogues by methods kno m in the synthetic organic literature, such as treatment with ~2S5 in benzene at reflu:~.

The appropriate ;ntermediate was reacted with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine, to prepare the desired compound. Work-up and purification procedures involved standard methods of extrac-tion, distillation or crystallization.

The compounds of the present invention and their pre-paration are more particularly illustrated by the following examples. Following the examples of preparation is a table of compounds which are prepared according to the procedures des-cribed herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE I

Preparation oS ~-m-nitro~henyl-3-dichloroa ~ELI_a~_ _idine.
Five and eight tenths (5.8) grams of 2-m-nitrophenyl oxazolidine was dissolved in 50 ml. methylene chloride con-taining 3.5 g. of triethylamine. Dichloroacetyl rhloride 4.4 g. was added dropwise with stirring to the reaction flask and cooled in a water bath at room temperature. When additlon was complete, the mixture was stirred at room temperat~re for about 30 minutes, washed with water, separated and dried over anhydrous magnesium sulfate. The solvent was stripped off under vacuum. There was obtained a yield of 8.6 g. of the title com-pound, .~13 = 1.5590.

' .

EXA~LE II
Preparation of 2-ethyl-3-dichloroacetyl-5-phenyl o~azolidine.
Twenty-one and three tenths (21.3) ml. of a solution containing 5.3 g. of 2-ethyl-5-phenyl oxazolidine was diluted with 25 ml. of benzene and 3.1 g. of triethylamine was added.
The mixture was cooled in a room temperature water bath and 4.4 g.
of dichloroacetyl chloride was added dropwise with st~rring.
The stirring was continued for about 30 minutes after addition was complete. The solution was washed with water, separated, dried over magnesium sulfate and removed under vacuum. There -lQ was obtained a yield of 8.7 g. of the title compound, an oil, ~= 1.5600.

XAMPLE III

Preparation of 2 2-dimethyl-3-dichloroacetvl-5-Dhenyl o~azolidine.
One hundred (100) grams of 1-phenyl-2-amino ethanol was dissolved in 250 ml. of benzene and 45 g. of acetone was added. The mixture was heated at reflux for several hours while about 15 ml. of water was removed with a modified Dean-Stark apparatus. The mixture was cooled and 75 ml. of triethylamine was added, followed by 108 g. of dichloroacetyl chloride added dropwise with stirring and cooling in a room temperature ~ater bath. The solution was allowed to stand after addition was com-plete, washed with water, dried over anhydrous magnesium sulfate, and the solvent stripped under vacuum. The thick oil wt. 170 g.
crystallized on standing and was triturated with dry ether to give 132 g. of the title compound, a white solid, m.p. 99.5-100.5C.

.

EXh~LE IV

Preparation of 2- ~-naPhthvl-3-chloroacetyl oxazolidine.
; Nineteen and nine tenths (19.9) ml. of a benzene solution containing 5 g. of 2- c~-naphthyl oxazolidine was com-bined with 50 ml. of benzene and 2.8 g. of chloroacetyl chloride.
To this was added 2.6 g. of triethylamine, dropwise with stirring in an ice bath. The mix~ure was stirred at room temperature for 30 minutes after addition was complete, washed with water, - separated and dried over magnesium sulfate. The solvent was stripped under vacuum. There was obtained a yield of 6.7 g.
of an oil, the title compound, N30 = 1.6030.

E~MPLE V

Preparation of 2-phenyl-3-chloroacetvl-4,4-dimethyl oxazolidine.
;
Twenty-one and three tenths (21.3) ml. of a benzene solution containing 5.3 g. of 2-phenyl-4,4-dimethyl o~azolidine was mixed with 50 ml. of benzene and 3.4 g. of chloroacetyl chloride. To this solution was added 3.1 g. of triethylamine, dropwise with stirring in an ice bath. The mixture was stirred for about 30 minutes after addition was complete and then washed with water, separated and dried over magnesîum sulfate and the solvent stripped. There was obtained a yield of 6.5 g. of an oil, the title compound, ~D0 = 1.5364.

.

1(~7~925 EXA~LE VI

Preparation of 2-~henyl-3-dichloroacetyl thiazolidine.
Five (5) grams of 2-phenyl thiazolidine was dissolved in 50 ml, of acetone, 3.1 g. of triethylamine was added and the mixture stirred in a room temperature water bath, while 4.4 g.
of dichloroacetyl chloride was added dropwise. The mixture was allowed to stand for about 30 minutes and then poured into water, extracted with methylene chloride, separated, dried over magnesium sulfate, and the solvent stripped under vacuum. There was obtained a yield of 7.3 g. of an oil, the title compound, ~D0 = 1.5836.
.~
EXAMPLE VII
.
Preparation of 2-m-chloro~henyl-3-dichloroacetyl thiazolidine.
Five (5) grams of 2-m-chlorophenyl thiazolidine was dissolved in 50 ml. of benzene and 2.6 g. of triethylamine and the mixture was stirred in a room temperature water bath, while 3.7 g. of dichloroacetyl chloride was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated and dried over magnesium sulfate and the benzene strip-ped under vacuum. There was obtained a yield of 7.2 g. of an oil, the title compound, N30 = 1.5805.

, .~ , .
_g_ ~759Z5 .
EXAMPLE VIII

Preparation of 2(2',6'-dichloro~henyl)3-chloroacetyl thiazolidine.
~enty-threç and five tenths (23.5) ml. of a benzene solution containing 5.9 g. of 2(2',6'-dichlorophenyl) thia-zolidine was combined with 25 ml. of benzene and 2.8 g. of chloro-acetyl chloride and the mixture stirred in an ice bath, while

2.6 g. of triethylamine was added dropwise. After standing for about 30 minutes the mixture was washed with water, separated, dried over magnesium sulfate and the benzene stripped off under vacuum. There was obtained a yield of 8 g. of an oil, the title compound, ND0 = 1.6041.

E~AMPLE I~

Preparation of 3(3-bromoDropionyl~5-phenyl oxazolidine.
Four and five tenths (4.5) grams of 5-phenyl oxazoli-dine contained in 44.7 g. of benzene solution was mixed with

3.1 g. of triethylamine and stirred in a room temperature water bath, while 5.2 g. of 3-bromopropionyl chloride was added drop-: wise. After standing for about 30 minutes, the solution was washed with water, separated, dried over magnesium sulfate and the solvent stripped under vacuum. There was obtained a yield of 6 g. of an oil, the title compound, N30 = 1.5591.

~075925 EXAMPLE X

Preparation of 2 2~4-trimethyl-3-dichloroacetyl-5-phenyl o~azolidine 1~7enty-three (23) ml. of a benzene solution containing 5.7 g. of 2,2,4-trimethyl-5-phenyl oxazolidine was mixed with 25 ml. of benzene and 3.1 g. of triethylamine and stripped at room temperature, while 4.4 g. of dichloroacetyl chloride was added dropwise. After standing for about 30 minutes, the mix-ture was washed with water, separated, dried over magnesium sulfate and stripped under vacuum. The product which crystal-lized was extracted with ether and precipitated with pentane.
There ~as obtained 3.9 g. of a solid, the title compound, m.p. 126C.

EXAMPLE XI

Preparation of 2-p-chloro~henyl-3-dichloroacetyl oxazolidine.
~7enty-two (22) ml. of a ben-ene solution containing 5.5 g. of 2-p-chlorophenyl oxazolidine was mixed with 25 ml.
of benzene and 3.1 g. of triethylamine and stirred at room temperature, 7hile 4.4 g. of dichloroacetyl chloride was added dropwise. The mixture was allowed to stand for about 30 minutes, washed ~7ith water, separated, dried over magnesium sulfate and then stripped. There ~7as obtained a yield of 8.4 g. of an oil, the title compound, ~DO = 1.5668.

EXA~PLE ~II

Preparation of 2 2 5-diDhenyl-3(2,~dibromoDroDionyl) oxazolidine.
Four and five tenths (4.5) grams of 2,5-diphenyl oxazolidine ~as dissolved in 50 ml. of methylene chloride and - 5 g. of 2,3-dibromopropionyl chloride was added and the mixturestirred in an ice bath, while 2.1 g. of triethylamine was added dropwise. After standing for about 30 minutes, the mixture was washed with water, separated and dried over magnesium sulfate and stripped under vacuum. There was obtained a yield of 7.1 g. of an oil, the title compound, ~ = 1.5734.

The following is a table of the compounds which are prepared according to the aforementioned procedures. Compound numbers have been assigned to them and are used for identifica-~ tion throughout the bala~ce ~f the specification.

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iO75925 Other examples of compounds falling within the generic formula presented herein, which are preparable by the aforedes-cribed procedures and which may be formulated into herbicidal compositions and applied as herein illustrated, are:

_ Rl R2 R3 R4 R5 R6 X y- - - - _ _ _ CH2Cl C6H5 H H H H H O S
CHCl2 C6H5 H H H H H O S

CH2Cl C6H5 H H H H H S S

: CH2Cl CH3 CH3 H H C6H5 H O S
CHC12 C~3 CH3 H H C6H5 H O S

CH2BrCHBr m-Cl-C6H4 H H H CH3 H O S
CH2 BrCHBr C6H5 H H H CH3 H S S
CH2BrCHBr CH3 CH3 H H C6H5 H O S
CH2BrCHBr CH3 CH3 H H C6H5 H S S

. --2n-The herbicides indicated in the tables and elsewhere are used at rates which produce effective contro1 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 t~at the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbi-cidal activity varies among specific compounds and among combi-nations of specific compounds within the classes. 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 com-pound or combination to control undesirable plant species readily may be made. I~ithin the present invention are 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 this method is not intended to be limited by the specific crops employed in the examples.

The herbicidal compounds employed in the utility of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effect ve against a wide range of pl2nt species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the herein described nerbicidal compounds to the area or pl2nt . .

~0759ZS

locus where control is desired. The compositions as set forth in this invention include those wherein the preferred active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichloro-allyl-diisopropyl thiocarbamate, S-ethyl cyclohexyl ethyl thio-carbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl he~ahydro-lH-azepine-l-carbothioate, 2-chlorQ-N-isopropyl-acetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl diethyl thiocarbamate, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6 bis(ethylamino)-3-triazine, 2(4-chloro-6-ethylamine-s-triazine-2-yl-amino)-2-methylpropionitrile, 2-chloro-~

4-cyclopropylamino-6-isopropylamino-s-triazine, 2,4-dichloro-phenoxyacetic acid, its esters and salts, and 3-(3,4-dichloro-phenyI)-l,l-dimethylurea and combinations thereof.

An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying ef~ects include all deviations from natural development; for e~ample, killing, retardation, defolia-tion, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants", it is meant germirant seeds~
emerging seedlings and established vegetation including the roots and above-ground portions.

~0759Z5 Evaluation Procedures Flats to be used for gro~ing the crops and weed species were filled with loamy sand soil, Stock solutions of herbicides and antidotes were prepared as follows:
A. Herbicide - 2-chloro-2',6'-diethyl-N-(methoxy~
methyl) acetanilide - LASS0 4E - 6,25 g. of LASS0 4E was diluted in 1000 ml. of water. 100 ml. of this solution was applied , using a linear spray table, such that the e~uivalent of 2 lb/A
of LASS0 was applied in 80 gal. of water per acre to each flat.
B. Antidote - of each candidate 95 mg. was dissolved in 15 ml. of acetone with 1% ~een 20 ~ (polyoxyethylene sorbit2n monolaurate) so that 1-1/2 ml. equals 5 lb/A per flat (based on 1/2 surface area of a flat).

PES and PPI Tank ~ixes ~n-furrow application of the antidote employed the above stock solutions (A and B). As a preparatory step, a one pint sample of soil was removed from each flat to be retained and used laier to cover the seeds after treatment with the additives. The soil was leveled before planting.

Rows one-quarter inch deep ~7ere made length~eise in each treated flat, preparatory to seeding. After seeding, the i 20 flats were sectioned into t~o equal portions using a wooden barrier and one and one-half ml. of additive stock solution (B) ; was atomized directly onto th2 e~posed seed and into the furro~
in one-half of the flat, The untreated section of the fiat served as an herbicide clleck 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 ~.ad been removed earlier, -~3-.~ .

1~759Z5 The herbicide was applied initially on an individual flat basis by spraying on the soil on a linear spray table the required amount of the herbicide stock solution onto the soil, after seeding and antidote treatment of the furrow.

For tank mixes to be applied as pre-emergence surface application or as pre-plant incorporation, application of the following solutions were used. For 2-chloro-2',6'-diethyl-N-methoxymethyl) acetanilide at 2 lb/A 800 mg. 4E was diluted to - 200 ml. with deionized water. To prepare a combined tank mix, 4 ml. of the acetanilide stock solution and 3 ml. of the antidote stock solution (B) were mixed. For the pre-plant incorporation, the same mixed stock solution was injected into the soil during incorporation in a 5 gallon rotary mixer. For pre-emergence sur-face application, the same stock solution was applied to soil surface after seeding.

The flats were placed on greenhouse benches where temperatures were maintained be~ween 70-90F. The soil was watered by sprinkling to assure good plant growth. Injury rat-ings were taken 2 and 4 weeks after the applications were made.
2~ Individual flats treated with the herbicide alone were included to provide a basis for determiring the amount Gf injury reductior.
provided by the herbicide antidotes.

Some of the candidate antidotes were assayed as anti-dotes to protect various crops against injury from tniocarbamate herbicides. Selected as representative thiocarbamate herbicides were S-ethyl N,N-dipropylthiocarbamate (EPTC, EPTA~ ) and S-propyl N,N-dipropylthiocarbamate ~VE~NA~ ). Stock solutions of herbicides and antidotes were prepared and applied in a " ' .

variety of ways. Soil incorporation, pre-emergence surface application and in-furro~ treatment were employed.

Stock solutions for ~PTAM ~ were prepared as follows:
A. 1/2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) was dilueed wi~h 500 mi. OI deionized water so that 2 ml. equals 1/2 lb/A/flat.
B. 5 lb/A: 6700 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 5 lb/A/flat.

Stock solutions for VERNAM ~ :

C. 3/4 lb/A: 95 mg. of VERNAM @ (75% a.i.) was diluted with 100 ml. of deionized water so that 4 ml. applied Dre-plant incorporated is equivalent to 3/4 lb/A per flat.
D. 1 lb/A: 633 mg. of VERNAM ~ (75% a.i.) was diluted with 500 ml. of deionized water so that 4 ml. applied is equivalent to 1 lb/A
per flat.
E. 5 lb/A: 633 mg. of VERNAM ~ (75% a.i.) was diluted ~7ith 100 ml. of deioni~ed water so that 4 ml. is equivalent to 5 lb/A per flat.

The following table includes results as per cent pro-tection of various crops according to the various procedures discussed above. The per cent protection is determined by a comparison with flats not treated with the candidate antidotes oi this invention.

.

.

~07592S
.
TABLE II
Application Method: In-Furrow - IF
Pre-Plant Incorporation - PPI (Tank Mix) Pre-Emergence Surface Application - P~S
(Tank Mix) Crop Species: Milo - (Sor~hum vul~are~
Weed Species: Shatter cane - SC (Sor~hum bicolor) Foxtail - ft (Satarla v~ridis) Crabgrass - CG (Digi~taria san~uinalis~
Watergrass - WG (Echinochloa crus~alli) * 2 Z injurY
** 8 % protectin _____ ________________~__________________________________________ PPI (5 lb/A) PES (5 lb/A) C0~ W ND 5 lb/A - IF (Tank ~ix) (Tank ~x) NUMBER Milo SC Milo Ft CG WG Milo Ft CG l7G
LASS0 2 lb/A 100~ 100~ 50 100 100 100 70 100 100 100 __________________________________________________________________ 1*~ .70 0 0 0 0 0 0 0 0 0 3 50 0 0 ~ 0 0 0 0 0 0 . -26-~~`` - 10'75925 TAB (contlnued) PPI ( 5 lb /A ) PES ( 5 lb /A ) CûMPOUND 5 lb/A - IF (Tank Mix) (Tank Mix) ER Milo SC Milo Ft CG WGMilo Ft CG WG

42 50 .0 20 0 0 0 0 0 0 0 0 40 0 ~ 0 0 0 0 0 `57 30 0 0 0 0 0 0 0 0 0 58 60 0 0 0 0 0 0 ~ 0 0 59 30 0 80 0 ~0 0 0 0 0 0 67 0 0 40 0 0 0 ~8 0 0 0 68 80 0 0 0 0 o o o o o TABLE II (cont. nued) 10'759ZS ``

PPI (5 lb/A) PES (5 lb/A) COMl?OUND 5 lb/A - IF (Tank Mix) (Tank Mix) NU~ER Milo SC Milo Ft CG ~7G MiloFt CG l7G
_ 84 60 - 50 0 0 0 50 . 0 0 0 87 50 o 40 0 0 0 67 0 0 0 - = not tested.

' :

,. ..

~07 S9 Z 5 Thiocarbamate Herbicide ~lulticrop Screen Treated flats were seeded ~ith DeKalb XL-44 corn (Zea maize), sugarbeets tBeta vul~are), small seeded gray striped sunflower (Helianthus annus), soybeans (GlYcine ma~) and oilseed rape (Brassica naDus), milo [sorghum] (sor~um vul~are), wheat (Triticum aestivum), green fo~tail (Sataria viridis), rice (OrYza sativa) and barley (Hordeum vulgare). Seeds were then covered with the pint soil sample removed prior to seeding.
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The flats were then placed on greenhouse benches where temperatures were maintained between 70-90F. The soil was watered by sprinkling to assure good plant gr~.7th.

Injury ratings were taken 2 and 4 weeks after the treatments were applied. Soil treated with the herbicide alone at the indicated rate was included to provide a basis for deter-mining the amount of injury reduction provided by the herbicide antidotes. The per cent protection of various representative crops is reported in Table III. The per cent protection is determined by a comparison with flats not treated with the candidate antidote.-: `
: .

TABLE III
MULTICROP SC~EEN RESULTS
Method of CO~SPOUND Antidote Herbicide/ Crop Per Cent NI~ER A~lication Rate lb/A ProtectedProtection 1 PPI EPTC/1i2 Milo 30 Rice 63 Barley 30 2 PPI . EPTC/5 Corn '100 (2 ~AS~
3 PPI EPTC/5 Rice 63 Corn 100 4 PPI ~PTC/1/2 Milo 50 6 PPI EPTC/1/2 Milo 40 9 PPI EPTC/1/2 Rice 100 ~ Barley 50 11 PPI EPTC/1/2 Milo 50 ; Corn 100 13 PPI EPTC/5 Sunflo~ter 67 PPI EPTC/1/2 Rice 100 EPTC/5 Corn 65 16 PPI EPTC/1/2 Rice 100 EPTC/5 Corn 65 17 . PPI EPTC/1/2 Rice 100 22 PPI EPTC/1/2 Milo .90 EPTC/5 Corn 100 23 PPI EPTC/1/2 Milo 67 EPTC/1/2 Rice 55 EPTC/5 Sunflower 30 28 PPI EPTC/5 Sunflower 67 : 31 PPI EPTC/5 Sugarbeet 70 33 PPI EPTC/1/2 Rice 44 EPTC/1/2 Barley 40 34 PPI EPTC/1/2 Milo 10 PPI EPTC/1/2 Milo 45 36 PPI EPTC/5 Sugarbeet 80 38 PPI EPTC/5 Corn 33 10759~5 TABLE III (continued) Method of . COMP W ND Antidote Herbicide/ Crop Per Cent NU~ER ApPlication Rate lb/A Protected Protection : 39 PPI EPTC/1/2 Barley 40 EPTC/5 Corn 55 PPI EPTC/5 Corn 22 41 PPI EPTC/5 Sunflower 67 42 PPI EPTC/5 Corn 22 47 PPI EPTC/1/2 Milo 75 Wheat 67 Rice 78 Barley 63 EPTC/5 Corn 100 48 PPI EPTC¦1/2 Milo 25 51 PPI EPTC/1/2 Barley 67 53 PPI EPTC/1/2 Barley 50 EPTC/5 Corn 100 .:
54 PPI EPTC/5 Corn 40.
57 PPI EPTC/5 Oilseed rape 67 PPI EPTC/5 Corn 100 PPI EPTC/5 Corn 50 ;. 67 PPI EPTC/1/2 Rice 100 68 PPI EPTC/1/2 Rice 100 PPI EPTC/1/2 Wheat 78 ` Barley 85 .: Rice 100 - 72 PPI EPTC/1/2 Rice 85 EPTC/1/2 Barley 85 73 PPI EPTC/1/2 Barley 50 PPI EPTC/1/2 Rice 85 Barley 72 EPTC/5 Corn 50 76 IF/5 lb/A EPTC/5 Corn 100 77 IF/5 lb/A EPTC/5 Corn 50 TABLE III (continued) Method of COMPOUND Antidote Herbicide/ Crop Per Cent NUM~ER Ap~lication Rate lb/A ProtectedProtection VERNAM 6E VERNA~I/5 Corn 60~ Inju~;
Milo 100 Wheat 98 Barley go ~__________________________~_______________________________________ 2IF/5 lb/A VERNA~I/5 Corn 50 3IF/5 lb/A VERNAM/5 Corn 50 4IF/5 lb/A VERNAM/5 Corn - 100 11 IF/5 lb/A VERNA~I/5 Corn 100 VERNAM/3/4 ~lo 50 18 IF/5 lb/A VERNAM/5 Corn 100 IF/5 lb/A VERNAM/5 Corn 100 VERNAM/3/4 Milo 60 22 IF/5 lb/A VERNAM/5 Corn 100 VERNAM/3/4 Milo 90 23 IF/5 lb/A VE~NA~I/5 Corn 100 24IF/5 lb/A VERNAM/5 Corn 84 VERNAM/3/4 Milo 40 26IF/5 lb/A VERNAM/3/4 Barley 67 35IF/5 lb/A VERNAM/3/4 Corn 67 VE~NAM/3/4 Milo 40 38 .IF/5 lb/A VE~NAM/5 Corn 50 39IF/5 lb/A VERNAM/5 Corn 100 VERNAM/3/4 Barley 55 40IF/5 lb/A VERNAM/5 Corn 67 47IF/5 lb/A VERNA~I/5 Corn 100 VERNA~I/3/4 Milo 50 53IF/5 lb/A VERNA~I/5 Corn 100 60IF/5 lb/A VEP~A~I/5 Corn 100 78IF/5 lb/A VE~NA~I/l Milo 50 VERNA~I/5 Corn 22 79IF/5 lb/A VE~A~ f;lo 60 VEP~NA~l/5 Corn 88 80IFi5 lb/A VERNA~ ~lo 30 VERNA~I/5 Corn 88 : -32-TABLE III (continued) Method of COMPOUND Antidote Herbicide/ Crop Per Cent NUMBER Application Rate lb/A Protected Protection 81 IF/5 lb/A VERNAM/5 Corn 20 82 IF/5 lb/A VERNAM/5 Corn 45 (2 wks) - 83 IF/5 lb/A VERNAM/l Barley 50 ~ 84 IF/5 lb/A VERNAM/l Milo 40 ; VERNAM/5 Corn 88 IF/5 lb/A VERNAM/l Wheat 40 VERNAM/l Barley 45 VERNAM/5 Corn 67 86 IF/5 lb/A VERNAM/l Barley 55 VERNAM/5 Corn 78 87 IF/5 lb/A VERNAM/l Milo 50 VERNAM/l Barley 45 -~ VERNAM/5 Corn 67 88 IF/5 lb/A VERNAM/l Barley 55 IF/5 lb/A VERNAM/l Barley 33 VERNAM/5 Soybeans 30 91 IF/5 lb/A VERNAM/5 Corn 36 94 IF/5 lb/A VERNAM/5 Corn 23 IF/5 lb/A VERNAM/l Wheat 44 VERNAM/l Barley 44 VERNAM/5 Corn 100 96 IF/5 lb/A VERNAM/l Wheat 67 VERNAM/l Barley 44 VERNAM/5 Corn 37.5 97 IF/5 lb/A VERNAM/5 Corn 87.5 98 IF/5 lb/A VERN~/5 Corn 37.5 99 IF/5 lb/A VERNAM/5 Corn 75 100 IF/5 lb/A VERNAM/l Milo 20 VERNAM/l Barley 22 101 IF/5 lb/A VERNAM/l Milo 20 VERNAM/l Barley 44 102 IF/5 lb/A VERNAM/6~* Corn 100 103 IF/5 lb/A VERNAM/l Wheat 33 VE~NAM/l Barley 33 *~Stock solution for VERNAM 6E at 6 lb/A PPI (pre-plant incorporated) 3800 mg/500 ml. water; such that 4 ml. =

1(~759Z5 The compounds and compositions of this invention ~7ere employed in effective herbicidal compositions comprising the antidote and a representative thiocarbamate herbicide and the antidote and a representative halogenated acetanilide herbicide, as described hereinabove. The herbicidal compositions were tested in the following manner.

The compositions of the present invention for the pro-tection of cultivated crop plants comprise an active herbicidal compound and an antidote therefor selected from the above-described compounds. The compositions of herbicide and antidote can be prepared by conventional methods through the thorough mixing and grinding of the ac~ive herbicide agents and the anti-dote with suitable carriers and/or other distribution media, possibly with the addition of dispersion agents or solvents.

The antidote compounds and compositions of the present invention can be used in any convenient form. Thus, the anti-dote compounds can be formulated into emulsifiable 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 herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated in~o the soil. ~oreover, the crop seed itself can be treated witll a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated ~7ith the herbicide and subsequently treated with the herbicide. The 10759~Z5 addition of the antidote compound does not affect the herbicidal activity of the herbicides.
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The amount of antidote compound present can range between about O.Oool to about 30 parts by weight of antidote compound described herein per each part by weight of herbicide.
The exact amount of antidote compound will usually be deter-mined on economic ratios for the most effective amount usable.
It is understood that a non-phytotoxic quantity of antidote compound will be employed in the herbicidal compositions des-cribed herein.

Claims (34)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An herbicidal composition comprising an active herbicidal compound selected from the group of thiocarbamate herbicides, halogenated acetanilide herbicides and mixtures thereof and an antidote therefor corresponding to the formula wherein X and Y are independently oxygen or sulfur; R is halo-alkyl or chloroalkenyl; R1 is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are mono-fluoro, mono- or di- chloro, nitro, methyl, methoxy, or hydroxyl;
R2 is hydrogen or lower alkyl; R3 is hydrogen, lower alkyl, hydroxymethyl, N-methylcarbamoyloxymethyl or dichloroacetoxymethyl; R4 is hydro-gen, or lower alkyl; R5 is hydrogen, lower alkyl or phenyl; and R6 is hydrogen; provided that at least one of R1 or R5 is phenyl, substituted phenyl or naphthyl and when R1 is hydrogen, lower alkyl or phenyl R5 is other than phenyl.

2. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is chloro-phenyl and R2, R3, R4, R5 and R6 are each hydrogen.

3. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is methyl-phenyl and R2, R3, R4, R5 and R6 are each hydrogen.

4. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is nitro-phenyl and R2, R3, R4, R5 and R6 are each hydrogen.

5. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R s haloalkyl, R1 is nitro-phenyl, R2, R5 and R6 are each hydrogen and R3 and R4 independently are lower alkyl.

6. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is phenyl, R2, R3, R4, R5 and R6 are each hydrogen.

7. The herbicidal composition according to Claim 6 in which R is dichloromethyl.

8. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is methoxy-phenyl, R2, R3, R4, R5 and R6 are each hydrogen.

9. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is phenyl, R2, R3, R4 and R6 are each hydrogen and R5 is lower alkyl.

10. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is phenyl, R2 and R6 are each hydrogen, R3, R4 and R5 are each lower alkyl.

11. The herbicidal composition according to Claim 1 in which X is sulfur, Y is oxygen, R is haloalkyl, R1 is phenyl, R2, R3, R4, R5 and R6 are each hydrogen.

12. The herbicidal composition according to Claim 1 in which X is oxygen or sulfur, Y is oxygen, R is haloalkyl, R1 is chlorophenyl and R2, R3, R4, R5 and R6 are each hydrogen.

13. The herbicidal composition according to Claim 1 in which X is oxygen or sulfur, Y is oxygen, R is chloroalkenyl, R1 is chlorophenyl and R2, R3, R4, R5 and R6 are each hydrogen.

14. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is naphthyl and R2, R3, R4, R5 and R6 are each hydrogen.

15. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkenyl, R1 is phenyl, and R2, R3, R4, R5 and R6 are each hydrogen.

16. The herbicidal composition according to Claim 1 in which X is sulfur, Y is oxygen, R is haloalkyl, R1 is nitro-phenyl and R2, R3, R4, R5 and R6 are each hydrogen.

17. The herbicidal composition according to Claim 1 in which X is oxygen or sulfur, Y is oxygen, R is haloalkyl, R1 is phenyl, R3 is lower alkyl and R2, R4, R5 and R6 are each hydrogen.

18. The herbicidal composition according to Claim 1 in which X is sulfur, Y is oxygen, R is haloalkyl, R1 is phenyl, R3 is lower alkyl, R4 is lower alkyl and R2, R5 and R6 are each hydrogen.

19. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is hydroxy-phenyl and R2, R3, R4, R5 and R6 are each hydrogen.

20. The method of protecting a crop from injury, said injury due to a thiocarbamate herbicide, comprising application to the soil in which said crop is to be planted and grown, a non-phytotoxic antidotally effective amount of a compound corres-ponding to the formula in which X and Y are independently oxygen or sulfur; R is halo-alkyl or chloroalkenyl; R1 is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are mono-fluoro, mono- or di- chloro, nitro, methyl, methoxy, or hydroxyl;
R2 is hydrogen or lower alkyl; R3 is hydrogen, lower alkyl, hydroxymethyl, N-methylcarbamoyloxymethyl or dichloroacetoxy-methyl; R4 is hydrogen, or lower alkyl; R5 is hydrogen, lower alkyl or phenyl; and R6 is hydrogen; provided that at least one of R1 or R5 is phenyl, substituted phenyl or naphthyl and when R1 is hydrogen, lower alkyl or phenyl R5 is other than phenyl.

21. The method according to Claim 20 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is phenyl, R2, R3, R4, R5, and R6 are each hydrogen.

22. The method according to Claim 20 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is chlorophenyl and R2, R3, R4, R5 and R6 are each hydrogen.

23. The method according to Claim 20 in which 2 is oxygen, Y is oxygen, R is haloalkyl, R1 is phenyl, R3 is lower alkyl, R2, R4, R5 and R6 are each hydrogen.

24. The method according to Claim 20 in which X is oxygen or sulfur, Y is oxygen, R is haloalkyl, R1 id chlorophenyl, R2, R3, R4, R5 and R6 are each hydrogen.

25. The method according to Claim 20 in which X is sulfur, Y is oxygen, R is haloalkyl, R1 is phenyl, R2, R3, R4, R5 and R6 are each hydrogen.

26. The method according to Claim 20 in which X is sulfur, Y is oxygen, R is haloalkyl, R1 is phenyl, R3 is lower alkyl and R2, R4, R5 and R6 are each hydrogen.

27. The method of protecting a crop from injury, said injury due to a substituted acetanilide herbicide, comprising pre-plant incorporation in the soil in which said crop is to be planted, a non-phytotoxic antidotally effective amount of a com-pound corresponding to the formula in which X and Y are independently oxygen or sulfur; R is halo-alkyl or chloroalkenyl; R1 is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are mono-fluoro, mono- or di- chloro, nitro, methyl, methoxy, or hydroxyl;
R2 is hydrogen or lower alkyl; R3 is hydrogen, lower alkyl, hydroxymethyl, N-methylcarbamoyloxymethyl or dichloroacetoxy-methyl; R4 is hydrogen, or lower alkyl; R5 is hydrogen, lower alkyl or phenyl; and R6 is hydrogen; provided that at least one of R1 or R5 is phenyl, substituted phenyl or naphthyl and when is hydrogen, lower alkyl or phenyl R5 is other than phenyl.

28. The method according to Claim 27 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is nitrophenyl, R2, R3, R4, R5 and R6 are each hydrogen.

29. The method according to Claim 27 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is phenyl and R2, R3, R4, R5 and R6 are each hydrogen.

30. The method according to Claim 29 in which R is dichloromethyl.

31. The method according to Claim 27 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is chlorophenyl and R2, R3, R4, R5 and R6 are each hydrogen.

32. The method according to Claim 27 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is phenyl, R2 and R6 are each hydrogen, R3, R4 and R5 are each lower alkyl.

33. The method according to Claim 27 in which X is oxygen or sulfur, Y is oxygen, R is haloalkyl, R1 is phenyl, R2, R3, R4, R5 and R6 are each hydrogen.

34. The method according to Claim 27 in which X is sulfur, Y is oxygen, R is haloalkyl, R1 is chlorophenyl and R2, R3, R4, R5 and R6 are each hydrogen.