WO1994026108A1

WO1994026108A1 - Safening pyridyloxyphenoxy propionic acid herbicides

Info

Publication number: WO1994026108A1
Application number: PCT/GB1994/000911
Authority: WO
Inventors: Lawrence L. Buren
Original assignee: Zeneca Limited
Priority date: 1993-05-10
Filing date: 1994-04-28
Publication date: 1994-11-24
Also published as: AU6576594A; ZA943205B

Abstract

An herbicidal composition comprising pyridyloxyphenoxy propionic acids, salts and esters thereof according to formula (I) wherein at least one of Y and Z represents a CF3 radical, the other being hydrogen, halogen or CF3 and R is (a) or (b) wherein R1 is hydrogen, C¿1?-C8 alkyl or C3-C6 alkoxyalkyl and M is Na, K, Mg or Ca; and a substantially non-phytotoxic, antidotally-effective amount of an antidote compound selected from the group consisting of amides of haloalkanoic acids, aromatic oxime derivatives, triazole carboxylic acids and derivatives thereof, substituted phenylpyrimidines, 1,8-naphthalic anhydride, 2-(dichloroacetyl)-2-methyl-1,3-dioxolane and 2-(dichloromethyl)-2-thiazoline.

Description

SAFENING PYRIDYLOXYPHENOXY PROPIONIC ACID HERBICIDES

FIELD OF THE INVENTION

This invention pertains to safened herbicidal compo¬ sitions and methods of use and particularly to herbicidal compositions comprising pyridyloxyphenoxy propionic acids, salts and esters thereof with or without co-herbicidal com¬ pounds and amides of dichloroacetic acid.

BACKGROUND OF THE INVENTION

Many herbicides injure crop plants at rates neces¬ sary to control weed growth. However, to be effective an herbicide must cause minimal damage, preferably no damage, to the beneficial crop while maximizing damage to weed species which infest the locus of the crop.

Herbicides have gained a high degree of commercial success because it has been shown that such compounds can increase crop yield and reduce harvesting costs. Some of these herbicides include types such as triazines, halogenated acetanilides, carbamates, thiolcarbamates, benzoic acid derivatives, urea derivatives, imidazolinones and the like.

In some cases, a crop species may be susceptible to the effects of the herbicide. To reserve protection of crop species from herbicidal injury along with the concomitant herbicidal effectiveness on weed species, use of chemical compounds called antidotes or safeners has been employed. See, for example, U.S. Patents 4,021,224 and 4,230,874. The use of safener compounds with herbicidal compounds is a widely accepted agronomic practice. These safener compounds are used on crops including agronomic and vegetable species such as corn, soybean, rice and sorghum.

The pyridyloxyphenoxy propionic acid compounds, their salts and esters, have been found to be very effective herbicides with broad herbicidal activity against a wide variety of plant species. In general, these compounds may be used to control unwanted grass species growing alone, or at suitable rates of application, they may be used to control grass weeds growing among broad-leafed crop plants. The compounds may be either applied to the soil before the emer¬ gence of the unwanted weed species or to the above-ground parts of growing weed species. Active pyridyloxyphenoxy propionic acid compounds are disclosed in U.S. Patent 4,551,170 (Johnston et al. , issued November 5, 1985) and U.S. Patent 4,840,664 (Cartwright, issued June 20, 1989).

The pyridyloxyphenoxy propionic acids and derivative compounds have been found in some instances to adversely effect or interfere with the culture of a variety of crops. Therefore, the effective use of these herbicides for control¬ ling weeds in the presence of such crops is further enhanced by, or may reguire in many instances, the addition of an antidotally-effective amount of a compound which is anti- dotally-effective with pyridyloxyphenoxy propionic acid herbi¬ cides.

Accordingly, it is an object of the invention to provide compositions of the above-mentioned herbicides in combination with antidotes thereof to reduce the injury to crops due to the phytotoxic effect of the herbicides. The invention further provides a composition comprising one or more active ingredients as well as preemergent and postemer- gent methods of controlling undesired plant growth. Such methods comprise applying a herbicidally effective amount of one or more active ingredients to the locus of the undesired plants; the seeds, foliage, rhizomes, stems, roots or other plant parts or soil in which the plants are growing or may be found.

SUMMARY OF THE INVENTION

This invention relates to herbicidal compositions comprising pyridyloxyphenoxy propionic acids, salts and esters thereof according to Formula (I) :

wherein at least one of Y and Z represents a trifluoromethyl radical, the other being hydrogen, halogen or a trifluoro¬ methyl radical and

hydrogen, C.-C- alkyl or C.-C- alkoxyalkyl and M is Na, K, Mg or Ca; and a substantially non-phytotoxic, antidotally-effec- tive amount of an antidote compound selected from the group consisting of amides of haloalkanoic acids, aromatic oxime derivatives, triazole carboxylic acids and derivatives, sub¬ stituted phenylpyrimidines naphthalic anhydrides, 2-(dichloro- acetyl)-2-methyl-l,3-dioxolane and 2-(dichloromethyl)-2- thiazoline and wherein said compound of Formula I being used alone or in combination with other known herbicidal compounds as co-herbicides, preferably a thiolcarba ate of the Formula (II):

O R²

II / CH.(CH„)SC

^{3 2} R³ wherein R 2 and R 3 are independently C-,-C, alkyl and n is 1 or 2.

DETAILED DESCRIPTION OF THE INVENTION

Preferred herbicidal pyridyloxyphenoxy propionic acids and derivative compounds of Formula I are those wherein Z is CF_; Y is hydrogen or chloro and R is — —OR wherein R

0 is hydrogen or C--C. alkyl.

The most preferred species are (R)-2-[4-(5-trifluoro- methyl-2-pyridyloxy)phenoxy] propionic acid (common name "fluazifop-P-butyl") ; (RS)-2-[4-(5-trifluoromethyl-2-pyridyl- oxy)phenoxy] propionic acid (common name "fluazifop-butyl") and (RS)-2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)- phenoxy] propionic acid (common name "haloxyfop", "haloxyfop- methyl" and "haloxyfop-etotyl") .

One group of preferred antidote compounds includes amides of haloalkanoic acids having the generalized formula

₄ιι y

R C—N

\ wherein R 4 i.s a mono- or poly-haloalkyl group. The halogens may be variously chloro, bromo or iodo; chloro is the pre-

4 ferred halogen, and the preferred R group is dichloromethyl,

C1_CH, i.e., the compound are amides of dichloroacetic acid.

In such compounds the nitrogen is further substituted by at least one other functional group or forms a portion of a heterocyclic ring, as will be described below.

In general, antidotes of this type are described in a number of publications such as U.S. Patents 4,021,224; 4,256,481; 4,294,764; EP 0 198 870; EPA 304,409. Preferred antidotes include N, N diallyl-dichloro- acetamide also known as dichlormid and the class of halo¬ alkanoic acid amides according to the general formula

In this formula X is oxygen or sulphur and R and R are hydrogen, C 1-CD- alkyl, haloalkyl, alkoxy, phenyl or when combined with the carbon atom to which they are attached form a C_-C- spirocycloalkyl group; R 7 and R8 are independently hydrogen or C.-C₈ alkyl; R 9 is hydrogen or -C- alkyl and R10 is hydrogen, £■, -£_* alkyl, alkylol, haloalkyl, alkoxy, -C₈ alkoxyalkyl, phenyl, di-(C -C alkyl)aminomethyl in which the alkyl group may be the same or different or a saturated or unsaturated heterocyclic radical having ₅-C₈ ring atoms containing oxygen, sulphur and/or nitrogen atoms.

Preferred antidote compounds according to the above include:

2,2,5-trimethyl-3-(dichloroacetyl) oxazolidine;

2,2-dimethyl-3-(dichloroacetyl) oxazolidine;

2,2-dimethyl-5-n-propyl-3-(dichloroacetyl) oxazoli¬ dine;

2,2-dimethyl-5-phenyl-3-(dichloroacetyl) oxazoli- dine;

2,2-spirocyclohexyl-3-(dichloroacetyl) oxazolidine;

2,2-dimethyl-5-(2-furanyl)-3-(dichloroacetyl) oxazolidine;

2,2-dimethyl-5-(2-thienyl)-3-(dichloroacetyl) oxazolidine; pyridine, 3-[3-(dichloroacetyl)-2,2-dimethyl-5- oxazolidinyl; 2-methyl,2-methylcarboxy ethy1-3-dichloroacetyl thiazolidine;

2,2-dimethyl-3-(dichloroacetyl) thiazolidine; and, 3-(dichloroacetyl)-2,2-spirocyclohexyl oxazolidine.

Another group of dichloroacetamide antidote com¬ pounds include:

4-(dichloroacetyl)3,4-dihydro-3-methyl-2H-2,4- benzoxazine, (also known as CGA-154281) ;

2,2-dichloro-l-(1,2,3,4-tetrahydro-l-methyl-2- isoquinolinyl) ethanone;

N-(dichloroacetyl)-1,2,3,4-tetrahydro quinaldine;

N-(1,3-dioxblan-2-yl-methyl)-N-(2-propenyl)-2,2- dichloroacetamide.

Other preferred antidotes which do have the dichloro¬ acetamide structure include substituted phenylpyridines as disclosed in U.S. Patent 4,493,726. One member of this group is 4,6-dichloro,2-phenylpyridine also known as fenchorum or CGA-123407. Oxime derivatives which are disclosed in U.S. Patent 4,269,775 and 4,070,389. A representative compound of this type is 0-[2-(1,3-dioxolanyl)methyl]-alpha-cyano-ben- zaldoxime. Triazole carboxylic acids and derivatives suitable for use as antidotes are generally disclosed in U.S. Patent 4,199,506. A representative compound of this class is benzyl- 2-chloro-4-trifluoromethyl-5-thiazole carboxyate. Other antidotes include the compounds 2-(dichloromethyl)-2-methyl- 1,3-dioxolane (MG-191) ; 2-(dichloromethyl)-2-triazoline and 1,8-naphthalic anhydride. Preferred benzhydryl derivatives which are disclosed in U.S. Patent 4,964,893. A representa¬ tive compound of this class is methyl-2-(diphenyl-methoxy)- acetate.

The herbicidal and antidotal compounds of this invention are known in the art. The amount of a given anti¬ dote to be utilized in combination with the herbicide of this invention and the manner of its utilization and resulting efficacy can vary according to various parameters such as the particular antidote to be employed, the crop which is to be protected, the amount or rate of herbicide to be applied, and the soil and climatic conditions of the agricultural environ¬ ment in which the mixture is to be applied. The selection of a specific antidote for use in the herbicide composition, the manner in which it is to be applied (e.g., tank mix, infurrow application, seed treatment, etc.), the determination of activity which is non-phytotoxic but antidotally-effective, and the amount necessary to provide this result, can be readily performed utilizing the test procedure in the cited patents such as U.S. Patent 4,021,224, in accordance with common practice in the art.

The term "alkyl" when used alone or in compound form, for example, haloalkyl, includes linear, branched or cyclic radicals having up to six members, the preferred members are methyl and ethyl.

The term "halogen" includes, chloro, bromo, fluoro and iodo radicals.

The term "haloalkyl" includes radicals wherein any one or more of the carbon atoms is substituted with one or more halogen groups. A monohaloalkyl group may have either a bromo, chloro or fluoro atom within the group. Polyhaloalkyl groups may be substituted with two or more of the same halogen groups or have a combination of different halogen groups.

The term "antidote" or "safener" is defined as a compound capable of reducing the phytotoxicity of a herbicide to a crop plant or crop seed.

The term "non-phytotoxic" is defined as an amount of an antidote which causes at most minor injury or no injury to the desired crop species. The term "antidotally-effective" is defined as the amount of antidote required to decrease the extent of injury caused by a herbicide to the desired crop species.

The term "herbicide" is used herein to mean an active ingredient which controls or adversely modifies the growth of plants because of phytotoxic or other effects sub¬ stantial enough to seriously retard the growth of the plant or further to damage the plant sufficiently to kill the plant.

The term "plants" is meant to include germinate seeds, emerging seedlings, rhizomes and established vege¬ tation. The term "locus" may include soil, seeds, seedlings, crop, crop seed and vegetation.

The term "herbicidally-effective" is defined as the amount of herbicide which causes a modifying effect and includes derivations from natural development, killing, regu¬ lation, desiccation, retardation and the like.

Herbicides which may be used as co-herbicides with the pyridyloxyphenoxy propionic acids and derivatives of Formula I include preferably thiocarbamates.

Examples of important thiocarbamate herbicides are the following:

S-ethyl dipropylthiocarbamate (common name "EPTC") ;

S-ethyl diisobutylthiocarbamate (common name "butylate") ;

S-ethyl cyclohexyl(ethyl) thiocarbamate (common name "cycloate") ;

S-propyl dipropylthiocarbamate (common name "vernolate") ;

S-2,3,3,-trichloroallyl-diisopropyl thiocarbamate (common name "triallate") ; and S-propyl butyl(ethyl) thiocarbamate (common name "pebulate") .

Still other classes of herbicidal compounds contem¬ plated for combination with this invention include acetamide herbicides such as 2-chloro-2' ,6^,diethyl-N-(methoxymethyl) acetanilide, (alachlor) , N-(butoxymethyl)-2-chloro-2^/ ,6'- diethylacetanilide (butachlor) , 2-chloro-N(ethoxymethyl)-6'- ethyl-O-acetotoluidide (acetochlor) and 2-chloro-N-(2-ethyl- 6-methylphenyl)-N-(2-methoxy-l-methylethyl) acetamide (metol- achlor) ; and benzoic acid and its salts, esters and amides such as 2-methoxy-3,6-dichloro benzoic acid (dicamba) ;

BIOLOGICAL EVALUATION

The following examples are provided for illustrative purposes only and are not intended to limit the invention in any way. As one skilled in the art is aware, the results obtained in herbicidal screening tests are affected by a number of factors that are not readily controllable. Environ¬ mental conditions, such as amount of sunlight and water, soil type, soil pH, temperature and humidity, are examples of such factors. Other factors which can affect test results are the depth of planting and the application rate of the herbicide, as well as the nature of the crops being tested. Results will also vary from crop to crop and within the crop varieties.

EXAMPLE 1

The herbicide, fluazifop-P-butyl (FUSILADE 2000^®) , and the antidotes 2,2,5-trimethyl-3-(dichloroacetyl) oxazoli¬ dine, 2,2-dimethyl-5-phenyl-3-(dichloroacetyl) oxazolidine 2,2-dimethyl-3-(dichloroacetyl) thiazolidine and naphthalic anhydride were applied preemergence onto soil in flats from a tank-mix solution. The flats were filled with loam soil fortified with 17-17-17 (N-P_0--K-0) on a weight basis. The flats were seeded with four corn cultivars and giant foxtail (Setaria faberi) . The solution of FUSILADE 2000^® was prepared by weighing the appropriate amount and dissolving the chemical in water. The antidote compounds were weighed and dissolved in water, except for naphthalic anhydride which was dissolved in a 50:50 acetone/water solution. The herbicide compound was applied to the appropriate flat followed by the respective antidote compound. The solutions were all applied at 25 gpa and 40 psi using a 80015E nozzle to the soil surface.

The flats were placed in the greenhouse and watered by overhead irrigation for the duration of the study. Green¬ houses were maintained at about 25°C and 20°C day/night temperature. Visual ratings of weed control and corn injury were assessed and recorded 14 and 22 days after treatment (Tables I and II) . Ratings are stated as percentage of corn tolerance and percentage of weed control for giant foxtail. The ratings range from 0 to 100%, where 0 represents no effect on growth or a given parameter (no injury) and 100 represents complete kill or complete effect on a given parameter. The determination of injury included consideration of all para¬ meters such as stunting, chlorosis, necrosis and the like.

Good protection from corn injury resulted with antidote compounds particularly with the higher application rates of FUSILADE 2000^®. The later ratings (Table II) exhibited better protection of corn than the earlier ratings (Table I) . TABLE I

ANTIDOTING OF FUSILADE 2000^® INJURY BY ERADICANE 14 DAYS AFTER TREATMENT

% % Corn

Herbicide + Control Variety Tolerance

Antidote Rate

Treatment (σ/a + lb/a) GF A B C D X

FUSILADE 2000^® 15 + 0 33 13 18 13 13 14

FUSILADE 2000^® 15 + 1.0 30 15 13 18 18 16 + ANTIDOTE 1

FUSILADE 2000^® 15 + 1.0 30 13 13 15 15 14 + ANTIDOTE 2

FUSILADE 2000^® 15 + 1.0 28 10 10 10 13 11 + ANTIDOTE 3

FUSILADE 2000^® 15 + 1.0 30 10 10 10 10 10 + ANTIDOTE 4

FUSILADE 2000^w 30 + 0 85 30 40 45 40 39

FUSILADE 2000^® 30 + 1.0 80 35 30 30 30 31

+ ANTIDOTE 1

FUSILADE 2000^® 30 + 1.0 80 28 33 28 28 29

+ ANTIDOTE 2

FUSILADE 2000^® 30 + 1.0 75 25 28 28 28 27 + ANTIDOTE 3

FUSILADE 2000^® 30 + 1.0 75 25 25 25 28 26 + ANTIDOTE 4

FUSILADE 2000^ 45 + 0 95 50 50 50 50 50

FUSILADE 2000^® 45 + 1.0 88 35 45 35 35 38

+ ANTIDOTE 1

FUSILADE 2000^® 45 + 1.0 85 33 40 40 40 38

+ ANTIDOTE 2

FUSILADE 2000^® 45 + 1.0 88 33 35 35 33 34 + ANTIDOTE 3 TABLE I (continued)

% Corn

Herbicide + Control Variety Tolerance

Antidote Rate

Treatment (a/a + lb/a) GF² B D X

FUSILADE 2000^® 45 + 1.0 88 55 55 48 45 51 + ANTIDOTE 4

FUSILADE 2000^® = (R)-2-[4-(5-trifluoromethyl-2- pyridyloxy) phenoxy]propionic acid (common name

"fluazifop-P-butyl") ANTIDOTE 1 = 2,2,5-trimethy1-3-dichloroacetyl oxazolidine ANTIDOTE 2 = 2,2-dimethyl-5-phenyl-3-dichloroacetyl oxazolidine ANTIDOTE 3 = 2,2 dimethyl-3-dichloroacetyl thiazolidine ANTIDOTE 4 = naphthalic anhydride

2, GF = Giant Foxtail 3, A = Garst 8532 B = Pioneer 3379 C = Pioneer 3475 D = DeKalb 8344 X = Mean value of 4 varieties

TABLE II

ANTIDOTING OF FUSILADE 2000^® INJURY BY ERADICANE 22 DAYS AFTER TREATMENT

% % Corn

Herbicide + Control Variety Tolerance

Antidote Rate

Treatment rσ/a + lb/a) GF² A³ B C D

FUSILADE 2000^® 15 + 0 78 28 65 45 35 43

FUSILADE 2000^® 15 + 1.0 73 25 30 40 33 32

+ ANTIDOTE 1

FUSILADE 2000^® 15 + 1.0 75 18 33 40 33 31

+ ANTIDOTE 2

FUSILADE 2000^® 15 + 1.0 73 13 15 28 20 19 + ANTIDOTE 3

FUSILADE 2000^® 15 + 1.0 75 13 15 23 13 16 + ANTIDOTE 4

FUSILADE 2000^® 30 + 0 96 85 95 94 88 90

FUSILADE 2000^® 30 + 1.0 96 70 78 75 70 73 + ANTIDOTE 1

FUSILADE 2000^® 30 + 1.0 94 68 83 78 73 75 + ANTIDOTE 2

FUSILADE 2000^® 30 + 1.0 93 38 65 58 55 54 + ANTIDOTE 3

FUSILADE 2000^® 30 + 1.0 94 38 70 63 55 56 + ANTIDOTE 4

FUSILADE 2000^® 45 + 0 100 94 99 96 90 95

FUSILADE 2000^® 45 + 1.0 100 63 83 80 75 75 + ANTIDOTE 1

FUSILADE 2000^® 45 + 1.0 97 60 93 85 65 76 + ANTIDOTE 2

FUSILADE 2000^® 45 + 1.0 97 63 83 78 63 71 + ANTIDOTE 3 TABLE II (continued)

% % Corn

Herbicide + Control Variety Tolerance

Antidote Rate

Treatment (a/a + lb/a) GF B D

FUSILADE 2000 ® 45 + 1.0 94 75 80 80 70 76 + ANTIDOTE 4

"fluazifop-P-butyl") ANTIDOTE 1 = 2,2,5-trimethyl-3-dichloroacetyl oxazolidine ANTIDOTE 2 = 2,2-dimethyl-5-phenyl-3-dichloroacetyl oxazolidine ANTIDOTE 3 = 2,2 dimethy1-3-dichloroacetyl thiazolidine ANTIDOTE 4 = naphthalic anhydride

2 GF = Giant Foxtail 3, A = Garst 8532 B = Pioneer 3379 C = Pioneer 3475 D = DeKalb 8344 X = Mean value of 4 varieties

FUSILADE 2000^® injury on corn was reduced by addition of the antidote compounds. As FUSILADE 2000^® appli¬ cation rate was increased, the phytotoxic effect on both corn and giant foxtail increased. Concurrently, the benefit of the addition of antidote compounds was observed on the tested corn varieties by reduced corn phytotoxicity. TABLE III

ANTIDOTING OF FUSILADE 2000^w INJURY BY ERADICANE 8 DAYS AFTER TREATMENT

% % Corn

Herbicide + Control Variety Tolerance Antidote Rate Treatment fmσ/a + lb/a) SC² ^J B C D

FUSILADE 2000^1S 33 + 0 10 + ERADICANE

FUSILADE 2000^® 33 + 6.0 99 + ERADICANE

FUSILADE 2000^® 100 + 0 10 + ERADICANE

FUSILADE 2000" 100 + 6.0 99 + ERADICANE

FUSILADE 2000^w 333 + 0 + ERADICANE

FUSILADE 2000^® 333 + 6.0 99 + ERADICANE

FUSILADE 2000" 1000 + 0 + ERADICANE

FUSILADE 2000^® 1000 + 6.0 99 + ERADICANE

FUSILADE 2000^® 3333 + 0 + ERADICANE

FUSILADE 2000 ® 3333 + 6.0 99 + ERADICANE

FUSILADE 2000" 10000 + 0 13 10 10 + ERADICANE

FUSILADE 2000 ® 10000 + 6.0 99 10 10 10 20 + ERADICANE TABLE III (continued)

1. FUSILADE 2000^® = (R)-2-[4-(5-trifluoromethy1-2- pyridyloxy)phenoxy]propionic acid (common name

"fluazifop-P-butyl") ERADICANE^® = S-ethyl-N,N,dipropylthiocarbamate (EPTC) plus 2,2,5-trimethyl-3-dichloroacetyl)-1,3-oxa- zolidine (Antidote 1) ERADICANE^® contains a 24:1 ratio of EPTC to Antidote 1,

2. SC - Shattercane

3. A = Garst 8532

B = Pioneer 3475 C = Pioneer 3379 D = Bantam T-51

TABLE IV

ANTIDOTING OF FUSILADE 2000^® INJURY BY ERADICANE 21 DAYS AFTER TREATMENT

% % Corn Herbicide + Control Variety Tolerance Antidote Rate _ _ Treatment (ma/a + lb/a) SC k_ B C D

FUSILADE 2000^® 33 + 0 0 0 0 0 0

+ ERADICANE

FUSILADE 2000^® 33 + 6.0 100 0 0 0 0 + ERADICANE

FUSILADE 2000^® 100 + 0 0 0 0 0 0 + ERADICANE

FUSILADE 2000^® 100 + 6 100 0 0 0 0 + ERADICANE

FUSILADE 2000^® 333 + 0 0 0 0 0 2 + ERADICANE

FUSILADE 2000^® 333 + 6.0 100 0 0 0 0 + ERADICANE

FUSILADE 2000^® 1000 + 0 0 0 0 0 0 + ERADICANE

FUSILADE 2000^® 1000 + 6.0 100 0 0 0 0 + ERADICANE

FUSILADE 2000^® 3333 + 0 0 0 0 0 0 + ERADICANE

FUSILADE 2000^® 3333 + 6.0 100 0 0 2 0 + ERADICANE

FUSILADE 2000^® 10000 + 0 83 20 37 33 30 + ERADICANE

FUSILADE 2000^® 10000 + 6.0 100 13 20 20 12 + ERADICANE TABLE IV (continued)

1. FUSILADE 2000^® = (R)-2-[4-(5-trifluoromethy1-2- pyridyloxy)phenoxy]propionic acid (common name "fluazifop-P-butyl")

ERADICANE^® = S-ethyl-N,N,dipropylthiocarbamate (EPTC) plus 2,2,5-trimethy1-3-dichloroacetyl)-1,3-oxa¬ zolidine (Antidote 1)

ERADICANE^ contains a 24:1 ratio of EPTC to Antidote l.

2. SC - Shattercane

3. A = Garst 8532

B = Pioneer 3475 C = Pioneer 3379 D = Bantam T-51

EXAMPLE 2

The experimental conditions were as described in Example 1. However, both FUSILADE 2000^® and ERADICANE^® were applied by tank-mix application to the soil. Corn tolerance was determined both 8 and 21 days after treatment. The results are exhibited in Table III and IV.

The antidote compounds and compositions of the present invention can be used in any convenient form.

The antidote compounds can be formulated into emul- sifiable liquids, emulsifiable concentrates, liquids wettable powders, powders, granules, microcapsules or any other con¬ venient form. In its preferred form, an herbicidal antidote compound in a non-phytotoxic quantity with respect to the crop is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed or applied preemer¬ gence. The soil may be treated with a tank-mix composition including the mixture of herbicide and the antidote in combi¬ nation or the herbicide and antidote can be supplied separ¬ ately or sequentially. Crop seed may be treated or coated with a non-phytotoxic quantity of the antidote compound either prior to seeding or after seeding. The addition of the anti¬ dote compound does not effect the herbicidal activity of the herbicide except to render the activity selective with respect to beneficial crops.

The amount of antidote compound employed in the methods and composition of the invention will vary depending on the particular herbicide with which the antidote is employed, the rate of application of the herbicide, the par¬ ticular crop to be protected, and the manner of application to the plant locus. In each instance the amount of antidote employed is a non-phytotoxic amount. The ratio of herbicidal pyridyloxyphenoxy propionic acids and derivatives thereof to antidote may vary depending upon the crop to be protected, weed to be inhibited and the herbicide and antidote compound used, but normally the herbi¬ cide to antidote ratio will range from about 1:60 to about 60:1, preferably 1:20 to about 20:1 parts by weight may be employed. An even more preferred weight ratio is from 1:5 to 20:l. In general, the effective herbicidal amounts are in the range of about 0.01 to about 12.0 kilograms/hectare (Kg/ha). The preferred range is from 0.01 to about 2.0 Kg/ha.

FORMULATIONS

The compounds and compositions can be formulated in the same manner in which herbicides are generally formulated. The object of the formulation is to apply the compounds and compositions to the locus where control is desired by conven¬ tional method.

Useful formulations of the compounds of this inven¬ tion can be prepared in conventional ways. They include dusts, granules, microcapsules, pellets, solutions, suspen¬ sions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly to the locus. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength composi¬ tions are primarily used as intermediates for further formu¬ lation. The formulations, broadly, contain about 0.1% to 99% by weight of active herbicide and antidote ingredient(s) and optionally at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s) . More specifically, they can contain these ingredients in the following approximate proportions. TABLE VII

Active

Herb. & Ant. Weiσht Percent *

Inσredients Diluentfs) Surfactant (s)

Wettable Powders 20-90 0-74 1-10

Oil Suspensions 3-50 40-95 0-15

Aqueous Suspension 10-50 40-84 1-20

Dusts 1-25 70-99 1-20

Granules and Pellel ; 0.1-95 5-99.9 0-15

Compositions 90-99 0-10 0-2

* Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.

Lower or higher levels of active ingredient can be present depending on the intended use and the physical proper¬ ties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incor¬ poration into the formulation or by tank mixing.

Dusts are free-flowing powder compositions con¬ taining the formulant impregnated on a particulate carrier. The particle size of the carriers is usually in the approxi¬ mate range of 30 to 50 microns. Examples of suitable carriers are talc, bentonite, diatomaceous earth, and pyrophyllite. The composition generally contains up to 50% of formulant. Anti-caking and anti-static agents may also be added. Dusts may be applied by spraying from boom sprayers, hand sprayers or airplanes.

Wettable powders are finely divided compositions comprising a particular carrier impregnated with the formulant and additionally containing one or more surface active agents. The surface active agent promotes rapid dispersion of the powder in an aqueous medium to form stable, sprayable suspen¬ sions. A wide variety of surface active agents can be used, for example, long chain fatty alcohols and alkali metal salts of sulfated fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omega-substituted polyethylene glycols of relatively long chain length. A list of surface active agents suitable for use in agriculture formulations can be found in Wade Van Valkenburg, Pesticide Formulations (Marcel Dekker, Inc., N.Y., 1973) at pages 79-84.

Granules comprise the formulant impregnated on a particulate inert carrier having a particle size of about l to 2 millimeters (mm) in diameter. The granules can be made by spraying a solution of the formulant in a volatile solvent onto the granular carrier. Examples of suitable carriers for the preparation of granules include clay, vermiculate, saw¬ dust, and granular carbon.

Microcapsules and other slow release formulations are advantageous as formulations to deliver and distribute the active ingredients. Microcapsules consist of fully enclosed droplets or granules containing the active materials in which the enclosing material is an inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified period of time. Encapsulated droplets are typically about 1 to 50 microns in diameter. The enclosed liquid typically constitutes about 50 to 95% of the weight of the entire capsule, and may contain an amount of solvent in addition to the active materials. Encap¬ sulated granules are characterized by porous membranes sealing the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 millimeter to l centimeter in diameter. In agricultural usage, the granule size is generally about 1 to 2 millimeters in diameter. Gran¬ ules formed by extrusion, agglomeration or prilling are useful in the present invention as well as materials in their natu¬ rally occurring form. Examples of such carriers are vermi- culite, starch sintered clay granules, kaolin, attapulgite clay, sawdust and granular carbon. Useful encapsulating mate¬ rials include natural and synthetic rubbers, cellulosic materials, styrenebutadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, poly- urethanes and starch xanthates.

Emulsifiable concentrates consist of an oil solution of the formulant plus and emulsifying agent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of oil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surfactants. Other additives, such as suspending agents and thickeners, may be included in the emulsifiable concentrate.

When the formulant is an antidote and herbicide com¬ position, the proportion of antidote compound to herbicide compound generally ranges from approximately 0.001 to 30 parts by weight of the antidote compound per weight of the herbicide compoun .

Formulations generally contain several additives in addition to the formulant and carrier or agent. Among these are inert ingredients, diluent carriers, organic solvents, water, oil and water, water in oil emulsions, carriers of dust and granules, and surface active wetting, dispersing and emul¬ sifying agents. Fertilizers, e.g., ammonium nitrate urea and superphosphate, may also be included. Aids to rooting and growth, e.g., compost, manure, humus and sand, may also be included.

Alternatively, the compounds and compositions of this invention can be applied to a crop by addition to irri¬ gation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. As another alternative, the formulation can be applied to the soil in the form of a solution in a suitable solvent. Solvents frequently used in these formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene and aromatic petroleum fractions rich in methylated naphthalenes. Liquid solutions, like dusts, may be applied by spraying from boom and hand sprayers or airplanes.

Although this invention has been described with respect to specific embodiments, these embodiments are not to be construed as limitations.

Claims

WHAT IS CLAIMED:

1. An herbicidal composition comprising an herbi¬ cidal compound selected from pyridyloxyphenoxy propionic acids, salts and esters thereof according to Formula I:

wherein at least one of Y and Z represents the other being hydrogen, halogen or CF₃ and R

—C— IT wherein R is hydrogen, C.-C_ alkyl or C₃~C₆

0 alkoxyalkyl and M is Na, K, Mg or Ca; and a substantially non-phytotoxic, antidotally-effec- tive amount of an antidote compound selected from the group consisting of amides of haloalkanoic acids, aromatic oxime derivatives, triazole carboxylic acids and derivatives thereof, substituted phenylpyrimidines, 1,8-naphthalic anhydride, 2-(dichloroacetyl)-2-methyl-l,3-dioxolane and

2-(dichloromethyl)-2-thiazoline.

2. An herbicidal composition according to Claim 1 wherein Z is CF 3_ and R is —Cii—OR .

3. An herbicidal composition according to Claim 2 wherein R is hydrogen.

4. An herbicidal composition according to Claim 1 wherein said herbicidal compound is fluazifop-P-butyl or haloxyfop.

5. An herbicidal composition according to Claim 3 wherein Y is halogen.

6. An herbicidal composition according to Claim 3 wherein said antidote compound is an amide of haloalkanoic acid.

7. An herbicidal composition according to Claim 6 wherein said antidote compound is N,N-diallyl dichloroacet- amide.

8. An herbicidal composition according to Claim 6 wherein said antidote is a substituted 1,3 oxazolidinyl or 1,3 thiazolidinyl dichloroacetamide having the formula

wherein X is 0 or S; R and R are hydrogen, C.-C₈ alkyl, haloalkyl, alkoxy, phenyl or when combined together with the carbon atom to which they are attached form a C_-C_ spirocyclo alkyl group; R 7 and R8 are independently hydrogen or C -C_fi alkyl; R 9 i.s hydrogen or .-C₈ alkyl and R10 i.s hydrogen,

C.-C alkyl, alkylol, haloalkyl, alkoxy, C_-C₈ alkoxyalkyl, phenyl, di-(C -C. alkyl)aminomethyl in which the alkyl group may be the same or different or a saturated or unsaturated heterocyclic radical having C₅-C₈ ring atoms containing oxygen, sulphur and/or nitrogen atoms.

9. An herbicidal composition according to Claim 8 wherein said antidote compound is 2,2,5-trimethyl-3-(dichloro¬ acetyl)-l,3-oxazolidine, 3-(dichloroacetyl)-2,2-spirocyclohexyl oxazolidine, 2,2-dimethyl-5-phenyl-3-(dichloroacetyl)-1,3- oxazolidine, 2,2-dimethy1-3-(dichloroacetyl) thiazolidine or 2,2-dimethy1-5-(furanyl)-(3-dichloroacetyl) oxazolidine.

10. An herbicidal composition according to Claim 6 wherein said antidote is 4-(dichloroacetyl)-3,4-dihydro-3- methyl-2H-l,4-benzoxazine.

11. An herbicidal composition according to Claim 1 wherein said herbicidal compound is fluazifop-P-butyl and said antidote is 2,2,5-trimethyl 3-(dichloroacetyl)-oxazolidine.

12. An herbicidal composition according to Claim 1 further comprising at least one additional herbicidal compound as a co-herbicide.

13. An herbicidal composition according to Claim 12 wherein said co-herbicide is a thiocarbamate.

14. An herbicidal composition according to Claim 13 wherein said thiocarbamate is S-ethyl dipropyl thiocarbamate ("EPTC") .

15. An herbicidal composition according to Claim 11 further comprising a thiocarbamate co-herbicide.

16. A method of controlling undesirable vegetation in the presence of a crop comprising applying to the locus of said vegetation or said crop an herbicidally effective amount of an herbicidal compound of the formula

wherein at least one of Y and Z represents a CF radical, the other being hydrogen, halogen or CF and R

—c— o i wherein R¹ is hydrogen, C^Cg alkyl or C₃~C₆

alkoxyalkyl and M is Na, K, Mg or Ca; and a substantially non-phytotoxic, antidotally-effec- tive amount of an antidote compound selected from the group consisting of amides of haloalkanoic acids, aromatic oxime derivatives, triazole carboxylic acids and derivatives thereof, substituted phenylpyrimidines, 1,8-naphthalic anhydride, 2-(dichloroacetyl)-2-methyl-l,3-dioxolane and 2-(dichloromethyl)-2-thiazoline.

17. A method according to Claim 16 wherein Z is

CF ; R is COOH and Y is hydrogen and said antidote is an amide of haloalkanoic acid.

18. A method according to Claim 16 wherein said antidote is 2,2,5-trimethyl-3-(dichloroacetyl) oxazolidine.

19. A method according to Claim 16 wherein the herbicidal compound is fluazifop-P-butyl and said antidote is 2,2,5-trimethyl-3-(dichloroacetyl) oxazolidine.

20. A method according to Claim 19 further com¬ prising an additional herbicidal compound as a co-herbicide and wherein said co-herbicide is a thiocarbamate.

21. A method according to Claim 16 wherein said herbicidal compound and said antidote are first combined into an herbicidal composition and the herbicidal composition is applied to the locus.

22. A method according to Claim 16 wherein said herbicidal compound and said antidote are separately applied to the locus.

23. A method according to Claim 16 wherein the antidote is applied as a seed treatment for the crop seed prior to seeding.