WO1995012977A1

WO1995012977A1 - Improved compositions for nematode control

Info

Publication number: WO1995012977A1
Application number: PCT/US1994/011731
Authority: WO
Inventors: Jeanette Tracy Ahlgrim; James Web Kassebaum; Barry James Shortt; James Michael Warner
Original assignee: Monsanto Company
Priority date: 1993-11-09
Filing date: 1994-10-20
Publication date: 1995-05-18
Also published as: NO961863D0; CA2173160A1; FI961949A; HUT75106A; CZ129196A3; JPH09506085A; EP0723397A1; SK50896A3; BG100581A; HU9601243D0; OA10290A; NO961863L; AU8078594A; BR9408011A; CN1134656A; FI961949A0; ZA948828B

Abstract

The present invention provides novel compositions, unexpectedly advantageous for controlling nematode, insect or acarid infestation of a plant, comprising a quantitatively variable combination of a compound of formula (I) in combination with selected adjuvants from among the typical wetting, dispersing or emulsifying agents, preferably, for example Tergitol®.

Description

IMPROVED COMPOSITIONS FORNEMATODE CONTROL

Field of the invention The present invention relates to unexpectedly improved novel compositions that contain a compound active on foliage in downward systemic control of plant pests, ie parasitic nematodes, insects and acarid infestation. The composition is a compound, particularly as disclosed in U.S. application Serial Number 07/827,231, filed February 3, 1992, which is a continuation-in-part of U.S. Serial number 07/663,218, filed March 1, 1991, incorporated herein by reference therefor, and published in the Patent Cooperation Treaty application Number PCT/US92/1474, in combination with an adjuvant selected from among typical wetting, dispersing or emulsifying agents used in agricultural formulations. The invention relates also to a method for controlling nematodes, insects, and acarids and to the use of the novel compositions. Background of the Invention

It is well-known to use wetting, dispersing or emulsifying agents in fluorinated alkene-containing nematocidal, insecticidal, or acaricidal compositions. For example, the above noted U.S. application discloses use of a blend of the calcium salt of dodecylbenzene sulfonate and nonionic 6- molar ethylene oxide condensation product of nonylphenol, a blend of the calcium salt of dodecylbenzene sulfonate and a nonionic 30-molar ethylene oxide condensation product of nonyl phenol, a nonionic paste of polyalkylene glycol ether, refined xylene solvent and preferably Tween 20. See also the above noted application, U.S. Patent 4,950,666, and U.S. 4,876,285 for other typical surface-active wetting dispersing, and emulsifying agents used in agricultural formulations. For example, such agents include the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylamide sulfonates, including fatty methyltaurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long- chain mercaptans and ethylene oxide. Additionally, U.S. Patent Nos. 5,237,100, 5,236,938, and 5,232,949 disclose nematocides in compositions together with adjuvants including synergists exemplified as piperonyl butoxide or sesamex.

However, there remains a need in the art for nematocide, insecticide, or acaridicide compositions having improved plant uptake, systemic mobility, and desirably low effective levels of use.

Summary of the Invention The present invention provides compositions for controlling nematode, insect or acarid infestation of a plant, comprising a quantitatively variable combination of a compound of the formula I having the structure

Y c - ( C H ₂ ) _n- r z

wherein: n = l, 3, 5, 7, 9, or 11; Q is CH₂NHR_€, CH₂N0₂, CH₂N=CHR2, CH₂N=C=0, CH₂N+R₃R4R₅W-, or (C=0)-Rn;

X, Y, and Z are independently H or F, provided that at least one of X and Y is F, and further provided that when Q is

(c=o)-Rιι ^{each of χ}> ^γ> ^{and z is F};

W" is an agronomically acceptable anion; Jtø is an aromatic group; each of R3, R4, and R5 is independently hydrogen; a lower alkyl group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxy-carbonyl, and phenyl; one of R3, R4, and Rs is hydroxy and the other two are hydrogen; or R3 , R4, and R5 taken together with the nitrogen of Q form a cyclic quaternary ammonium group; BQ is hydrogen; an aliphatic group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; an amino acid amide of Q; (C=0)-R7; Cχ-Cι₂ aliphatic amines, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; C -Cχ aliphatic carboxylic acids, their esters, thiol esters, and amides, all optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; dihydro-3-oxo-pyrazolidinyl; or phenyl or thiophene, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or Rg taken with the nitrogen of Q is guanidine; hydrazine; alkyl or aryl hydrazine, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or an alkyl or aryl sulfonamide, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; R7 is (C=0)-Ri4; Cι-Cι₂ aliphatic group optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; C₂-Cι₂ aliphatic carboxylic acid, esters, thiol esters, or amides thereof, all optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or a N, 0, or S group such that when taken with the carboxamide is a urea, semicarbazide, carbamate, or thiocarbamate group, all optionally substituted with an alkyl or aryl group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxy-carbonyl, and phenyl; Ril is -ORι , -SRι , halogen, -NHOH, or -N ι₂Ri3 wherein each of ι₂ and R13 is independently hydrogen; an aliphatic or an aromatic group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; a Cι-Cι aliphatic a ine, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; a C₂-Cι aliphatic carboxylic acid, esters, amides and salts thereof, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or Rι and R13 taken together with the N of Rn are a protein amino acid or a cyclic group selected from morpholine, piperidine, piperazine, or pyrrolidine, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; Rl4 is OH, alkoxy, NH₂, or NHNH₂; or any agronomically acceptable salt thereof; together with or in combination with an activity enhancing amount of an adjuvant of the

(a) formula II which is alkyl glycosides wherein the alkyl group is a mixture of from about eight to fourteen carbons and the number of glycoside groups present in the formula are from one to about six but preferably one to two, and more preferably APG 325 or APG 225 where the alkyl group is a mixture of from nine to eleven carbons or Atplus 258 or either Rhodonat LMO which is coconut oil based sucroglyceride or Rhodonat MLP 704 which is modified LMO sucroglyceride; (b) formula III which is a quaternized fatty amine ethoxylate wherein the fatty amine is an alkylamine wherein the alkyl group is a mixture of from about eight to twenty carbon atoms, preferably a mixture of from eight to sixteen carbon atoms, more preferably a mixture of from eight to twelve carbon atoms such as is found in cocomethyl ammonium chloride, and most preferably Ethoquad C/12 (the quaternized fatty amine ethoxylate may be represented by the formula

wherein:

R 0 is a mixture of alkyl groups of from about eight to twenty-two carbon atoms, inclusive;

R 1 is an alkyl of from one to four carbons, inclusive; EO is an ethylene oxide monomer wherein x and y are independently a number of from zero to fourteen and are the number of moles of ethoxylation present with the proviso that x and y taken together must be from two to fourteen, preferably two; and Z- is an agronomically acceptable anion); (c) formula IV which is a mixture of a fatty amine ethoxylate and ethoxylated alkylphenol, preferably Improve® (the fatty amine ethoxylate may be represented by the formula

^ (EO)nH

R22 _

²² ^- (EO)mH

wherein: R₂₂ represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive,

EO is an ethyleneoxide monomer; and n and m represent the number of moles of ethoxylation in the formula and are when taken together about from one to fifty, preferably five to fifteen, and the ethoxylated alkylphenol may be represented by the formula

wherein:

R 3 is a mixture of alkyl groups of from zero to twenty carbons, inclusive, preferably from about eight to ten carbons, inclusive, and more preferably nine carbons; EO is an ethylene oxide monomer; and w is the number of moles of ethoxylation in the formula and is from about two to twenty, inclusive, and preferably from six to ten moles, inclusive);

(d) formula V which are ethoxylated acetylated diols, preferably Surfynol 485, and more preferably present in the range from about 0.5% (the ethoxylated acetylated diols may be represented by the formula

wherein: * is a number of carbons to provide a total number of carbons in the chain of from 10 through 12 carbons, inclusive; and EO is an ethylene oxide monomer wherein q and p independently are numbers which represent the number of moles of ethylene oxide monomers in the formula and are when taken together in the range of from about 10 through 30, inclusive, preferably 30);

(e) formula VI which is a secondary alcohol ethoxylate wherein the number of moles of ethylene oxide monomers is from 7 to 15, inclusive, preferably Tergitol® 15-S-7, Tergitol® 15-S-9, or Tergitol® 15-S-12, and more preferably Tergitol® 15-S 12 (the formula VI may be shown as follows:

wherein:

R 4_a represents hydroxy or a Polyoxyethylene group wherein a represents the number of moles of ethylene oxide monomers present in the formula and is from about seven to fifteen, inclusive, preferably about nine to twelve, inclusive, and C* represents the ends of the carbon chain such that altogether the chain is a mixture of carbons having a total of from eleven to fifteen carbons, inclusive, preferably from twelve to fourteen carbons, inclusive);

(f) formula VII which is an alkoxylated fatty amine oxide, preferably Emcol XE 1656, including ethoxylated fatty amine oxide, preferably Flo-Mo 3153 (the alkoxylated fatty amine oxide is represented by the formula

wherein

R 5 represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive;

R' is hydrogen or methyl; and z and zi represent the number of moles of alkoxylation or preferably ethoxylation in the formula and are when taken together about from one to fifty, preferably five to fifteen);

(g) formula VIII which is an alkyl dimethyl amine oxide, preferably Empigen OB (the alkyldimethyl amine oxide may be represented by the formula

O^"

I

wherein

R₂6 represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive;

(h) formula IX which is a fatty alcohol polyglycol ether, preferably Genapol T250 or Neodol (the fatty alcohol polyglycol ether may be represented by the formula

R' I

R₂₁ O(CHCH₂k₂ OH

wherein

R₂₇ represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive; R' represents alkyl of from about one to two carbons, inclusive;

Z₂ represents the number of moles of ethoxylation in the formula and are when taken together about from one to fifty, preferably five to fifteen)

(i) formula X which is a fatty acid esterified polyethoxyether, preferably Kaomul 230 or which is stearic acid polyethoxylate, preferably Simusol M52( the coco esterfied polyethoxyether and stearic acid polyethoxylate may be represented by the formula R₂₈ CO₂ (EO H

wherein

R₂8 represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive;

EO represents ethoxylation in the formula and Z₃ is from one to fifty, preferably five to fifteen); or (j) formula XI which is a quaternary ammonium, preferably

Dodigen 226 (the quaternary ammonium may be represented by the formula

R₂₉ N⁺(CH₃)₂(CH₂(C₆H₅)) Q wherein R₂₉ represents alkyl from C8 to C20, preferably CIO to C16 and Q is an agronomically acceptable anion);

(k) formula XII which is a quaternary ammonium, preferably Dodigen 4022 (the quaternary ammonium may be represented by the formula

R₃₀R₃₁R₃₂N (EO)_n-(PO)_n„ Q^"

wherein R₃₀, R₃₁ and R3₂ are independently alkyls of from one to three carbons which together are from two to seven carbons, preferably all methyl, or one of R30, R3₁, R3₂ is ((EO)_nι(PO)_n2); EO is ethylene oxide; PO is propylene oxide; ni is an integer of one to two; and n₂ is an integer of three to fifteen, preferably six to ten; and Q is an agronomically acceptable anion);

(1) formula XIII which is diamine ethoxylate, preferably

Ethoduomeen (the diamine ethoxylate may be represented by the formula

wherein R₃₃ represents alkyl of from C8 to C20, preferably CIO to C16; and n₃, 11₄, ns represent the number of moles of ethoxylation in the formula and are when taken together about from one to fifty, preferably five to fifteen); (m) formula XIV which is an alkoxylated primary fatty alcohol, preferably Ethylan CPG 945 (the alkoxylated primary fatty alcohol may be represented by the formula

^R— 0 (PO)_n6(EOj_i7

wherein R3₄ represents alkyl of from C8 to C18, preferably C13 to C15;

EO is ethylene oxide; PO represents propylene oxide; ng is an integer of from 6 to 50, preferably from 6 to 9; n₇ is an integer from 4 to 8, preferably 4.5 to 6; and (n) mixtures thereof.

Most preferably the adjuvant is of the formula represented by Improve® or Tergitol® 15-S-12.

More preferably the compound of the formula I is an agronomically acceptable salt of 3,4,4-trifluoro-3-butene-l-amine, preferably the monohydrochloride salt thereof; N-(3,4,4-trifluoro-3- butenyDglycine, preferably the monohydrochloride salt thereof; 2- amino-N-(3,4,4-trifluoro-2-butenyl)propanamide, preferably the monohydrochloride salt thereof; (S)-2-amino-4-(methylthio)-N-(3,4,4- trifluoro-3-butenyl)butanamide, preferably the monohydrochloride salt thereof; 4,4-difluoro-3-buten-l-amine, preferably the monohydrochloride salt thereof; 3,4,4-trifluoro-3-butenoic acid, preferably the sodium salt thereof; a combination of 3,4,4-trifluoro-3- butenoic acid and 3,4,4-trifluoro 3-buten-l-amine in a one to one ratio (1:); (S)-2-amino-3-hydroxy-N-(3,4,4-trifluoro-3-butenyl)butanamide, preferably the monohydrochloride salt thereof; N-(4,4-difluoro-3- butenyDglycine, methyl ester, preferably the monohydrochloride salt thereof; a combination of 3,4,4-trifluoro-2-butenoic acid and 2- propanamine in a one to one ratio (1:1); N-(3,4,4-trifluoro-l-oxo-3- butenyDglycine; 2-[(3,4,4-trifluoro-3-butenyl)amino]acetamide, preferably the monohydrochloride salt thereof; or 3,4,4-trifluoro-3- butenoic acid, 2-aminoethyl ester, preferably the monohydrochloride thereof. More preferably the parasitically active ingredient is 3,4,4- trifluoro-3-butene-l-amine, preferably the monohydrochloride salt thereof; or N-(3,4,4-trifluoro-l-oxo-3-butenyl)glycine and most preferably the active ingredient is N-(3,4,4-trifluoro-l-oxo-3- butenyDglycine. It is surprising that a combination of a compound of the formula I and from about 0.05 to 20 % but less than an amount toxic to an infested plant, preferably about 0.10 to 2 %, of an adjuvant active ingredient of the formula II, III, IV, V, VI or mixtures thereof increases the effectiveness of the compound of formula I against parasitic, particularly nematode infestation when applied to foliage of the infested plants by an unexpected difference compared to the a combination of the compound of formula I with other known surface- active wetting dispersing, and emulsifying agents commonly used in agricultural formulations. An ordinarily skilled artisan would be able to find the % of adjuvant effective for a particular compound of the formula. The percentage expressed is by volume.

Therefore, the present invention is also a method for controlling nematodes, insects, and acarids and for the use of the novel compositions for controlling nematodes, insects, and acarids comprising treating an infestation of nematodes, insects, and acarids either on the foliage or the soil of infested plants with a compound of the formula I together with an activity enhancing amount of an adjuvant of the formula II which is alkyl glycoside, preferably APG® 325 or Atplus 258 in the amount of 0.25-1%; an adjuvant of the formula III which is ethoxylated cocomethyl ammonium chloride, preferably Ethoquad C/12 in the amount of 0.25-

1%; an adjuvant of the formula IV which is fatty amine ethoxylate, preferably Improve® in the amount of 0.25-2%; an adjuvant of the formula V acetylenic diol ethoxylate, preferably Surfynol 485 and preferably in the amount of 0.5-1%; or an adjuvant of the formula VI an ethoxylated secondary alcohol, preferably Tergitol® 15-S-7 in the amount of about 0.5%, Tergitol® 15- S-9 in the amount of about 0.5%, or Tergitol® 15-S-12 in the amount of 0.5%.

Detailed Description of the Invention The novel compositions of the present invention are useful as an unexpectedly effective systemic composition for controlling nematode, insect, and acarid infestation of a plant. These compositions provide a lower effective foliar use rate of compound of formula I while maintaining efficacy in nematode, insect, and acarid disease control. That is, when applied to the foliage or stems of a plant they are able to move through the phloem and xylem of the plant and provide control of nematodes, insects, or acarids at other locations of the plant.

The present methods for systemic control of nematodes, insects, and acarids use unexpectedly enhanced phloem mobile compositions of the present invention. These compositions having a compound of Formula I and a sufficient amount of an adjuvant to unexpectedly provide enhanced effectiveness. It has been proposed the enhanced effectiveness of the present compositions results from improved phloem mobility in order to relocate the compound of Formula I downward in a plant without eliminating the nematode-, insect- or acarid-controlling activity of the compound of Formula I.

To effectively control nematodes or other pests systemically by application to the above-ground surfaces of a plant, the present compositions may improve the active ingredient capability of passing through the cuticle of the foliage or stem of a plant, passing into the phloem, and remaining there long enough to be transported throughout the plant so as to move to untreated areas including the roots. There such a compound of formula I may leak out or in some way contact the pests to such an extent that they are killed or repelled and the damage they would do to the plant is reduced or eliminated. During these steps throughout the plant, a compound of formula I may undergo chemical reactions, such as hydrolysis, or biological reactions, such as enzymatic actions. In addition, the formula I of the present invention may be devised which, when placed on the plant, prior to absorption into the plant, may undergo reactions that result in a compound that is readily absorbable, translocatable, and effective in preventing pest damage. An example of such compounds are those having UV-labile protecting groups which when exposed to natural light undergo reaction and result in active and mobile derivatives of compounds of the formula I. Another example is silylated amine derivatives.

Therefore, what is placed on the foliage or stem of the plant may not be a composition wherein the compound of formula I is actually transported or the compound of formula I that actually controls the pest. Thus, the methods of the present invention provide for compositions that may be transformed through chemical or biological reactions to have proper polarity for systemic activity. Although the methods of the present invention include applying composition to the plant locus, preferably to the foliage, are known, the present compositions are surprising combinations of compounds of the formula I as defined above and selected adjuvants of the formulae II, III, IV, V, VI or mixtures thereof. These combinations are for adjuvants that can not be predicted from among those commonly used in agronomics. Among the compounds of the formula I, in order to control nematodes it is preferred that n is 1 and X, Y, and Z are all F, and QI is then CH₂NH3+ W-, that is, a salt of 3,4,4-trifluoro-3-butene-l-amine. When QI is CH₂NHRβ, Re is preferably an alpha-amino acid linked by a peptide (amide) bond, more preferably a protein amino acid. When QI is (C=0)-Rn, Rn is preferably hydroxyl and the compound is thus 3,4,4-trifluoro-3-butenoic acid or a salt thereof, including a salt formed with 3,4,4-trifluoro-3-butene-l-amine, that is, 3,4,4-trifluoro-3-butene-l-amine 3,4,4- trifluoro-3-butenoate .

W- may be any agronomically acceptable anion. This includes, but is not limited to chloride, iodide, bromide, oxalate, sulfate, phosphate, citrate, acetate, or a fluoroalkene carboxylate, for example, F₂C=CFCH₂COO-.

In addition to the compounds specifically described above, all agronomically acceptable salts of the compounds are within the scope of the present invention. For example, a compound of the present invention having a free amine group may also exist as the protonated form having various anions associated therewith, for example, but not limited to, chloride, bromide, iodide, phosphate, oxalate, sulfate, citrate,and acetate. In addition, a fluoroalkene carboxylate ion, such as F2C=CFCH2COO-, may be the counter-ion.

A compound of the present invention having a carboxylic acid or hydroxyl group may exist as the salt having various cations associated therewith, for example, but not limited to, alkali earth metals, such as sodium, calcium, and potassium; magnesium; or quaternary ammonium ions, such as ammonium, mono-, di-, or trialkylammonium, for example, isopropylammonium, or pyridinium. In addition, a fluoroalkenyl ammonium ion, such as F2C=CFCH2CH2NH3+, may be the cation. All such compounds and others having similar characteristics, being agronomically acceptable, are encompassed by the present invention.

As used herein, the term "halo", "halide", or "halogen" means fluorine, chlorine, iodine, or bromine or cognates thereof.

The term "alkyl" in the definitions of the formula I means straight-chain or branched groups of from one to about seven carbon atoms. The term "lower alkyl" means a such a group containing from one to about four carbon atoms. The term "aliphatic" means saturated or unsaturated, branched or straight-chain, alkyl groups having from one to ten carbon atoms. The term "alkoxy" means a lower alkyl group bonded via an oxygen atom. The term "alkylthio" means a lower alkyl group bonded via a sulfur atom. The term "alkoxycarbonyl" means the lower alkyl ester of a carboxyl group.

The term "aliphatic amine" means an aliphatic group wherein at least one hydrogen is replaced with -NH₂. The term

"aliphatic carboxylic acid, its esters, thiol esters, and amides" means an aliphatic group wherein at least one carbon is a carboxylic group, -COOH, or is the lower alkyl ester, lower alkyl thiol ester, or amide thereof. The term "aromatic group" or "aryl" means phenyl, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl. It should be obvious to one of ordinary skill in the art that heterocycles could also be used for the aromatic group, for example, thiadiazole, pyridine, thiazole, isothiazole, oxazole, pyrazole, triazole, benzothiazole, thiophene, furan, and the like, all of which may also be optionally substituted.

As used herein, the phrase "amino acid amide of Q" (or Qi) means that Rg is an amino acid coupled via a peptide (amide) bond to the N of CH₂NHRg. This amino acid may be a natural, i.e., protein, amino acid or a nonnaturally occurring amino acid. The amino group of the amino acid may be a substituent of any carbon in the group, for example, alpha, beta, or gamma to the carbonyl.

The term "alkyl or aryl hydrazine" means a hydrazine group substituted with a lower alkyl or phenyl group, which in turn may be optionally substituted. The term "alkyl or aryl sulfonamide" means a sulfonamide group substituted with a lower alkyl or phenyl group, which in turn may be optionally substituted. COMPOUND SYNTHESIS Methods of preparation for the compounds of formula I of the present invention are described in PCT application Number PCT/US92/1474 which is incorporated by reference therefor. FORMULATIONS

In normal use, the compositions usually will not be employed free from further admixture or dilution, but ordinarily will be used in a suitable formulated composition compatible with the method of application and comprising an effective amount of the composition. The compositions of this invention may be blended with additional agriculturally acceptable surface-active agents and carriers normally employed for facilitating the dispersion of active ingredients, recognizing the accepted fact that the formulation and mode of application may affect the activity of the composition. The present composition may be applied, for example, as sprays, dusts, or granules, to the area where pest control is desired, the type of application varying with the pest and the environment. Thus, the compositions of this invention may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solution, and the like.

Granules may comprise porous or nonporous particles, such as attapulgite clay or sand, for example, which serve as carriers for the present compounds. The granule particles are relatively large, a diameter of about 400-2500 microns typically. The particles are either impregnated with the composition of the invention from solution or coated with the composition, adhesive sometimes being employed. Granules generally contain 0.05-10%, preferably 0.5-5%, active ingredient.

Dusts are admixtures of the compounds, with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which act as carriers for the compound. These finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation contains 1 part of compound and 99 parts of talc.

The compositions of the present invention may be made into liquid concentrates by dissolution or emulsification in suitable liquids 5 and into solid concentrates by admixture with talc, clays, and other known solid carriers used in the agricultural chemical art. The concentrates are compositions containing about 5-50% active composition of which 98.00-99.25% may be of the formula I and 0.25- 2% may be adjuvant and 95-50% inert material, which includes surface-

10 active dispersing, emulsifying, and wetting agents not within the definition of adjuvant herein, but even higher concentrations of pesticidal active ingredient or adjuvant active ingredient may be employed experimentally. The concentrates are diluted with water or other liquids for practical application as sprays, or with additional

15 solid carrier for use as dusts.

A typical 50% wettable powder formulation would consist of 50.0% (wt/wt) of the composition, 22.0% attapulgite diluent, 22.0% of kaolin diluent, and 6.0% sodium salts of sulfonated Kraft lignin emulsifier.

20 Typical carriers for solid concentrates (also called wettable powders) include fuller's earth, clays, silicas, and other highly absorbent, readily wetted inorganic diluents. A suitable solid concentrate formulation may contain 1.5 parts each of sodium lignosulfonate and sodium lauryl sulfate as additional wetting agents,

25 25 parts of active compound and 72 parts of attapulgite clay.

Manufacturing concentrates are useful for shipping low melting products of this invention. Such concentrates are prepared by melting the low melting solid products together with one percent or more of a solvent to produce a concentrate which does not solidify on

30 cooling to the freezing point of the pure product or below.

Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions readily dispersed in water or other liquid carriers. They may consist entirely of the active compound with a liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively non-volatile organic solvents. For application, these concentrates are dispersed in water or other liquid carriers and normally applied as sprays to areas to be treated.

A typical 50 gram per liter emulsifiable concentrate formulation would consist of 5.9% (wt/wt) of a composition of the invention; as emulsifiers a 1.80% of a blend of the calcium salt of dodecylbenzene sulfonate and nonionic 6-molar ethylene oxide condensation product of nonylphenol, 2.70% of a blend of the calcium salt of dodecylbenzene sulfonate and a nonionic 30-molar ethylene oxide condensation product of nonylphenol, 1.50% of a nonionic paste of polyalkylene glycol ether, and 88.10% refined xylene solvent.

Typical surface-active wetting, dispersing, and emulsifying agents for use in formulations in addition to the adjuvants of the present invention are other agricultural formulations which include, for example,, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. The surface active agent normally comprises about 1-15% by weight of the active ingredient. Thus, in the present compositions the surface active agent in addition to the adjuvant of the present invention composition may reduce this percentage of other surface active agents used to formulate this composition.

Other useful formulations include simple solutions of the invention composition in a solvent in which it is completely soluble at the desired concentration, such as water, acetone, or other organic solvents. The preferred formulation for foliar application is an aqueous solution, more preferably containing a sufficient amount of adjuvant to provide an enhanced parasitically active compound of the formula I as well as provide the desired concentration. However, glycerin and other surface active agents such as T ween® 20, and most preferably 1% glycerin and 0.1% Tween®20 may also be part of the formulation. The compositions may be formulated and applied with suitable pesticidal active ingredients, including insecticides, acaricides, fungicides, plant regulators, herbicides, fertilizers, etc.

METHODS OF USE The present invention provides methods of controlling various pests that prey on agricultural crops, namely nematodes, insects, and acarids. An infestation of a plant by any of these pests may be controlled by applying to the plant locus an effective amount of any of the compounds of the present invention. The application may be made in a variety of ways, including applying the compound or a composition containing it to the soil before or after planting or emergence, to the seed or seed pieces prior to or at planting, and to the plant foliage, stems, or trunks. The treatment may be made more than once during a growing season with one or more days between treatments. An appropriate treatment schedule will depend on the life cycle of the pest to be controlled, ambient temperatures, and moisture levels. In addition the age or size of the plant may influence the treatment schedule.

The methods of the present invention may be carried out on a variety of crops. These include, but are not limited to, fruit and vegetable crops, such as potatoes, sweet potatoes, carrots, tomatoes, grapes, peaches, citrus, bananas, corn, and soybeans; tobacco; and cotton.

Compounds of the present invention may be used to control any of the phytopathogenic nematodes. Insects which may be controlled by the methods of the present invention include, but are not limited to, foliar pests such as green peach aphids, and soil-borne pests such as southern corn rootworm. Acarids which may be controlled by the methods of the present invention include, but are not limited to two spotted spider mites. Although no tests have been specifically performed using the compositions tests conducted with a few of the parasitically active compounds of the present invention revealed no significant level of control of tobacco budworm or Colorado potato beetle. A preferred rate of application of a composition wherein the compound of the formula I is enhanced by combination with from 0.25% to 2% by weight of active adjuvant of the formula II, for example in combination is found to be about 4 or 8 oz/acre to obtain levels of control (80-100%) that are comparable at 16 oz/acre with Triton CS7 for control of root knot nematodes.

TEST EXAMPLES The following methods were used to evaluate adjuvants that are combined with a compound of formula I, specifically, for example, N-(3,4,4-trifluoro-l-oxo-3-butenyl)glycine. A track sprayer is used for foliar applications to approximate application procedures and volumes commonly used in the field ( 25 gal/A). Twenty mis of each test solution is formulated in water, estimating that 10 mis would actually be applied to the 5 plants/treatment (5" or 6" round pots; soil mix: 50% Metromix, 25% fine sand, 25% medium sand , with 136 g Osmocote 14-14-14/ft³; one 3-4 week old Rutger tomato plant/pot). Plants are often transplanted into the 5" or 6" pots; at least one day is allowed between transplanting and treatment. Pots are spaced along the track sprayer's 5 ft long center strip. A single 8001E nozzle tip is placed in a boom directly over the plants and adjusted to 6-9" above the leaf canopy. Pressure is set to lδpsi, resulting in 4.2-4.5 ml/sec release. The track sprayer speed is adjusted to approximately 95 on the dial giving an LCD speed readout of 1.75-1.85. Generally, tests are comprised of 20 treatments plus an uninoculated control treatment. After chemical application, plants are allowed to dry for 2-4 hours and are then inoculated.

4-6 shallow holes are made in proximity to the plant stem using a thick pen, for the addition of Meloidogyne incognita (root knot) nematode eggs. 30 mis of egg suspension (720 eggs/ml, 21,000 eggs/plant) are distributed among all holes in a pot using a large syringe. Plants are randomized before inoculation and then moved to either Greenhouse 16 or 21 for 3-4 weeks incubation. Greenhouse day temperatures are 25-30° C and supplemental overhead light brought day length to 12 hours. At evaluation, foliage is examined for phytotoxic effects and then stems are cut to 1-2 inches above soil level. Excess soil is shaken from root ball and roots are washed free of soil mix using a high pressure water nozzle. Roots are evaluated for severity and quantity of galling visible and each replicate given a disease severity rating 0-100%. This data is entered into a SAS program and results are compared to both the inoculated control and (S)-2-amino-4-(methylthio)-N-(3,4,4-trifluoro-3- butenyDbutanamide, monohydrochloride, with Triton CS7 or (S)-2- amino-4-(methylthio)-N-(3,4,4-trifluoro-3-butenyl)butanamide, monohydrochloride, without adjuvant. Several commercial and experimental adjuvants were tested and are listed below with their active ingredient and percentages identified as follows:

TABLE 1

Adj u va nt %ai Active Ingred ient

NH3SO4 1 00 ammonium sulfate

APG® 225 70 alkyl glycoside

APG® 300 50 alkyl glycoside

APG® 325 70 alkyl glycoside

Arquad T 127W 27 trimethyl tallow ammonium chloride

Buffercide 1 0 phosphoric acid

Cayuse 42.5 phosphate ester of polyglycoethers + 16.5 ammonium salts

Improve® 64 fatty amine ethoxylate + 14 ethoxylated nonylphenol CropOil 17 polyoxyethylated polyol fatty acid ester + polyol fatty acid ester

Ethoquad C/25 100 cocomethyl 15EO ammonium chloride

Ethoquad C/12 100 cocomethyl 2EO ammonium chloride

Emcol® CC9 100 propoxylated quaternary amine

Glycerin 100 glycerin

MON0818 15 polyoxyethylene alkyl (tallow) amine

Nitrogen 28 28% nitrogen nonylphenol 4EO 100 nonylphenol 4EO nonylphenol 6EO 100 nonylphenol 6EO nonylphenol 8EO 100 nonylphenol 8EO nonylphenol 10EO 100 nonylphenol 10EO nonylphenol 12EO 100 nonylphenol 12EO

R-11 90 octyl phenoxy ethanol

Silwet L77 100 organosilicone ethoxylate

Surfynol 465 100 10 mole EO acetylenic diol ethoxylate

Surfynol 485 100 30 mole EO acetylenic diol ethoxylate

Tergitol® 15-S-3 100 C-J1-C-I5 secondary alcohol EO

Tergitol® 15-S-5 100 Cf|-C-|5 secondary alcohol EO

Tergitol® 15-S-7 100 C11-C15 secondary alcohol EO

Tergitol® 15-S-9 100 C11-C15 secondary alcohol EO Tergitol® 15-S-12 1 00 Cι ι-C-|5 secondary alcohol EO

Tergitol® 15-S-15 1 00 C11-C15 secondary alcohol EO

Tween 20 1 00 polyoxyethylene (20) sorbitan monolaurate

Triton® CS-7 60 alkyl aryl polyethoxylate and sodium salt of alkyl sulfonated alkylate

Varion CDG-K 28 lauryl betaine

The following results using the above methods show compounds of the formula I, ie 2-amino-N-(3,4,4-trifiuoro-2-butenyl)propanamide, monohydrochloride salt (denoted as A hereinafter), (S)-2-amino-4- (methylthio)-N-(3,4,4-trifluoro-3-butenyl)butanamide, monohydrochloride salt (denoted as B hereinafter), 3,4,4-trifluoro-3- butenoic acid, sodium salt (denoted as C hereinafter), N-(3,4,4- trifluoro-l-oxo-3-butenyl)glycine(denoted as D hereinafter), 2-[(3,4,4- trifluoro-3-butenyl)amino]acetamide, monohydrochloride salt (denoted as E hereinafter), 3,4,4-trifluoro-3-butenoic acid, 2-aminoethyl ester, monohydrochloride salt (denoted as F hereinafter), thereof that the selected adjuvants of the present invention combination provide an unexpected enhancement of the compound of the formula I. (*FOR I)

B Silwet L77 5 62p 26p

B Silwet L77 5 48p 32p

B Silwet L77 .25

C Tergitol® 15-S-12 • 5(ai)

+glycerin Kai) 91 68 29

p = phytotoxicity noted on foliage Boldface % control indicates statistically significant improvement in disease control compared to I-B, at the same rate, with either no adjuvant or Triton CS7, in the same test. Adj. % is as defined in Table I, except (ai) in the % Adj column means the volume of adjuvant noted in Table I is adjusted for the concentration of adjuvant active ingredient. The surface-active or metting agents identified above are sold under the noted names as follows. APG® is sold by Henkel APG, Arquad is sold by Akzo, Chemical Division, Buffercide is sold by Custom Chemicals. Cayuse® is sold by Wilbur-Ellis Co. Improve® is sold by Dow-Elanco. CropOil is available from various sources. Ethoquad is also sold by Akzo, Chemical Division, Emcol is available from Witco Corp. Organics Div., 28% Nitrogen can be made from usual nitrogen containing compounds. Nonylphenol is sold by, for example, Witco S.A. R-11 is available from Wilbur-Ellis Co. Silwet is from Union Carbide Corp., Special Chemicals Div. Surfynol is a product of Air Products and Chemicals, Inc. Tergitol is also a product of Union Carbide Corp., Industrial Chemicals Div. Tween 20 is from ICI Americas, Inc. Triton® is from Rohm and Haas Co. Varion is from Sherex Chemical Co., Inc.

The following methods are also used to evaluate adjuvants that are combined with a compound of formula I, specifically, for example,

N-(3,4.4-trifluoro-1 -oxo-3-butenyl)glycine, for effectiveness in controlling root knot nematodes (Meloidogyne incognita) on tomato roots when the adjuvant plus compound mixture is applied to the foliage of young plants. Tomato plants (cultivar "Rutgers') were grown one per pot in six cm square plastic pots containing a mixture of equal parts fine sand, coarse sand, silt loam soil, and commercial potting medium. Compound/adjuvant mixtures were prepared by adding the compound to water to achieve final concentrations of 2400, 1200, and 600 ppm, and then adding the adjuvant to the solution to achieve a final concentration of 0.5% volume of adjuvant/volume of water. This single adjuvant concentration was used with all 3 rates of the test compound, unless otherwise specified.

When the tomato plants were 18-21 days old the test solutions were sprayed onto the leaves and stems using a track sprayer which approximates application procedures and volumes used in the field. The track sprayer is calibrated to apply the test solution at a volume of 25 gallons per acre, resulting in application rates of the compound of 8, 4, and 2 ounces active ingredient per acre. Three plants were sprayed for each treatment and then were air dried and kept under fluorescent lights for 15-18 hours prior to inoculation. All plants then were inoculated with mature root knot nematode eggs containing Jl larvae, with 8,000 eggs per plant applied in 5 ml of water onto soil at the stem base. Plants then were incubated in a growth chamber at 27C and 60% RH with all replicate pots randomized throughout the chamber. During the two weeks immediately following application of the test mixtures all plants received sub-irrigation and the foliage was kept dry. Three to 7 days after treatment the plant foliage was examined for symptoms of phytotoxicity and assigned a rating value of 0-3 where 0= no damage, 1= mild spotting or chlorosis, 2= moderate damage but no stunting, and 3= severe damage and stunting. After three weeks incubation as described above the plant roots were washed and nematode disease severity was assessed. Each root system was rated individually and a visual estimate of the percent of the root system damaged by nematode galling was determined and assigned a value of 0, 1, 3, 5, 10, 25, 50, 75 or 100% root damage.

ADJUVANTS TESTED

trade name chemical name concentration

Atplus 258 alkylpolyglucoside 62% a.i.

CS-7 alkyl aryl polyethoxylate and Na salt alkyl sulfonated alkylate 60% a.i.

Dodigen 226 cocoalkyldimethyl benzyl ammonium chloride 50% a.i.

Dodigen 4022

Emcol XE 1656 alkoxylated fatty amine oxide 70% a.i.

Empigen OB alkyldimethyl amine oxide 30% a.i.

Ethylan CPG 945 modified alcohol alkoxylate 100% a.i.

Flo-Mo 3153 ethoxylated fatty amine oxide 70% a.i.

Genapol T250 fatty alcohol polyglycol ether 100% a.i.

Improve fatty amine ethoxylate 64% a.i.

+ ethoxylated nonylphenol 14% a.i.

Kaomul 230 coco esterfied polyethoxyether 100% a.i. piperonyl butoxide 100% a.i.

Rhodonat LMO coconut oil based sucroglyceride 100% a.i.

Rhodonat MLP704 modified LMO sucroglyceride 100% a.i.

Simusol M52 stearic acid polyethoxylated 100% a.i.

Ethoduomeen ethoxylated alkyl amine 100% a.i.

Ethomeen C-15 ethoxylated alkyl amine diamine 100% a.i.

MANUFACTURERS OF ADJUVANTS TESTED

Atplus 258 Imperial Chemical Industries

Triton CS-7 Rohm & Haas Co.

Dodigen 226 Hoechst AG

Dodigen 4022 Hoechst AG

Emcol XE 1656 Witco Corp.

Empigen OB Albright & Wilsons Ethylan CPG 94 Harcros Chemicals Inc. Flo-Mo 3153 Witco Corp. Genapol T250 Hoechst AG Improve DowElanco Kaomul 230 KAO Spain piperonyl butoxide Fluka Chemika Rhodonat LMO Rhone-Poulenc Rhodonat MLP704 Rhone-Poulenc Simusol M52 Seppic France Ethoduomeen AKZO Corp. Ethomeen C-15 ALZO Corp.

Table 3. Mean percent root damage due to nematode galling (% disease), the standard deviation of that mean (std dev), the % control of root damage (% control), and foliar phytotoxicity rating (0=no phyto, 3=severe phyto) after treatment of tomato plants with (MON 45700) mixed with the indicated adjuvants.

Adjuvant % disease phytotox

D average std dev % control average

(0.5% v/v unless noted) qai/ha

CS-7 560 33.33 11.79 50.00 1.67

280 66.67 11.79 0.00 1.00

Improve 560 20.00 7.07 70.00 2.00

280 28.33 16.50 57.50 1.00

140 58.33 11.79 12.50 0.67

Witco C5867 560 20.00 7.07 70.00 1.33

280 50.00 20.41 25.00 0.67

140 50.00 0.00 25.00 1.33

Dodigen 226 560 20.00 7.07 70.00 2.67

280 41.67 11.79 37.50 2.67

140 33.33 11.79 50.00 2.33

Neodol 25-9 560 20.00 7.07 70.00 1.67

280 58.33 11.79 12.50 1.33

140 58.33 11.79 12.50 0.67

Stepwet DF-90 560 20.00 7.07 70.00 1.67

280 41.67 11.79 37.50 0.33

140 58.33 11.79 12.50 0.33

Emcol XE 1656 560 41.67 11.79 37.50 1.00

280 58.33 11.79 12.50 1.67

140 66.67 11.79 0.00 1.00

Simusol M52 560 41.67 11.79 37.50 0.67

280 66.67 11.79 0.00 0.33

140 66.67 11.79 0.00 0.67

CS-7 560 15.00 7.07 77.50 2.00

280 33.33 11.79 50.00 0.67

Improve 560 6.00 2.94 91.00 2.67

280 15.00 7.07 77.50 2.33

140 41.67 11.79 37.50 1.67

Ethylan CPG945 560 13.33 8.50 80.00 3.00

280 41.67 11.79 37.50 2.33

140 58.33 11.79 12.50 2.00

Rhodonat MLP704 560 8.33 2.36 87.50 2.67

280 33.33 11.79 50.00 1.33

140 58.33 11.79 12.50 0.67 Adjuvant % disease phytotox

D average std dev % control average

(0.5% v/v unless noted) αai/ha

Rhodonat LMO 560 33.33 11.79 50.00 1.33

280 58.33 11.79 12.50 0.67

140 66.67 11.79 0.00 0.33

Kaomul 230 560 15.00 7.07 77.50 1.67

280 33.33 11.79 50.00 1.33

140 62.50 12.50 6.25 0.67

Genapol T 560 5.00 0.00 92.50 2.67

280 15.00 7.07 77.50 1.67

140 41.67 11.79 37.50 0.67

Atplus 258 560 6.00 2.94 91.00 1.67

280 10.00 0.00 85.00 0.67

140 41.67 11.79 37.50 0.67

CS-7 560 4.33 0.94 93.50 1.00

280 15.00 7.07 77.50 0.67

Improve 560 1.67 0.94 97.50 1.67

280 6.00 2.94 91.00 2.00

140 28.33 16.50 57.50 1.67

Flomo 3153 560 2.00 2.16 97.00 2.00

280 6.67 2.36 90.00 0.67

140 33.33 11.79 50.00 0.00

Ethomeen C150.3% + 560 0.33 0.47 99.50 3.00

Tergitol 15S90.2%

280 3.33 2.36 95.00 2.67

140 41.67 11.79 37.50 2.00

Ethoduomeen T25 560 1.00 0.00 98.50 2.00

280 8.33 2.36 87.50 2.33

140 41.67 11.79 37.50 1.33

Ethomeen C150.18% + 560 11.67 9.43 82.50 2.67

Tergitol 15S120.12% +

Tergitol 15S90.2%

280 0.00 0.00 100.00 3.00

140 0.00 0.00 100.00 3.00

Tergitol 15S9 280 0.00 0.00 100.00 3.00

140 0.00 0.00 100.00 3.00

Empigen OB 560 3.00 0.00 95.50 2.67

280 11.67 10.27 82.50 2.67

140 33.33 11.79 50.00 1.67

CS-7 560 3.67 1.89 92.67 1.67

280 8.33 2.36 83.33 1.33

Claims

1. A composition comprising a combination of a compound of the formula

(I)

\

/ - C - ( C H ₂ ) _n -

I wherein: n = 1, 3, 5, 7, 9, or 11;

Q is CH₂NHR6, CH₂N0_2> CH₂N=CHR₂, CH₂N=C=0, CH₂N⁺R₃R4R₅W-, or (C=0)-Rn; X, Y, and Z are independently H or F, provided that at least one of X and Y is F, and further provided that when Q is (C=0)-Ru each of X, Y, and Z is F; W" is an agronomically acceptable anion; R is an aromatic group; each of 3 , R4, and R5 is independently hydrogen; a lower alkyl group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxy¬ carbonyl, and phenyl; one of R3 , R4, and R5 is hydroxy and the other two are hydrogen; or R3, R4, and R5 taken together with the nitrogen of Q form a cyclic quaternary ammonium group; Rg is hydrogen; an aliphatic group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; an amino acid amide of Q; (C=0)-R7; Cj-Cι aliphatic amines, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; C₂- Cχ₂ aliphatic carboxylic acids, their esters, thiol esters, and amides, all optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; dihydro-3-oxo-pyrazolidinyl; or phenyl or thiophene, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or Rg taken with the nitrogen of Q is guanidine; hydrazine; alkyl or aryl hydrazine, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or an alkyl or aryl sulfonamide, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; R7 is

Cj-C 2 aliphatic group optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; C₂- Cj₂ aliphatic carboxylic acid, esters, thiol esters, or amides thereof, all optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or a N, 0, or S group such that when taken with the carboxamide is a urea, semicarbazide, carbamate, or thiocarbamate group, all optionally substituted with an alkyl or aryl group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxy-carbonyl, and phenyl; R_n is -OR₁₂, -SR₁₂, halogen, -NHOH, or -NR₁₂Ri3; each of Rχ₂ and R13 is independently hydrogen; an aliphatic or an aromatic group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; a Cχ-Cι₂ aliphatic amine, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; a C₂-Cι aliphatic carboxylic acid, esters, amides and salts thereof, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or Rχ₂ and R13 taken together with the N of R ι are a protein amino acid or a cyclic group selected from morpholine, piperidine, piperazine, or pyrrolidine, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; Rl4 is OH, alkoxy, NH₂, or NHNH₂; or any agronomically acceptable salt thereof; together with or in combination with (a) formula II which is alkyl glycosides wherein the alkyl group is a mixture of from about eight to about fourteen carbons and the number of glycoside groups present in the formula are from one to about six;

(b) formula III which is a quaternized fatty amine ethoxylate wherein the fatty amine is an alkylamine wherein the alkyl group is a mixture of from about eight to about twenty carbon atoms, inclusive, and the ethoxylate is an ethylene oxide monomer from about two to about fourteen moles of ethoxylation;

(c) formula IV which is a mixture of (i) a fatty amine ethoxylate wherein the fatty amine is an alkylamine wherein the alkyl group is a mixture of from about six to about thirty carbon atoms, inclusive, and the ethoxylate is an ethylene oxide monomer of from one to about fifty moles of ethoxylation and (ii) ethoxylated alkylphenol wherein the alkyl is of from zero to about twenty carbons, inclusive, the ethoxylate is an ethylene oxide monomer of from about two to about twenty moles of ethoxylation; (d) formula V which is ethoxylated acetylated diols wherein the number of carbons in the acetylated chain is of from ten to twelve carbon atoms, inclusive, and the ethoxylate is an ethylene oxide monomer of from ten to about thirty moles of ethoxylation;

(e) formula VI which is a secondary alcohol or ethoxylate wherein the ethoxylate is of from seven to fifteen, inclusive, of an ethylene oxide monomer and the alkyl of the secondary alcohol or ethoxylate is of from about seven to about fifteen, inclusive;

(f) formula VII which is an alkoxylated fatty amine oxide wherein thealkyls are of from about six to thirty carbons, inclusive; and the number of moles of alkoxylation are when taken together about from one to fifty;

(g) formula VIII which is an alkyldimethyl amine oxide wherein the alkyls are of from about six to thirty carbons;

(h) formula IX which is a fatty alcohol polyglycol ether wherein the fatty alcohol represents a mixture of alkyls of from about six to thirty carbons, inclusive; and the number of moles of ethoxylation are when taken together about from one to fifty;

(i) formula X which is a coco esterified polyethoxyether wherein the coco ester represents a mixture of alkyls of from about six to thirty carbons, inclusive; and the ethoxylation is from one to fifty; (j) formula XI which is a quaternary ammonium including an alkyl of from C8 to C20 and an agronomically acceptable anion;

(k) formula XII which is a quaternary ammonium having groups which are independently alkyl of from one to three carbons and together are from two to seven carbons; and of from three to fifteen ethylene oxide and propylene oxide groups and an agronomically acceptable anion;

(1) formula XIII which is diamine ethoxylate with an alkyl of from C8 to C20 and ethoxylation of from about from one to fifty;

(m) formula XIV which is an alkoxylated primary fatty alcohol with an alkyl of from C13 to C18 and of from 6 to 50 propylene oxide groups; and

(n) mixtures thereof. 2. A composition of claim 1 wherein the compound of the formula I is an agronomically acceptable salt of 3,4,4-trifluoro-3-butene-l-amine, or the monohydrochloride salt thereof; N-(3,4,4-trifluoro-3-butenyl)glycine or the monohydrochloride salt thereof; 2-amino-N-(3,4,4-trifluoro-2- butenyDpropanamide or the monohydrochloride salt thereof; (S)-2- amino-4-(methylthio)-N-(3,4,4-trifluoro-3-butenyl)butanamide or the monohydrochloride salt thereof; 4,4-difluoro-3-buten-l-amine or the monohydrochloride salt thereof; 3,4,4-trifluoro-3-butenoic acid or the sodium salt thereof; a combination of 3,4,4-trifluoro-3-butenoic acid and 3,4,4-trifluoro-3-buten-l-amine in a one to one ratio (1:); (S)-2-amino-3- hydroxy-N-(3,4,4-trifluoro-3-butenyl)butanamide or the monohydrochloride salt thereof; N-(4,4-difluoro-3-butenyl)glycine, methyl ester, or the monohydrochloride salt thereof; a combination of 3,4,4-trifluoro-2-butenoic acid and 2-propanamine in a one to one ratio (l:l); N-(3,4,4-trifluoro-l-oxo-3-butenyl)glycine; 2-[(3,4,4-trifluoro-3- butenyl)amino]acetamide or the monohydrochloride salt thereof; or 3,4,4-trifluoro-3-butenoic acid,

2-aminoethyl ester or the monohydrochloride thereof.

3. A composition of Claim 1 wherein the adjuvant is

(a) the alkyl glycosides of the formula II wherein the alkyl group is a mixture of from about nine to eleven carbons, inclusive, and the number of glycoside groups present in the formula are from one to two;

(b) the quaternized fatty amine ethoxylate of the formula III wherein the alkyl group of the fatty amine is a mixture of from eight to sixteen carbon atoms and the number of moles of ethoxylates is two;

(c) the mixture of the formula IV is (i) the fatty amine ethoxylate of the formula

^ (EO)nH

²² (EO)mH

wherein: R₂₂ represents a mixture of alkyls of from about twelve to twenty carbons, inclusive; EO is an ethylene oxide monomer and n and m represent the number of moles of ethoxylation in the formula and are when taken together about from five to fifteen, and (ii) the ethoxylated alkylphenol is the formula

wherein: R₂3 is a mixture of alkyl groups of from about eight to ten carbons;

EO is the ethylene oxide monomer and w is the number of moles of ethoxylation in the formula and is from about six to ten moles; (d) the ethoxylated acetylated diols of the formula V is of formula

wherein:

* is a number of carbons to provide a total number of carbons in the chain of from 10 through 12 carbons, inclusive; EO is ethylene oxide monomer wherein q and p represent the number of moles of ethoxylates in the formula and are when taken together 30; (e) the secondary alcohol ethoxylate of the formula VI is wherein:

R₂4_arepresents hydroxy or an ethylene oxide monomer wherein a represents the number of moles of ethoxylate present in the. formula and is from nine to twelve, inclusive, and C* represents the ends of the carbon chain such that altogether the chain is a mixture of carbons having a total of from twelve to fourteen carbons, inclusive;

(f) formula VII which is an alkoxylated fatty amine oxide, preferably Emcol XE 1656, including ethoxylated fatty amine oxide, preferably Flo- Mo 3153 (the alkoxylated fatty amine oxide is represented by the formula

wherein

R₂5 represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive;

R' is hydrogen or methyl; and z and zi represent the number of moles of alkoxylation or preferably ethoxylation in the formula and are when taken together about from one to fifty, preferably five to fifteen); (g) formula VIII which is an alkyldimethyl amine oxide, preferably Empigen OB (the alkyldimethyl amine oxide may be represented by the formula

O^"

wherein R₂₆ represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive;

R"

R₂₁ O(CHCH₂ OH

wherein

R₂₇ represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons, inclusive; R' is of hydrogen or alkyl of from one to two carbons; Z₂ represents the number of moles of ethoxylation in the formula and are when taken together about from one to fifty, preferably five to fifteen)

(i) formula X which is a fatty acid esterified polyethoxyether, preferably Kaomul 230 or which is stearic acid polyethoxylate, preferably Simusol M52( the coco esterfied polyethoxyether and stearic acid polyethoxylate may be represented by the formula

R₂₈ CO₂ — (EO) H

wherein

R₂₈ represents a mixture of alkyls of from about twelve to twenty carbons, inclusive; EO represents ethoxylation in the formula and Z₃ is from five to fifteen;

(j) formula XI which is a quaternary ammoniummay be represented by the formula

R₂₉ N⁺(CH₃)₂(CH₂(C₆H₅)) Q^" wherein R₂₉ represents alkyl from CIO to C16 and Q is an agronomically acceptable anion;

(k) formula XII which is a quaternary ammonium represented by the formula

R₃₀R₃₁R₃₂N⁺(EO)_nι(PO)_n2 Q-

wherein R30, R3₁ and R3₂ are all methyl or one of R30, R3₁, R3₂ is ((EO)_nι(PO)n2); EO is ethylene oxide; PO is propylene oxide; ni is an integer of one to two; and n₂ is an integer of about six to ten; and Q is an agronomically acceptable anion);

(1) formula XIII which is diamine ethoxylaterepresented by the formula

wherein R₃₃ represents alkyl of from about CIO to C16; and n₃, 11₄, ns represent the number of moles of ethoxylation in the formula and are when taken together about from five to fifteen;

(m) formula XI which is an alkoxylated primary fatty alcohol, represented by the formula wherein R₃₄ represents alkyl of from about C13 to C15; EO is ethylene oxide; PO represents propylene oxide; nβ is an integer of from about 6 to 9; n₇ is an integer from about 4.5 to 6; and (j) mixtures thereof.

4. A composition of Claim 2 wherein the formula is

(a) the alkyl glycosides which is APG 325 where the number of glycoside groups is one to two and the alkyl group is a mixture of from nine to eleven carbons; (b) the quaternized fatty amine ethoxylate is cocomethyl ammonium chloride or Ethoquad C/12;

(c) a mixture which is Improve®;

(e) the secondary alcohol ethoxylate is Tergitol 15-S-9, or Tergitol 15- S-12; or (f) mixtures thereof;

5. A composition of claim 4 wherein the adujuvant is the alkyl glycosides of the formula II wherein the alkyl group is a mixture of from about nine to eleven carbons, inclusive, and the number of glycoside groups present in the formula are from one to two.

6. A composition of claim 5 wherein the formula I is N-(3,4,4-trifluoro- 3-butenyl)glycine or the monohydrochloride salt thereof.

7. A composition of claim 5 wherein the formula I is 3,4,4-trifluoro-3- butene-1-amine, or the monohydrochloride salt thereof.

8. A composition for controlling nematode, insect, or acarid infestation of a plant comprising an effective amount of a composition of Claim 1 in an agronomically acceptable carrier.

9. A composition for controlling nematode, insect, or acarid infestation of a plant comprising an effective amount of a composition of claim 5 in an agronomically acceptable carrier.

10. A composition for controlling nematode, insect, or acarid infestation of a plant comprising an effective amount of a composition of claim 6 in an agronomically acceptable carrier.

11. A composition for controlling nematode, insect, or acarid infestation of a plant comprising an effective amount of a composition of claim 7 in an agronomically acceptable carrier.

12. A method of controlling nematode, insect, or acarid infestation of a plant, comprising applying to a plant locus an effective amount of a composition of claim 1.

13. A method of systemically controlling nematode, insect or acarid infestation of a plant, comprising applying to a plant locus an effective amount of a composition of claim 9 that has or is transformed after application to have polarity providing phloem mobility without reducing nematode-controlling effectiveness.

14. A method of claim 12 wherein the compound of the formula I in the composition is N-(3,4,4-trifluoro-3-butenyl)glycine or the monohydrochloride salt thereof.

15. A method of claim 12 wherein the compound of the formula I in the composition is 3,4,4-trifluoro-3-butene-l-amine, or the monohydrochloride salt thereof.