CA1072566A - Haloacyl and thiohaloacyl aryl-substituted oxazolidines and thiazolidines-herbicidal antidotes - Google Patents

Abstract

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

~7;~:5~6 Back6~e9y:-5t~ n 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 the like. Some examples of these compounds are described in U.S.
Patents No, 2,913,327~ 3,037,853, 39175,897, 3,185,720, 3,1989786 and 3,582,314.

The side effect of injury to a cultivated cxop by various herbicidqs is particularly inconvenient and unfortunate.
When used in the recommended amounts in the soil to control broadleaf weeds and grasses9 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 these prior processes are largely specific to certain cultivated plant species. The antagonistic agents

-2- ~

~0725G~
have not been notably successful. The aforementioned patents specifically exempli~y and describe the treatment of seeds employing compounds of a different chemical class, not sugges-tive of the present invention.

It has been discovered that cultivated crop plants can be protected against injury b~ thiocarbamate-type herbicides and by halogen~ted acetanilide herbicides, each alone or in mix-tures or combina~ion 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 -~R6 R-C-N_____~
~X ' .
Rl R2 wherein X and Y are independently oxygen or sulfur, R is halo-alkyl or chloro allcenyl; Rl is hydrogen, lower alkyl, phenyl, naphthyl, substituted phenyl wherein said substituents are mono-fluoro9 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 follo~ing formul~

,,,,~

~725~;~

Y ~--R6 RC~N ______ ~\- X, 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.

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 atoms7 inclusive, in both straight chain and branched chain configurations and the term halo includes chloro and bromo as mono, di, tri and tetra substitutions. As exemplary of the alkyl por~ion within the preferred embodiment are the following~
Methyl, ethyl, n-propyl, isopropyl, n-buty1~ sec,-butyl, 1,1-dimethylbutyl, amyl, isoamyl, n~hexyl and isohe;yl. For R, chloro alkenyl preferably includes those members which contain ; 15 from 2 to 4 carbon atoms and at least one olefinic double bond and the chloro substituents are present as mono- 9 di-, tri-, or tetra- substitutions, such as trichlorovinyl. For Rl, R2, R3, 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, t _ .~butyl and the like.

As an alternative mode o~ actlon, the compounds of this invention may interEere with the normal herbicidal action -4;

~IL07;Z 5~6 of the thiocarbamate-type and o-ther herbicides to render thèm 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 with the accom-panying decreased herbicidal effect on de ired 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 produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect which is desirable, is the result of the method of treating the soil in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpose.
The compounds of this invention represented by the above formula can be prepared by several different 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 water. This method is described by Bergmann et al., JACS 75 358 (1953). Usually, the oxazolidines and thiazolidines intermediates were pure enough to be used directly without further purification. Aliquots of these solu-tions were then used to prepare the compounds of this invention.
Compounds having a 3-thioacyl substitution may be pre-pared from the corresponding oxygen analogues by methods known in the synthetic organic literature, such as treatment with P2S5 in benzene at reflux.

~07ZS~6 The appropriate intermediate 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 extraction, distillation or crystallization.
The compounds of the present invention and their preparation 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 described herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE I

Prepara~tion of 2-m-nitrophenyl-3-dichloroacetyl oxazolidine.
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 chloride 4.4 g. was added dropwise with stirring to the reaction flask and cooled in a water bath at room temperature. When addition was complete, the mixture was stirred at room ~emperature for about 30 minutes, washed wi-th water, separated and dried over anhydrous magnesium sulfa-te. The solvent was stripped off under vacuum. There was obtained a yield of 8.6 g. o~ the title compound, N30 = 1.5590.

' .
EXAMPLE II
Preparation of 2 ethyl-3-dichloroacetyl-5-~henyl o:~azolidine.
Twenty-one and three tenths (21.3) ml. of a solution contaîning 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 was obtained a yield of 8.7 g. of the title compound, an oil, ~= 1.56~0.

EXAMPLE III

Preparation of 2 2-dimethyl-3-dichloroacetyl-5~phenyl oxazolidine.
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 water bath. The solution was allowed ~o stand af~er 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, mOp. 99.5-130.5C.

~72~6 EXAMPLE IV
._ :
Preparation of 2-~-naphthyl-3-chloroacetyl oxazolidine.

Nineteen and nine tenths (19.9) ml. of a benzene ; solution containing 5 y. of 2-~-naphthyl oxazolidine was combined 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 mixture 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 6.7g. of an oll, the title compound, ND = 1.6030.

EXAMPLE V

Prepara*ion of 2-pheny1-3-ch-loroacety1-4, 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 oxazolidine 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 magnesium sulfate and the solvent stripped. There was obtained a yield of 6.5 g.
of an oil, the title compound, ND0 = 1.5364.

.

~7Z566 EXAMPLF VI

Preparation of 2-phenyl-3-dichloroacetyl thiazolidine.
Five (5) grams of 2-phenyl thiaæolidine 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, ~ = 1.5836.

EXAMPLE VII

Preparation of 2-m-chlorophenyl-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 miYture 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 water9 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, ND = 1.5805.

~C~7;~

EXA~LE VIII

Preparation of 2(2',6 '-dichlorophenyl)3-chloroacetyl thiazolidine.
~enty-threç and five tenths (23.5) ml. of a benzene solution containing 5.9 g. of 2(21,6'-dichlorophenyl) thia-zolidine was combined with 25 ml. of benzene and 2.8 g. of chloro-acetyl chloxide and the mixture stirred in an ice bath, while 2.6 g. of triethylami~e was added dropwise. After standing for about 30 minutes the mixture was washed with water, separated, dried over magnesium sulfate and ~he benzene stripped off under vacuum. Therç was obtained a yield of 8 g of an oil, the title compound, N30 = 1.6041.

EX~MPL~ I~

Preparation of 3(3-bromo~ropionyl~5~phenyl o azolidine.
~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 lS bath, while 5.2 g. of 3-bromopropionyl chloride was added drop-t~ise. After standing for about 30 minutes, the solution ~7as washed with ~ater, separated, dried ovex 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.

7'~566 EXAMPLE X

Preparation of 2,2,'4-trimethyl-'3-d'ich'loroacetyl-5-phenyl oxazo-lidine.

Twenty-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 was obtained 3.9 g. of a solid, the title compound, m.p. 126C.

EXAMPLE XI

Preparation of 2-p-chloropheny1-3-dichloroacetyl oxazolidine.

Twenty-two (22) ml. of a benzene 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, while 4.4 g. of dichloroacetyl chloride was added dropwise. The mixture was allowed to stand for about 30 minutes, washed with water, separated, dried over magnesium sulfate and then stripped. There was obtained a yield of 8.4 g. of an oil, the title compound, ND0 = 1.5668.

~'72566 EXA~IPLE ~II

Pre~aration of 2 5-diDhenyl-3(2~3-dibromopropionyl) 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 dibxomopropionyl chloride was added and the mixture stirred in an ice bath, while 2.1 g. of triethylamine was added dropwise. After standing for about 30 mi~utes, 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. o 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 balance of the specification.

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Other examples o~ compounds falling wi~hin the generic ormu1a presented herein, which are preparable by the aforedes-cribed procedures and ~7hich may be formu~ated into herbicidal compositions and applied as herein illustrated, are:

R ~1 R2 R3 R4 R5 R6 X Y
CH2Cl C6H5 H H H H H O S

CH2Cl C6H5 H H H H H S S

CC13 ~H5 H H H H H S S
CH2Cl ~H3 CH3 H H C6H5 H O S
CHC12 CH3 CH3 H H ~6H5 H O S

CH2Cl CH3 CH3 H H C6H5 H S S
CHC12 CH3 ~H3 H H ~6H5 H S S

CH2BrCHBr m-Cl-C6H4 H M H CH3 H O S
CH2 BrCHBr C6H5 H H H CH3 H S S
CH2BrCHBr CH3 CH3 H H C6H5 H O S
CH2BrCH~r C~3 CH3 H H C6H5 H S S

1~ 7~ ~6 The herbicides indicated in the tables and eisewhere are used at rates ~7hich produce effective control of undesir-able vegetation. The range of rates employed herein produce representative results within the recommended amounts set forth ~y the supplier. Therefore, the weed control in each instance is commercially acceptable ~7ithin the desired or recommended amount~ , It is clear that 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 ~7hich 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 ls, the members of the classes are herbicidally effective against a ~7ide range of plant species ~7ith no discrimination bet~een desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the herein describcd herbicidal compounds to the area or plant ~21-~ 1~7251~;6 locus where control is desired. The compositions as set forth in this invention include those wherein the preferred active herbicidal compound is selected from Eprrc~ S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichloroallyl-diisopropyl thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, 2-chloro-2', 6'-diethyl-N-(methoxymethyl) acetanilide, S-ethyl hexahydro-lH-azepine-1-carbothioate, 2-chloro-N-isopropylacetanilide, 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-isopropyl-amino-s-triazine, 2,4-dichlorophenoxyacetic acid, its esters and salts, and 3-(3~4-dichlorophenyl)-1, 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 effects include all deviations from natural development; for example, killing, retardation, de~oliation, 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.

~ 7;i~566 Evaluation Procedures Flats to be used for growing 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 - LASSO 4E - 6.25 g. of LASSO 4E was diluted in 1000 ml. of water. 100 ml. of this solution was applied using a linear spray table, such that the equivalent of 2 lb/A of LASSO 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 with1% Tween 20 ~ (polyoxyethylene sorbitan 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 Mixes In-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 later to cover the seeds after treatment with the additives. The soil was leveled before planting.
Rows one-quarter inch deep were made lengthwise in each treated flat, preparatory to seeding. After seeding, the flats were sectioned into two equal portions using a wooden barrier and one and one-half ml. of additive stock solution (B) was atomized directly onto the exposed seed and into the furrrow in one-half of the flat. The untreated section of the flat served as an herbicide check and also made it possible to observe any lateral movement of the antidote through the soil. The seeds were covered with the one pint sample of untreated soil which had been removed earlier.

l~Z~i66 The herbicide ~as applied initially on an ind`ividual 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 incorporationg application of the ollowing 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-~ace application, the same stock solution was applied to soil surface after seeding.

The flats were placed on greenhouse benches where temperatures were maintained between 70~90~F. The soil was watered by sprinkling to assure good plant growth. Injury rat-ings were talcen 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.

Some of the candidate antidotes were assayed as anti-dotes to protect various crops against injury from thiocarbamate hexbicides. Selected as representative thiocarbamate herbicides were S-ethyl N,M-dipropylthiocarbamate (EPTC, EPTAM ~ ) and S-propyl N,N-dipropylthiocarbamate (VERNA~ ). Stock solutions of herbicides and antidotes uere prepared and applied in a ~2~

~072566 .

`variety of ways. Soil incorporation, pre-emergence surface application and in-furrow treatment ~7ere employed.

Stock solutions for EPTAM ~ were prepared as follows:
A. 1/2 lb/A 670 mg. of EPTC 6E (75.5% a.i.) ~as diluted with 500 ml, of 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% aui,) was diluted with 100 ml. of deionized water so that 4 ml. applied pre-plant incorporated is equivalent to 3/4 lb/A per flat.
Do 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 with 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 ~he various procedures discussed above. The per cent protection is deter~ined by a comparison with flats not treated ~ith the candidate antidotes of this invention.

~L~7;25~i6 .

TABLE II
Application ~ethod: In-Furrow ~ IF
Pre-Plant Incorporation - PPI (Tank Mix) Pre-Emergence Surface Application - PES
(Tank Mix) Crop Species: Milo - (Sor~hum vulgare) Weed Species: Shatter cane - SC ~Sor~hum bicolor Foxtail - :ft (Sataria virldis) Crabgrass - cG-~b~ arla san~uinalis) Watergrass - WG ~ ) * - % injury ** = ~/O protection PPI (5 lb/A) PES (5 lb/A) CO~ WND 5 lb/A ~ IF (Tank Mix) (Tank ~x) NUMBER Milo SC Milo Ft CG WG Milo Ft CG WG
LASSO 2 lblA 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 0 ?.3 70 70 0 0 0 0 0 0 0 0 . -26-.
.

7;~S616 : TABIE II (continu~d) PPI (5 lb/A) PES (5 lb/A) COMPOUI~ 5 lb/~ - IF(Tank Mi:~) (Tank Mix) NU~ER MiloSC Milo Ft CG WG lo ~t CG T.1G
32 0 0 40 0 0 0 14 ~ 0 0 42 50 . ~ 20 0 0 0 0 0 0 0 48 30 ' 0 0 0 0 0 0 0 0 0 4~ 40 0 0 0 0 0 0 0 0 0 52 ~ 0 40 0 0 ~ 28 0 0 0 0 20 0 0 0 ~8 0 0 0

5~ 3~ 0 0 0 0 0 0 0 0 0 58 60 0 0 0 0 0 0 û O O

63 20 0 80 û O 0 14 0 0 0 0 0 0 0 0 0 0 ~ 0 67 0 0 ~0 0 0 0 28 0 0 0 /~0 0 ~30 0 0 0 65 0 0 0 ~72~ 6 ~ TABLE II (contirlued) , . , PPI (5 lb/A) PES (5 lb/A) COMPOUND S lb/A - IF (Tank Mix) (Tanlc Mix) NU~ER M:i lo SC Mi lo Ft CG I~GMi loFt CG WG
78 5 ~ 16 0 0 ~ 20 0 0 0 79 - 80 ~ 50 0 0 0 50 0 0 0 ~0 20 - 0 0 0 0 16 0 0 0 8~ 60 - 50 0 0 ~ 50 . O 0 O
0 o 20 0 0 0 50 0 0 0 87 50 - 40 0 û 0 6~ 0 0 0 - ~8 0 - 30 0 0 0 15 0 0 0 9~ 40 - 0 ~ 0 0 0 0 0 0 g4 40 - 5û 0 0 0 40 0 0 0 - = not tested, -28~

7 ~S~ 6 Thiocarbamate llerbicide ~lticrop Screen Treated flats were seeded ~ith DeKalb XL-44 corn - (Zea maize), sugarbeets (Beta vulgare), small seeded gray striped sunflower (Helianthus annus), soybeans (GlYcine max) and oilseed rape (Brassica napus~, milo [sorghum~ (sor~um vul~are), ~heat S (Triticum aestlvum) green foxtail (Sataria viridi~, rice (Oryza sativa) and barley (Hordeum ~ . Seeds were then covered with the pint soil sample removed prior to seeding.

The flats were then placed on greenhouse benches ~7here temperatures ~ere maintained between 70-90F~ The soil ~as watered by sprinkling to assure good plant gr~1th.

Injury ratings ~ere ta~en 2 and 4 ~7eeks after the treatments l~ere applied. Soil treated ~ith the herbicide alone at the indicated rate ~as included to provide a basis for deter~
mining the amount of injury reduction provided by the herbicide antidotes. The pex cent protection of various representative crops is reported in Table III The per cent protection is determined by a comparison ~ith flats not treated witl the candidate antidote.

_~9_ ` 1~7;~:566 TABLE III
MVLTICROP SCREEN RESULTS
.
Method of COMPOUND Antidote Herbicide/ Crop Per Cent NUMBER Appli~at.ion Rate lb/A Protected Protection . _ 1 PPI EPTC/1/2 Milo 30 Rice 63 Barley 30 2 PPI EPTC/5 Corn100 (2 wks) 3 PPI EPTC/5 Rice 63 Corn 100 4 PPI EPTC/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~er67 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 Sunflower30 28 PPI EPTC/5 Sunfl.ower 67 31 PPI EPTC/5 Sugarbeet70 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 Sugarbeet80 3~ PPI EPTC/5 Corn 33 ~0~66 , TABLE III (continucd) . .
Method of COMPOUND Antidote Herbicide/ Crop Per Cent NUMBER Application Rate lb/A rotectedProtection 39 PPI EPTC/l/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/l/2 Milo 75 . Wheat 67 Rice 7 Barley 63 EPTC/5 Corn l00 48 PPI EPTC/l/2 Milo 25 51 PPI EPTC/l/2 Barley ~7 53 PPI EPTC/l/2 Barley 50 EPTC/5 Corn l00 54 PPI EPTC/5 Corn 40 57 PPI EPTC/5 Oilseed rape67 PPI EPTC/5 Corn l00 PPI EPTC/5 Corn 50 67 PPI EPTC/l/2 Rice lO0 68 .PPI EPTC/l/2 Rice 100 PPI EPTC/1/2 Wheat 78 Barley ~5 Ric e 100 72 PPI EPTC/l/2 Rice 85 EPTC/l/2 Barley 85 73 PPI EPTC/l/2 Barley 50 PPI EPTC/ll2 Rice 85 Barley 72 EPTC/5 Corn 50 : 76 IF/5 lb/A EPTC/5 Corn l00 77 IF/5 lb/A EPTC/5 Corn 50 ~L~7Z~6 TABLE III (continued~

Method of COMPOUND Antidote Herbicide/ Crop Per Cent NUMBER Application Rate lb/A Protected Protection VERNAM 6EVERNAM/5 Corn 60* Injury Milo 100 Wheat 98 Barley go 2IF/5 lb/A VERNAM/5 Corn 50 3IF/5 lb/A VERNA~I/5 Corn 50 4IF/5 lb/A VERNAM/5 Corn - 100 11IF/5 lbiA V~RNAM/5 Corn 100 VERNAM/3/4 Milo 50 18IF/5 lb/A VERNAM/5 Corn 100 20IF/5 lb/A VERNAM/5 Corn 100 VERNAM/3/4 Milo 60 22IF/5 lb/A VE~NAM/5 Corn 100 YERNAM/3/4 Milo 90 23. IF/S lb/A VERNAM/5 Corn 100 24IF/5 lb/A VERNAM/5 Corn 84 VERNAM/3/4 Milo ~0 26IF/5 lb/A VERNAM/3/4 Barley 67 35IF/5 lb/A VE~NAM/3/4 Corn 67 VEP~AM/3/4 Milo 40 38 .IF/5 lb/A VERNAM/5 Corn 5 39IF/5 lb/A VERNAM/5 Corn 100 VERNAM/3/4 Barl~y 55 40IF/5 lb/A VERNAM/5 Corn 67 47IF/5 lb/A VE~IAM/5 Corn 100 VERNhM/3/4 Mi~o 50 53IF/5 lb/A VE~A~l/5 Corn 100 60IF/5 lb/A VEP~AM/5 Corn 100 78IF/5 lb/A VERNAM/l Milo 50 VEP~AM/5 Corn 22 79IF/5 lb/A VERNAM/l Milo 60 VERNA~l/5 Corn 88 80IFi5 lb/A VER~AM/l Milo 30 VERNAM/5 Corn 88 ~32-

7;~:S~
TABLE III (continuecl) Method of COMPOUND Antidote Herbicide/ Crop Per Cent NUM~ER ~pplication 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 IFt5 lb/A VERNAM/l Barley 55 VERNAM/5 . Corn 78 ~7 IF/5 lb/A VERNAM/l Milo 50 VERNAM/l Barley 45 VERNAM/5 Corn 67 ~8 IF/5 lb/A VERNAM/l Barley 55 IF/5 lb/A VERNAM/l Barley 33 VE~NAM/5 Soybeans 30 91 IF/5 lb/A VERNAM/S Corn 36 94 IF/5 lb/A VERNAM/5 Co~n 23 IF/S lb/A VERNAM/l Wheat ~
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 8705 98 IF/5 lb/A VE~NAM/5 Corn 37.S
99 IF/5 lb/A VERNAM/5 Corn 75 100 IF/5 lb/A VERNAM/l Milo 20 VERN~I/l Barley 22 101 IF/5 lb/A VERNAM/l Milo 20 VERNAM/l Barley 44 : 102 '~F/5 lb/A VERNAM/6** Corn 100 103 IF/5 lb/A ~ERMAM/l Wheat 33 VERNAM/l Barley 33 **Stock solution for VERNAM 6E at 6 lb/A PPI (pre-plant incorporated) 3800 mg/500 ml. wa~er; such that 4 ml. a 6 lb/A PPI

~ 66 The compounds and compositions of this invention were employed in effecti~e 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 ~ollowing 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 th~ above-described compounds. The compositions of herbicide and antidote can be prepared by conventional methods through the thorough mixing and grinding o~ the active 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 p~der, 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, h~Jever, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytoto~ic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The -3~-addition of the antidote compound does not affect the herbicidal activity of the lierbicides.

The amount of antidote compound present can range between about 0.0001 to abou~ 30 par~s 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 (33)

WHAT IS CLAIMED IS:

1. Compounds according to the formula in which X and Y are independently oxygen or sulfur; R is halo-alkyl or chloroalkenyl; R1 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 R6 is hydrogen.

2. Compounds according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is hydrogen, R2 is hydrogen, R3 is hydrogen and R4 is hydrogen.

3. Compounds according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is lower alkyl, R2, R3 and R4 are each hydrogen.

4. Compounds according to Claim 3 in which R is dichloromethyl and R1 is ethyl.

5. Compounds according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is lower alkyl, R2 is lower alkyl, R3 and R4 are each hydrogen.

6. Compounds according to Claim 5 in which R is dichloromethyl, R1 is methyl and R2 is methyl.

7. Compounds according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is lower alkyl, R2 is lower alkyl, R3 is lower alkyl and R4 is hydrogen.

8. Compounds according to Claim 1 in which X is sulfur, Y is oxygen, R is haloalkyl, R1 is phenyl, R2, R3 and R4 are each hydrogen.

9. Compounds according to Claim 1 in which X is oxygen or sulfur, Y is sulfur, R is haloalkyl, R1 is lower alkyl, R2 is lower alkyl, R3 and R4 are each hydrogen.

10. Compounds according to Claim 1 in which X is oxygen or sulfur, Y is sulfur, R is haloalkyl, R1 is hydrogen, R2 is hydrogen, R3 is hydrogen and R4 is hydrogen.

11. Compounds according to Claim 1 in which X is oxygen or sulfur, Y is sulfur, R is haloalkyl, R1 is lower alkyl, R2, R3 and R4 are each hydrogen.

12. Compounds according to Claim 1 in which X is oxygen or sulfur, Y is sulfur, R is haloalkyl, R1 is lower alkyl, R2 is lower alkyl, R3 is lower alkyl and R4 is hydrogen.

13. An herbicidal composition comprising an active herbicidal compound 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 or phenyl;
R2 is hydrogen or lower alkyl; R3 is hydrogen or lower alkyl;
R4 is hydrogen or lower alkyl; R5 is phenyl; and R6 is hydrogen.

14. The herbicidal composition according to Claim 13 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is lower alkyl, R2, R3, R4 and R6 are each hydrogen and R5 is phenyl.

15. The herbicidal composition according to Claim 14 in which R is dichloromethyl and R1 is ethyl.

16. The herbicidal composition according to Claim 13 in which X is oxygen, Y is oxygen, R is haloalkyl, R1 is lower alkyl, R2 is lower alkyl, R3, R4 and R6 are each hydrogen, and R5 is phenyl.

17. The herbicidal composition according to Claim 16 in which R is dichloromethyl, Rl is methyl and R2 is methyl.

18. The herbicidal composition according to Claim 13 in which X is oxygen; Y is oxygen, R is haloalkyl, R5 is phenyl and R1, R2, R3, R4 and R6 are each hydrogen.

19. The herbicidal composition according to Claim 13 in which X is oxygen, Y is oxygen, R is haloalkyl, R5 is phenyl, Rl, R2 and R3 are each lower alkyl and R4 and R6 are each hydrogen.

20. The herbicidal composition according to Claim 13 in which X is sulfur, Y is oxygen, R is haloalkyl, Rl is phenyl, R5 is phenyl and R2, R3, R4 and R6 are each hydrogen.

21. The herbicidal composition according to Claim 13 in which X is oxygen, Y is oxygen, R is haloalkyl, Rl is hydrogen,.
R2 is hydrogen, R3 is hydrogen and R4 is hydrogen.

22. The herbicidal composition according to Claim 13 in which X is oxygen, Y is oxygen, R is haloalkyl, Rl is lower alkyl, R2, R3 and R4 are each hydrogen.

23. The herbicidal composition according to Claim 1 in which X is oxygen, Y is oxygen, R is haloalkyl, Rl is lower alkyl, R2 is lower alkyl, R3 and R4 are each hydrogen.

24. The herbicidal composition according to Claim 13 in which X is oxygen, Y is oxygen, R is haloalkyl, Rl is lower alkyl, R2 is lower alkyl, R3 is lower alkyl and R4 is hydrogen.

25. 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; 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 R6 is hydrogen.

26. The method according to Claim 25 in which X is oxygen, Y is oxygen, R is haloalkyl, Rl is lower alkyl, R2, R3, R4 and R6 are each hydrogen and R5 is phenyl.

27. The method according to Claim 25 in which X is oxygen, Y is oxygen, R is haloalkyl, Rl is lower alkl, R2 is lower alkyl, R3, R4 and R6 are each hydrogen and R5 is phenyl.

28. The method according to Claim 25 in which R is dichloromethyl, Rl is methyl and R2 is methyl.

29. 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; 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 R6 is hydrogen.

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

31. The method according to Claim 30 in which R is dichloromethyl and Rl is ethyl.

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

33. The method according to Claim 32 in which R is dichloromethyl, Rl is methyl and R2 is methyl.