SK50896A3 - Compositions for nematode control - Google Patents

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 Tergitol3.

Description

Technical field

The present invention relates to unexpectedly improved novel compositions comprising a compound acting on foliage in descending systemic control of plant pests, i. parasitic nematodes, insects and mites. The composition is a compound, particularly as disclosed in U.S. Patent Application Ser. No. 07 / 827,231, filed February 3, 1992, which is a continuation of application no. No. 07 / 663,218, filed Mar. 1, 1991, incorporated herein by reference and published in PCT / US92 / 1474, in combination with an adjuvant selected from conventional humectants, dispersing or emulsifying agents used in agricultural compositions. The invention also relates to a method for destroying nematodes, insects and mites and to the use of novel formulations.

BACKGROUND OF THE INVENTION

The use of wetting, dispersing and emulsifying agents in fluorine-containing alkene formulations is well known. For example, the aforementioned U.S. patent application discloses mixtures of calcium reindeer dodecylbenzenesulfonate with a nonionic six-mole condensation product of ethylene oxide and nonylphenol, further mixtures of calcium reindeer dodecylbenzenesulfonate with a non-ionic thirty-mole condensation product of a polyolefin, and nonylphenol xylene ester.

See also the aforementioned patent application, U.S. Patent 4,950,666 and U.S. Pat. No. 4,876,285 for other typical surface-active humectants, dispersing and emulsifying agents used in agricultural preparations. Such agents are, for example, alkyl and alkylarylsulfonates and sulfates and their sodium salts; alkyl amide sulfonates including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; poly ethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; polyhydric alcohol fatty acid esters and ethylene oxide addition products of such esters; and addition products of long chain mercaptans and ethylene oxides.

Next, U.S. Pat. U.S. Pat. Nos. 5,237,100, 5,236,938 and 5,232,949 disclose nematicides (nematode killers) in admixture blends with adjuvants including co-agents such as piperonyl butoxide or sesamex.

Nevertheless, there is a continuing need for nematicides, insecticides and acaricides (mite control agents) that are better accepted by plants, have better systemic mobility, and preferably low effective doses of use.

SUMMARY OF THE INVENTION

The present invention provides compositions for the control of nematode, insect or mite infestations which consist of a quantitatively variable combination of compounds of formula I having the structure \

C = C- (CH ₂ ) _n -QY 1 z wherein: n = 1, 3, 5, 7, 9 or 11;

Q is CH ₃ NH 6, CH ₂ NO ₂ , CH ₂ N = CHR ₂ , CH ₂ N = C = O, CH ₂ N ⁺ R ₃ R ₄ R ₅ W- or (C = O) -R 8;

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) -R 11, then each X, Y and Z is F;

W 'is an agriculturally acceptable anion;

R ₂ is an aromatic group;

each of R ₃ , R ₅ , and R ₅ is independently hydrogen; a lower alkyl group optionally substituted by at least one group selected from hydroxy-, alkoxy-, halogen-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl- and phenyl groups; one of R ₃ , R 4 and R 5 is hydroxyl and the other two are hydrogen; or R _3, R 4 and R _s together with the nitrogen of Q form a cyclic quaternary group;

R 6 is hydrogen; an aliphatic group, optionally substituted with at least one group selected from hydroxy-, alkoxy-, halogen-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl-, and phenyl-; amino acid Q amide; (C = O) R ?; C 1 -C ₁₂ aliphatic amines, optionally substituted with at least one of the groups

- 3 hydroxy-, alkoxy-, halogen-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl- and phenyl-; C ₂ -C ₁₂ aliphatic carboxylic acids, their esters, thioesters and amides, all optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl- and phenyl-; dihydro-3-oxo-pyrazolidinyl; or phenyl or thiophene, optionally substituted with at least one of hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl;

or R 6 together with the nitrogen of Q is guanidine;

hydrazine; alkyl or arylhydrazine, optionally substituted with at least one group selected from hydroxy-, alkoxy-, halogen-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl-, and phenyl-; or an alkyl or arylsulfonamide, optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl;

R? is (C = O) -R 14, C 1 -C ₁₂ aliphatic, optionally substituted with at least one group selected from hydroxy-, alkoxy-, halogen-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl- and phenyl-; C ₂ -C ₁₂ aliphatic carboxylic acid, esters, thioesters or amides thereof, all optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl - and phenyl-; or an N, O or S group such that when taken together with the carboxamide is a urea, semicarbazide, carbamate or thiocarbamate group, all optionally substituted with at least one group selected from hydroxy-, alkoxy-, halogen-, nitro-, amino- , thio-, alkylthio-, carboxy-, alkoxycarbonyl- and phenyl-;

R is -OR, -SR _2, halogen, -NHOH, or _-NR] Ri3 _2, wherein each of _{R] 2} and R ₃ are each independently hydrogen; an aliphatic or aromatic group optionally substituted by at least one group selected from hydroxy-, alkoxy-, halogen-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl-, and phenyl-; C 1 -C ₁₂ aliphatic amine optionally substituted with at least one group selected from hydroxy-, alkoxy-, halogen-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl-, and phenyl-; A C ₂ -C ₁₂ aliphatic carboxylic acid, esters, thioesters or amides thereof, all optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl - and phenyl-;

- 4 or Ri? and R _3, together with the N of R is 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, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl;

R 14 is OH, alkoxy, NH ₂ or NHNH ₂ ;

or any agriculturally acceptable salt thereof;

together with or in combination with an activity-enhancing adjuvant according to (a) of formula Π, which are alkyl glycosides, wherein the alkyl group is a mixture of about eight to fourteen carbons and the number of glycoside groups present in the formula is from one to six, even more preferably APG 325 or APG 225, wherein the alkyl group is a mixture of nine to eleven carbons or Atplus 258 or alternatively Rhodonat LMO which is a coconut oil saccharoglyceride or Rhodonat MLP 704 which is a modified LMO carbohydrate;

(b) the formula ΙΠ, which is a quatized fatty aminoethoxylate wherein the lipidic amine is an alkylamine, wherein the alkyl group is a mixture of about eight to twenty carbon atoms, preferably a mixture of eight to twelve carbon atoms, as found in cocomethylammonium chloride, and most preferably Ethoquad C / 12 (quaternized lipidic amino ethoxylate, which may be represented by the formula (EO) xH

RzoRzNT - (EO) yH Z where

R ₂₀ is a mixture of alkyl groups having from about eight to twenty carbon atoms inclusive;

R ₂₁ is alkyl of one to four carbons, inclusive;

EO is an ethylene oxide monomer wherein x and y are independently from zero to fourteen and are the number of moles of ethoxylation present, provided that x and y, taken together, must be from two to fourteen, preferably two; and

Z 'is an agriculturally acceptable anion);

- 5 (c) of Formula IV, which is a mixture of a lipidic aminoethoxylate and an ethoxylated alkylphenol, preferably Improve® (the lipidic aminoethoxylate may be represented by the formula

R22N (EOJnH (EO) mH where

R 22 represents a mixture of alkyls of from about six to thirty carbons, inclusive, but preferably from 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 their sum is from one to fifty, preferably from five to fifteen, and the ethoxylated alkylphenol may be represented by the formula

R ₂₃ -O / -O (EO) wH where

R 23 is a mixture of alkyl groups having from zero to twenty carbons, inclusive, preferably from about eight to ten inclusive, and most 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 inclusive;

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

CH ₃ ch ₃ ch ₃ ch ₃ 'II 11'

I

C * -1-C — C — C — C — C = C — C — C — C — C-4-C *

I (EO) q (EO) p

- 6 where * is the number of carbons indicating the total number of carbons in the chain from 10 to 12 carbons inclusive; and EO is an ethylene oxide monomer, wherein q and p are, independently of each other, numbers that indicate the number of moles of ethylene oxide monomer in the formula and the sum is in the range of about ten to thirty 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 Terginol® 15-S-7, Terginol® 15-S-9 or Terginol® 15-S-12 and most preferably Terginol ® 15-S-12 (Formula VI can be illustrated as follows:

where

R.24a represents a hydroxy- or polyethylene group in which a indicates the number of moles of ethylene oxide monomers present in the formula and is from seven to fifteen inclusive, preferably from nine to twelve inclusive, and C * represents the ends of the carbon chain, such that together chain a mixture of carbons having a total of from eleven to fifteen carbons inclusive, but preferably from twelve to fourteen carbons inclusive);

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

0 'R

R ₂₅ - N * - (CHCH ₂ O) _z - H (CHCH ₂ O) _Z —H

R where

R ₂₅ represents a mixture of alkyls of from about six to thirty carbons, inclusive, preferably from about twelve to twenty carbons inclusive;

R 7 is hydrogen or methyl; and z and zi indicate the number of moles of alkoxylation or preferably ethoxylation in the formula and icb sum is from one to fifty, but preferably from five to fifteen);

(g) of formula VIII, which is an alkyldimethylamine oxide, preferably Empigen OB (alkyldimethylamine oxide may be represented by the formula

ABOUT

R26 —N * —CH ₃ ch ₃ wherein

R 26 represents a mixture of alkyls having from about six to thirty carbons inclusive, preferably from about twelve to twenty carbons inclusive);

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

R

I

R @ ₁ - (XCHCH2) 2 -OH wherein

R 27 represents a mixture of alkyls having 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 indicates the number of moles of ethoxylation in the formula and, in total, from one to fifty, preferably from five to fifteen);

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

R28-CO2- (EO) z, ₃ -H

- 8 where

R 28 is a mixture of alkyls having from about six to thirty carbons inclusive, preferably from twelve to twenty carbons inclusive;

EO represents ethoxylation in the formula and ₃ is from one to fifty, preferably from five to fifteen); or (j) of formula XI, which is a quaternary ammonium, preferably Dodigen 226 (quaternary ammonium may be represented by the formula

R ₂₉ - ((CH 2 CH 2 CH 2 Cl)) Q ⁺ where

R 29 represents alkyl from C 8 to C 20, preferably C 10 to C 16 and Q is an agriculturally acceptable anion);

(k) of the formula ΧΠ, which is quaternary ammonium, preferably Dodigen 4022 (quaternary ammonium can be represented by the formula

R 50, R 31 and R 32 are independently alkyl having from one to three carbons, which in total have from two to seven carbons, preferably all of the methyl, or one of R ₃₀ , R 31, R 32 is ((EO) n i (PO) n 2 ); EO is ethylene oxide; PO is propylene oxide; ni is an integer from one to two; and n ₂ is an integer from three to fifteen, preferably from six to ten; and Q is an agriculturally acceptable anion);

(1) of the formula ΧΙΠ, which is diaminoethoxylate, preferably Ethoduomeen (diaminoethoxylate can be represented by the formula ^ EO) n ₅ (EO) n ₃ (EO) n ₄ where

R ₃₃ represents alkyl from C 8 to C 20, preferably C 10 to C 16; and au, ₃ , n ₄ , n ₅ represent the number of moles of ethoxylation in the formula and give in total from one to fifty, but preferably five to fifteen);

- 9 (m) of formula XIV which is an alkoxylated primary fatty alcohol, preferably Ethylan CPG 945 (an alkoxylated primary fatty alcohol may be represented by the formula

R34 - O (PO) _n6 (EO) ₇ where

R 34 represents alkyl from C 8 to C 18, in particular from C 13 to C 15; EO is ethylene oxide; PO represents propylene oxide; n ₆ is an integer from 6 to 50, but preferably from 6 to 9; n ₇ is an integer from 4 to 8, preferably from 4.5 to 6; and (n) mixtures of the above.

Most preferably, the adjuvant is a composition represented by Improve® and Tergitol® 15-S-12.

A more preferred compound of formula I is an agriculturally acceptable salt of 3,4,4-trifluoro-3-buten-1-amine, but especially its monochloride; N- (3,4,4-trifluoro-3-butenyl) glycine, in particular its monohydrochloride; 2-amino-N- (3,4,4-trifluoro-2-butenyl) propanamide, in particular its monohydrochloride; (S) -2-amino-4 (methylthio) -N- (3,4,4-trifluoro-3-butenyl) butanamide, in particular its monohydrochloride; 4,4-difluoro-3-buten-1-amine, in particular its monohydrochloride; 3,4,4-trifluoro-3-butenoic acid, and in particular its sodium salt; a combination of 3,4,4-trifluoro-3-butyric acid and 3,4,4-trifluoro-3-buten-1-amine in a one to one ratio (1: 1); (S) -2-amino-3-hydroxy-N- (3,4,4-trifluoro-3-butenyl) butanamide, and in particular its monohydrochloride; N- (4,4-difluoro-3-butenyl) glycine methyl ester and in particular its monohydrochloride; 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-1-oxo-3-butenyl) glycine; 2 - [(3,4,4-trifluoro-3-butenyl) amino] acetamide, in particular its monohydrochloride; or

3,4,4-trifluoro-3-butenoic acid, 2-aminoethyl ester and in particular its monohydrochloride.

A particularly parasitic active ingredient is 3,4,4-trifluoro-3-buten-1-amine, and in particular its monohydrochloride salt; or N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine and the most suitable active ingredient is N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine.

It is surprising that the combination of a compound of formula I and auxiliary active ingredients of formulas H, ΙΠ, IV, V, VI in amounts of 0.05% to 20%, but less than the toxic amount for the infested plant or mixtures thereof, increases efficacy Compounds of formula I against parasitic, but especially non-nematode infestation when applied to infested plant leaves, with an unexpected difference when compared to the compound of formula I with other known surfactant wetting, dispersing and emulsifying agents commonly used in agricultural preparations. The ordinarily skilled worker should be able to find the percentage of adjuvant effective for a particular compound of the formula. The percentage is expressed in volume.

Therefore, the present invention is also a method for controlling nematodes, insects and acarias, and for the use of these new agents for controlling nematodes, insects and acarias, including treating the infestation with nematodes, insects and mites either on the leaves of infested plants or in soil with a compound of formula I with an activity-enhancing amount of the adjuvant of formula Π, which is an alkyl glycoside, but preferably APG® 325 or Atplus 258 in an amount of from 0.25% to 1%; further with an adjuvant of the formula EU which is ethoxylated cocomethylammonium chloride, in particular Ethoquad C / 12 in an amount of from 0.25% to 1%; further with an adjuvant according to Formula IV which is a fatty aminoethoxylate, preferably Improve® in an amount of from 0.25% to 2%; further with an adjuvant according to Formula V which is acetylenediol ethoxylate, preferably Surfynol 485, and in particular in an amount of from 0.5% to 1%; or with an adjuvant of formula VI which is an ethoxylated secondary alcohol, preferably Tergitol® 15-S-7 in an amount of about 0.5%, Tergitol® 15-S-9 in an amount of about 0.5%, or Tergitol® 15-S- 12 in an amount of 0.5%.

DETAILED DESCRIPTION OF THE INVENTION

The novel formulations of the present invention are useful as unexpectedly effective systemic formulations for controlling nematode, insect and mite infestations of a plant. These preparations can be used in a lower effective ratio of the compound of formula I to the leaf area, while maintaining the effectiveness of controlling nematodes, insects and mites infestation. That is, when applied to the leaves or stems of a plant, they penetrate through the bark (floem) and xylem plants and destroy nematodes, insects or mites at other locations in the plant. These presented systemic methods

11 the removal of nematodes, insects and mites utilize the compositions of the present invention with unexpected penetration of the vascular bundles. These formulations, consisting of a compound of formula I and a sufficient amount of adjuvant, provide enhanced efficacy. The increased efficacy of these formulations is believed to be the result of improved penetration of the lycar tissue, thereby relocating the compound of Formula 1 downwardly (down the plant) without losing the elimination activity of the compound of Formula I against nematodes, insects or mites.

In order to effectively destroy systemically nematodes and other pests by spraying above-ground plant surfaces, the present compositions may improve the ability of the active ingredient to penetrate the cuticle of the leaves or stems of the plant, penetrate the lycar tissue and stay there long enough to be transformed by the plant into untreated parts Plants, including roots. There, such a compound of formula I may be released or in some way come into contact with the pest to the extent that it destroys or repels the pest, and the damage that the pest would cause would be limited or totally excluded. During this plant process, the compound of formula I may undergo chemical reactions such as hydrolysis or biological reactions such as enzymatic reactions. In addition, Formula I of the present invention can be designed such that when a compound is placed on a plant and prior to absorption into it, it can undergo reactions that provide a compound that is readily absorbable, transportable, and effective in preventing pest damage. They are, for example, those compounds which have UV-labile protecting groups which, when exposed to natural light, undergo a reaction and give active and mobile derivatives of the compounds of formula I. Another example is the silylated amino derivatives.

Thus, what is placed on the leaves or stems of a plant need not be a composition in which what is actually transported or actually destroys a pest is a compound of Formula I. The methods of the invention provide compositions that can be transformed by chemical or biological reactions so that they have appropriate polarity for systemic activity.

Although the methods of the present invention, including the use of a plant locus composition, preferably foliar, are known, the present compositions are surprising combinations of compounds of formula 1 as defined above and selected adjuvants of formulas Π, ΙΠ, IV, V, VI or mixtures thereof. These combinations are for those adjuvants that cannot be predicted from those commonly used in agriculture.

In terms of nematode control, among those compounds of Formula I, those where n is 1 and X, Y and Z are all F are preferred, and Q 1 is then CH 2 NH 3 + W-, i.e., 3,4,4-trifluoro-3-butene salt -l-amine. If Q1 is CH2NHR6, R * is preferably an alpha-amino acid bound by a peptide bond, more preferably a proteinaceous amino acid. If Q 1 is (C = O) -R h, R 11 is preferably hydroxyl and the compound is thus

3,4,4-trifluoro-3-butenoic acid or a salt thereof, including the salt formed with 3,4,4-trifluoro-3-buten-1-amine, which means 3,4,4-trifluoro-3-butene- l-amino-3,4,4-trifluoro-3butenoát.

W may be any agriculturally acceptable anion.

This includes, but is not limited to, chloride, iodide, bromide, oxalate, sulfate, phosphate, citrate, acetate or fluoroalkene carboxylate, for example F ₂ C = CFCH ₂ COO '.

In addition to the compounds specifically described above, all agriculturally acceptable reindeer compounds within the scope of the present invention are included. For example, a compound of the invention having a free amino group may also exist as a proton form that can associate with various anions such as (but not limited to) chloride, bromide, iodide, phosphate, oxalate, sulfate, citrate, and acetate. In addition, a fluoroalkene carboxylate anion such as F ₂ C = CFCH ₂ COO 'may be a counterion.

A compound of the invention having a carboxylic acid or hydroxyl group may exist as a salt associated with various cations, for example, but not limited to, alkali earth metals such as sodium, calcium and potassium; magnesium; or quaternary ammonium ions such as ammonium, mono-, dialkyl or trialkylammonium, for example isopropylammonium, or pyridinium. In addition, a fluoroalkenylammonium ion, such as F ₂ C = CFCH ₂ CH ₂ NH 3 ⁺ , may also be a cation. All such compounds and others having similar agriculturally acceptable characteristics are provided by the present invention.

The term "halo", "habd" or "halogen" as used herein refers to fluorine, chlorine, iodine or bromine or compounds thereof.

The term "alkyl", as defined in formula I, means straight or branched groups of one to seven carbons. The term "lower alkyl" refers to a group containing one to four carbon atoms. The term "aliphatic" means saturated

Or unsaturated, branched or unbranched alkyl groups having from one to ten carbon atoms.

The term "alkoxy" refers to 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 a lower alkyl ester of a carboxyl group.

The term "aliphatic amine" means an aliphatic group wherein at least one hydrogen is replaced by -NH 2. The term "aliphatic carboxylic acid, esters, thioesters, and amides thereof" means an aliphatic group wherein at least one carbon is a carboxyl group, HOOC-, or is a lower alkyl ester, a lower alkylthioester, or an amide thereof.

The term "aromatic group" means phenyl, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxyl, alkoxycarbonyl, and phenyl. It will be appreciated by one of ordinary skill in the art that heterocycles may also be used as an 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.

For purposes herein, the phrase "amino acid amide" (or Qi) means that R e is an amino acid linked by a peptide bond to N of CH ₂ NHR 6. This amino acid may be natural, i.e. protein, or non-natural. The amino group of the amino acid may be a substituent of any carbon in the group, for example alpha, beta or gamma relative to the carbonyl.

The term "alkyl or arylhydrazine" means a hydrazine group substituted with a lower alkyl or phenyl group which in turn may be substituted. The term "alkyl or arylsulfonamide" means a sulfonamide group substituted with lower alkyl or phenyl, which may be alternately optionally substituted.

SYNTHESIS OF THE COMPOUND

Methods for preparing the compounds of Formula I of the present invention are described in PCT application no. PCT / US92 / 1474, which is hereby incorporated by reference.

APPLICATION FORMS

In conventional use, the formulations are not usually used alone without further impurities or dilutions, but are generally used in a suitably formulated formulation compatible with the mode of administration and containing an effective amount of the formulation. The formulations of this invention may be admixed with additional agriculturally acceptable surfactants and carriers that are normally used to facilitate dispersion of the active ingredients, confirming the acknowledged fact that the resulting formulation and method of administration may affect the activity of the formulation. The present composition can be used in the form of sprays, powders or granules for areas where pest control is desired, the type of application varying depending on the type of pest and the environment. Thus, the compositions of the invention may be formulated as large diameter granules, as dusts, as wettable powders, as emulsifiable concentrates, as solutions, and the like.

The granules may contain porous and non-porous particles, such as attapulgite clay or sand, which serve as carriers for the present compounds. The granular particles are relatively large, with a typical diameter of about 400-2500 microns. The particles are either impregnated with a substance prepared according to the invention or coated with the substance, sometimes using an adhesive. The granules generally contain 0.05-10%, but preferably 0.5-5% of the active ingredient.

Powders are admixtures of compounds with finely divided solids such as talc, attapulgite clay, diatomaceous earth, pyrophytes, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flour, and other organic and inorganic solids that serve as carriers. this compound. These finely divided substances have a diameter of less than 50 microns. A typical powder formulation contains 1 part of the compound and 99 parts of talc.

The compositions of the present invention can be made in the form of liquid concentrates by dissolving or emulsifying them in suitable liquids and in the form of solid concentrates as admixtures with talc, clay and other known solid carriers used in agricultural chemistry. Concentrates are formulations containing about

5-50% of the active ingredient, of which 98.00-99.25% may be a compound of Formula I and 0.25-2% may be an adjuvant; 95-50% of the formulation is an inert material that includes surfactant dispersing, emulsifying and wetting agents that are out of

Within the scope of the term adjuvant as defined herein, even higher concentrations of the active ingredient or its excipient may be used experimentally. The concentrates are for practical use in the form of sprays diluted with water or other liquids, or solid carriers for use as powders are added.

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

Typical solid concentrate carriers (also called wettable powders) include fuller's earth, ,y, silicates and other strongly absorbing and easily wettable inorganic diluents. A suitable solid concentrate formulation may contain both 1.5 parts of sodium lignosulfonate and 1.5 parts of sodium lauryl sulfate as additional wetting agents, 25 parts of the active compound and 72 parts of attapulgite clay.

The production of the concentrate is useful for conveying the low melting point products of the present invention. Such concentrates are prepared by melting low melting solid products together with one percent or more solvent to form a concentrate that does not solidify upon cooling to or below the freezing point of the pure product.

Useful liquid concentrates include emulsifiable concentrates which are homogeneous liquids or paste formulations readily dispersible in water or other liquid carriers. They may consist only of the active ingredient with a liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophrone or other relatively nonvolatile organic solvents. These concentrates are dispersed in water or other liquid carriers for use and are normally used as sprays on the surfaces to be treated.

A typical emulsifiable dosage form of a concentrate of 50 grams per liter consists of 5.9% by weight of the preparation of the present invention and contains as emulsifiers a 1.80% mixture of calcium dodecylbenzenesulfonate and a nonionic 6-molar condensation product of ethylene oxide and nonylphenol, 2.70 % of a mixture of calcium salt of dodecylbenzenesulfonate and a non-ionic 30-molar condensation product of ethylene oxide and nonylphenol, 1.50% of a non-ionic paste of polyalkylene glycol ether and 88.10% of purified xylene solvent.

Typical surfactant wetting, dispersing and emulsifying agents for use in the adjuvant compositions of the present invention are other agricultural formulations including, for example, alkyl and alkylarylsulfonates and sulfates and their sodium salts; alkyl amide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; poly ethylene oxides; sulfonated animal and vegetable oils; sulfonated kerosene; polyhydric alcohol fatty acid esters and ethylene oxide addition products of these esters; and addition products of long chain mercaptans and ethylene oxides. The surfactant typically contains about 1-15% by weight of the active compound. Thus, in the present compositions, the surfactant together with the adjuvant of the invention may reduce the percentage of other surfactants used to prepare the composition.

Other useful formulations include simple solutions of a compound of the invention in a solvent in which the substance is completely dissolved at the desired concentration, such as water, acetone or other organic solvents. A preferred dosage form for foliage use is an aqueous solution, more preferably containing a sufficient amount of adjuvant to provide an increased parasitic active compound of Formula I, as well as to provide the desired concentration. However, the formulation may also comprise glycerol and other surfactants such as Tween ® 20, most preferably 1% glycerol and 0.1% Tween ® 20 may also be included.

The formulations may be prepared and used with suitable pesticidally active ingredients including insecticides, acaricides, fungicides, plant regulators, herbicides, fertilizers, etc.

APPLICATIONS OF USE

The present invention provides methods for destroying and repelling various pests that parasitize on agricultural crops, especially nematodes, insects and mites. Infestation of the plant by any of these pests can be prevented by applying an effective amount of any of the compounds of the invention to a particular site of the plant. Administration can be accomplished in a variety of ways, including applying the compound or composition comprising the compound to the soil

- 17 before or after planting, or in the case of danger to seeds or parts thereof before or during sowing, and to leaves, stems or trunks of a plant or tree. Treatment can be performed multiple times during the growth season with one or two days between applications. The appropriate application schedule will depend on the pest life cycle, ambient temperatures and humidity. In addition, the treatment schedule may be affected by the age or size of the plant.

The methods of the present invention can be carried out on different crops. Their designation includes, but is not limited to, fruit and vegetable crops such as potatoes, sweet potatoes, carrots, tomatoes, vines, peaches, citrus, bananas, corn and soybeans, tobacco and cotton.

The compounds of the invention may be used against any of the phytopathogenic nematodes. The listing of insects that can be destroyed or repelled by the methods of the invention includes, but is not limited to, leaf pests such as aphids of green peaches and soil pests such as a Southern corn root worm. The mites that can be destroyed by the methods of the invention include, but are not limited to, two spotted spider mites. Although no tests were performed specifically using the above preparations, tests performed with several anti-parasitically active compounds of the present invention did not show any significant effect against a mammal or potato worm.

It has been found that a suitable amount when administering a composition wherein the compound of formula I is boosted by combination with an active adjuvant of 0.25 to 2 wt. % according to the formula Π, for example, in this combination is approximately 28 to 56 mg / m ² to achieve a destruction level (¢ 80-100%) that is comparable to 112 mg / m ² Triton CS7 for root nematode destruction.

EXAMPLES OF TESTING

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-1-oxo-3-butenyl) glycine.

For foliar application, a through-spray was used to specify application procedures and field volumes (233 liters per hectare). twenty

- 18 milliliters of each test solution was treated in water, assuming that 10 ml were currently used per 5 plants per treatment (five or six inch pots, soil mix: 50% Metromix, 25% fine sand, 25% medium coarse sand, 136 g Osmotot 14-145-14 per cubic foot, one to four weeks old Rutger tomatoes per pot). Plants are often planted in five or six-inch pots; at least one day was left between transplanting and f

treatment. Flower pots placed along the 5 foot long central belt of the through-sprayer. One tip of the 8001E nozzle was placed in the arm directly above the plants and adjusted to a position 6-9 inches above the leaves. The pressure was set at 15 psi so that the nozzle flow rate was 4.2-4.5 ml / s. The spray rate was adjusted to a value of about 95 on the dial so that the LCD rate was read 1.75-1.85. The assays were usually based on 20 treatments and control treatments without inoculation.

After chemical treatment, the plants were allowed to dry for 2-4 hours and then inoculated. Using a thick pen, 4-6 shallow holes were cut in close proximity to the stem of the plant for the application of Meloidogyne incognita nematode eggs. Using a large syringe, 30 ml of the egg suspension (720 eggs / ml,

000 eggs per plant) between all holes in pots. Prior to inoculation, the plants were randomly distributed and then moved to either a 16 or 21 greenhouse

3-4 weeks incubation. The daytime temperatures in the greenhouses were 25-30 ° C and the additional light / top simulated a day length of 12 hours. For evaluation, the leaves were examined for phytotoxic effects and then the stalks were cut at ± 2 inches above soil level. Excess soil was shaken out of the root jug and the soil washed well out of the roots with water using a high pressure nozzle. The roots were visually evaluated for the proliferation and abundance of cecidia and each replicate was assigned a value of 0-100%, indicating the severity of the disease. This data was entered into the SAS program and the results were compared with incubated control and with (S) -2-amino-4- (methylthio) -N- (3,4,4-trifluoro-3-butenyl) butanamide hydrochloride with Triton CS7 or with (S) -2-amino-4- (methylthio) -N- (3,4,4-trifluoro-3-butenyl) butanamide without adjuvant. Several commercial and experimental adjuvants have been tested. They are listed in the following list, with their active ingredient and percentage:

Table 1 adjuvant % ai Active ingredient NH3SO4 100 ammonium sulphate APG® 225 70 alkyl glycoside APG® 300 50 alkyl glycoside APG® 325 70 alkyl glycoside Arquad T 127W 27 trimethylammonium Buffercide 1 0 orthophosphoric acid Cayuse 42.5 polyglycol- ethers + 16.5 ammonium salts Improve® 64 fatty aminoethoxylate + 14 ethoxylated nonylphenol CropOil 17 polyoxyethylated polyol fatty acid ester + polyol fatty acid ester. Ethoquad C / 25 100 cocomethyl ammonium chloride 15E0 Ethoquad C / 12 100 cocomethyl ammonium chloride 2E0 Emcol® CC9 100 propoxylated quartz, amine glycerin 100 glycerol MON 0818 1 5 polyoxyethylene alkylamine nitrogen 28 28% nitrogen e noňylphenol 4EO 1 00 nonylphenol 5E0

nonylphenol 6EO 1 00 nonylphenol 6E0 nonylphenol 8EO 1 00 nonylphenol BEO nonylphenol 10EO 100 nonylphenol 10E0 nonylphenol 12EO 100 nonylphenol 12E0 R-11 90 oktylfenoxyetanol Silwet L77 100 organosilicon ethoxylate Surfynol 465 100 10 moles E0 of acetylovary diolethoxylate Surfynol 485 100 30 moles of acetylated E0 diolethoxylate Tergitol® 15-S-3 100 Ρΐ1’θ15 sec. alcohol E0 Tergitol (R) 15-S-5 100 CI-j-C-js sec. alcohol E0 Tergitol® 15-S-7 100 θ11’θ15 sec. alcohol EO Tergitol® 15-S-9 100 θ11θ15 sec. alcohol E0 Tergitol® 15-S-12 100 Cl1'Cl5sek. alcohol EO Tergitol® 15-S-15 100 θ11θ15 sec. alcohol E0 Tween 20 100 polyoxyethylene (20) sorbitan monolaurate Triton® CS-7 60 alkylaryl polyethoxylate and sodium alkyl sulfonate alkylate Varion CDG-K 28 lauryl

The following results, using the above methods, show compounds of Formula I, i.e. 2-amino-N- (3,4,4-trifluoro-2-butenyl) propanamide monohydrochloride (designated as A below), (S) -2- amino-4- (methylthio) -N- (3,4,4-trifluoro-3-butenyl) butanamide monohydrochloride (designated as B below), 3,4,4-trifluoro-3-butenoic acid, sodium salt (designated as C v) below), N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine (designated as D below), 2 - [(3,4,4-trifluoro-3-butenyl) amino] acetamide monohydrochloride ( 3,4-trifluoro-3-butenoic acid 2-aminoethyl ester monohydrochloride (designated as F below) with which the selected adjuvants of the present invention then provide unexpected enhancement of the compound of Formula I. ( * FOR I)

Tab. 2 cont. FOR l ‘ adjuvant Adj% 1 6 8 4 2 B without adjuvant 35 38 B bez adj. 29 19 B bez adj. 28 13 B bez adj. 35 22 B . bez adj. 38 24 B without adi. 24 9 B bez adj. 19 6 B NH3SO4 2 22 9 B APG® 225 .25 59 14 B APG® 225 .25 (ai) 47 9 B APG® 225 .5 62 36 B APG® 225 1 56 34 B APG® 225 1 (i) 88 49 B APG® 300 .25 37 16 B APG® 300 .25 (ai) 58 7 B APG® 300 .5 73 19 B APG® 300 1 67 40 B APG® 300 1 (i) 92 55 B APG® 325 .25 88 49 B APG® 325 .25 (ai) 64 9 B APG® 325 .5 74 69 B APG® 325 1 7Q 29 B APG® 325 1 (i) 96 47 B Arquad T , 25 (i) 31 2 B Buffercide .25 1 2 8

B Cayuse .25 41 21 B Cayuse .75 47 27 B CropOil .5 43 1 8 B CropOil 2 30 25 B CS7 .5 28 Ί B CS7 .5 98 33 3 B CS7 Γ5 81 28 13 B CS7 • 5. 81 24 1 1 B CS7 .5 92 62 21 B CS7 .5 51 1 8 9 B CS7 5 (i) 95 58 21 B CS7 5 (i) 93 63 54 B CS7 -5 (i) 100 81 21 B CS7 5 (i) 50 1 1 B CS7 5 (i) 55 1 5 B CS7 5 (i) 55 13 B CS7-NH3SO4 .5 + 2 23 14 B CS7 + 28% N .5 + 2 17. 8 · B CS7. .5 90 40 B Emcol® CC9 1 5 5 B Emcol® CC9 5 18 5 B Ethoquad C / 12 .25 91 B Ethoquad C / 12 , 25 (i) 67 16 B Ethoquad C / 12 .5 91 B Ethoquad C / 12 1 98 B Ethoquad C / 12 1 (i) 79 50 B B Ethoquad C / 25 1 21 8 B Ethoquad C / 25 5 38p 28 B Ethoquad C / 25 2.5 (i) 36 1 1 B Ethoquad C / 25 1 + Surfynol 465 .5 (ai) 62 26 C glycerin 1 (i) 82 4 0 D glycerin 1 (i) 61 27 B Improve® .25 73 10 B Improve® .25 100 7 3 1 5 B Improve® .5 80 23 B Improve® .5 93 30 B Improve® .5 100 98 28 B Improve® .5 (ai) 94 56 B Improve® • 5 (i) 9 6 62 B Improve® 5 (i) 93 34

B Improve® 1 80 20 B Improve® 1 1 00 91 28 B Improve® 1 (i) 99 74 B Improve® 2 9 1 46 B Improve® 2 83 38 B Improve® 2 100 88 48 B Improve® 5 (i) + glycerol 1 (i) 73 3 7 E Improve® .5 (ai) 97 93 E Improve® 5 (i) 97 8 6 54 C Improve® .5 (ai) 100 9 9 93 C Improve® -5 (i) 97 97 C Improve® -5 (i) 1 00 83 38 C Improve® -5 (i) + qlvcerol 1 (i) 68 44 D Improve® .5 (ai) 100 99 92

Tab. 2 □ nadaljevanje. * FOR I adjuvant A d j% 1 6 8 4 2 D Improve® • 5 (i) 100 96 D Improve® 5 (i) 92 37 21 D Improve® .5 (ai) + glycerin 1 (i) 88 80 51 A Improve® -5 (i) 97 88 59 F Improve® .5 100 8 7 F Improve® • 5 (ai) 19 F Improve® 5 (i) 76 46 F Improve® 1 100 94 B MON 0818 .25 42 26 B MON 0818 .25 69 22 B MON 0818 1 35 13 B 28% N 42 6 B 28% N 2 56 12 B nonv.lfenol 4E0 .5 (ai) 1 1 9 B nonylphenol 6E0 • 5 (ai) 20 18 B nonylphenol 8E0 5 (i) 29 4 B nonvlfenol 10E0 • 5 (i) 18 8 B nonylphenol 12E0 5 (i) 38 9 B R-11 .06 33 13 B R-11 .25 • 28 1 0 B Silwet L77 .25 (ai) 22 1 1 B Silwet L77 .5 24 15 B Silwet L77 1 18 23 B Silwet L77 2 23p 9p B Silwet Ľ77 5 62p 26p B Silwet L77 5 48p 32p B Silwet L77 .25

Tab. 2 i Cont. * FOR 1 adjuvant Ad j% 1 6 8 4 2 + MON 0818 .25 54 22 B Silwet L77 .5 + MON 0818 .25 47 18 B Surfynol 465 1 18 15 B Surfynol 465 5 33p 5p B Surfynol 485 .25 (ai) 67 1 1 B Surfynol 485 .25 (ai) 57 14 B Surfynol 485 .5 (ai) 83 13 B Surfynol 485 1 (i) 7 1 30 B Surfynol 485 1 (i) 92 51 B Tergitol® 15-S-3 • 5 (i) 49 7 B Tergitol (R) 15-S-5 .5 (ai) 51 21 B Tergitol (R) 15-S-5 • 5 (i) 40 0 B Tergitol® 15-S-7 • 5 (i) 86 49 B Tergitol® 15-S-7 .5 (ai) 74 26 F Tergitol® 15-S-7 5 (i) 35 B Tergitol® 15-S-9 .5 (ai) 90 23 B Tergitol® 15-S-9 • 5 (i) 91 58 B Tergitol® 15-S-12 5 (i) 88 9 B Tergitol® 15-S-12 • 5 (i) 100 78 B Tergitol® 15-S-12 • 5 (i) 96 58 B Tergitol® 15-S-12 • 5 (i) 96 60 B Tergitol® 15-S-12 .5 (ai). 83 54 C Tergitol® 15-S-12 .5 {i) 97 76 C Tergitol® 15-S-12 5 (i) 97 80 37 C Tergitol® 15-S-12 .5 (ai) + glycerol 1 (ai) 91 68 29

Tab. 2 _; cont. * FOR 1 adjuvant A d j% 1 6 8 4 2 D Tergitol® 15-S-12 .5 (ai) 99 88 D Tergitol® 15-S-12 5 (i) 96 88 43 D Tergitol® 15-S-12 .5 (ai) + glycerin 1 (ai) 95 55 B Tergitol® 15-S-15 .5 (ai) 67 49 B Tergitol® 15-S-15 -5 (i) 7 4 5 B Tween 20 .25 36 7 B varion , 25 (i) 47 0

p = cytotoxicity recorded on the leaves

Roughly printed% efficacy means a statistically significant improvement in disease control compared to I-B, with the same amount used either without adjuvant or with Triton CS7 in the same assay. Adj. % has the same meaning as in Table I, except t

that (ai) in the% Adj column means the volume of the adjuvant of Table I adjusted to the concentration of the active ingredient of the adjuvant.

The surfactants or wetting agents mentioned above are sold under the following names: 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 getting from various sources. Ethoquad is sold by Akzo, Chemical Division, and Emcol is available from Witco Corp. Organics Div., 28% nitrogen can be prepared from conventional nitrogen-containing compounds. Nonylphenol is sold, for example, by Witco S.A. R-II is available from Wilbur-Ellis Co. Silwet is from Union Carbide Corp., Special Chemicals Div. Surfynol is from the company

27 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 Chemicals Co., Inc.

The following methods to evaluate the root nematode killing efficiency (Meloidogyne incognita) were also used to evaluate adjuvants that were combined with a compound of formula I, specifically, for example, N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine. ) on tomato roots when the mixture of adjuvant and compound is applied to the leaves of young plants.

Tomato plants (Rutgers cultivar) were grown one by one in 6 cm diameter plastic flower pots containing a mixture of equal portions of fine sand, coarse sand, sandy-loamy soil and commercial flower soil.

Compounds of adjuvant compounds were prepared by adding the compound to water to give a final concentration of 2400, 1200 and 600 ppm, and then adding the adjuvant to the solution to achieve a final concentration of 0.5% by volume of adjuvant per volume of water. This single concentration of adjuvant was used with all three ratios of test substance, unless otherwise specified.

When the tomatoes were 18-21 days old, the test substances were sprayed onto the leaves and stems using a through sprayer, which simulates field application procedures. The sprayer is calibrated to spray 233 liters of test solution per hectare, resulting in 0.56, 0.28 and 0.14 kg of active ingredient per hectare. Three plants were sprayed at each treatment and then air dried and left under fluorescent lamps for 15-18 hours before inoculation. All plants were then incubated with mature root nematode eggs containing larvae J1; 8000 eggs were applied per plant in 5 ml of water to the soil at the base of the stem. The plants were then incubated in a growth chamber at 27 ° C and 60% room humidity, with all replication pots randomly distributed within the chamber. Over the next two weeks, the plants were watered from below and the leaves were kept dry. Three to seven days after treatment, the leaves of the plants were examined for symptoms of phytotoxicity and assigned a relative value of 0 to 3, where 0 = no damage, 1 = mild spot or chlorosis, 2 = mild damage but without growth inhibition, 3 = severe damage and stunting. After three weeks of incubation as described above, plant roots were washed and examined for nematode severity. Every root system

- 28 were evaluated individually - a visual estimate of the percentage of the root system was established,

damaged by nematode proliferation and values of 0, 3, 5, 10, 25, 100% root damage were assigned. 50, 75 or business name Adjuvant tested chemical name concentration Atplus 258 alkylpolyglucoside 62% a.s. CS-7 alkyl aryl polyethoxylate and Na salt alkyl sulfonated alkylate 60% a.s. Dodigen 226 kokoalkyldimetylbenzylamóniumchlorid 50% a.s. Dodigen 4022 EmcolXE 1656 an alkoxylated fatty amine oxide 70% a.s. Empigen OB alkyldimethyl 30% a.s. Ethyl CPG 945 modified alkoholalkoxylate 100% a.s. Flo-Mo 3153 ethoxylated fatty amine oxide 70% a.s. Genapol T250 fatty alcohol polyglycol ether 100% a.s. Improve fatty amine ethoxylate 64% a.s. + ethoxylated nonylphenol 14% a.s. Kaomul 230 esterified coconut polyethoxy ether 100% a.s. piperonyl butoxide 100% a.s. Rhodonat LMO carbohydrate based coconut oil 100% a.s. Rhodonat MLP704 modified LMO saccharoglyceride 100% a.s. Simusol M52 polyethoxylated acid. stearic 100% a.s. ethoduomeen ethoxylated alkylamine 100% a.s. Ethomeen C-15 ethoxylated alkylamino diamine 100% a.s.

- 29 Manufacturers of tested additives

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.

- 30 Table 3

Mean percent root damage caused by nematode growth (% disease), standard deviation of this mean,% root damage removal, and leaf phytotoxicity assessment (0 = none, 3 = severe) after treatment of the tomatoes with the formulation (MON 45700) mixed with the indicated adjuvant.

Adjuvants (0.5% v / v if not) ie Note) D QAI / ha % of disease % potlar čení average. fytotoxi average standard, odchvlkí CS-7 560 33.33 11.79 50.00 1.67 280 66.67 11.79 00:00 1:00 Improve 560 20:00 7.7 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 7.7 70.00 1:33 280 50.00 20:41 25.00 0.67 140 50.00 00:00 25.00 1:33 Dodigen 226 560 20:00 7.7 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 7.7 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 7.7 70.00 1.67 280 41.67 11.79 37.50 00:33 140 58.33 11.79 12:50 00:33 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 00:00 1:00 Simusol M52 560 41.67 11.79 37.50 0.67 280 66.67 11.79 00:00 00:33 140 66.67 11.79 00:00 0.67 CS-7 560 15:00 7.7 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 7.7 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 (0.5% v / v if not is a note) 0 QAI / ha % of disease % potia- tion average fytotoxi- he reads average Was · 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 00:00 00:33 Kaomul 230 560 15:00 7.7 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 00:00 92.50 2.67 280 15:00 7.7 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 00:00 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 7.7 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 00:00 Ethomeen C15 0.3% + 560 00:33 00:47 99.50 3:00 Tergitol 15S9 0.2% 280 3:33 2:36 95.00 2.67 140 41.67 11.79 37.50 2:00 Ethoduomeen T25 560 1:00 00:00 98.50 2:00 280 8:33 2:36 87.50 2:33 140 41.67 11.79 37.50 1:33 Ethomeen Cl5 0.18% + 560 11.67 9:43 82.50 2.67 Tergitol 15S12 0.12% + Tergitol 15S9 0.2% 280 00:00 00:00 100.00 3:00 140 00:00 00:00 100.00 3:00 Tergitol 15S9 280 00:00 00:00 100.00 3:00 140 00:00 00:00 100.00 3:00 Empigen OB 560 3:00 00:00 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

adjuvant (0.5% v / v if not is a note) 0 OAI / ha % of disease % potia- appreciate average. phyto toxicity average standard variation Improve 560 00:33 00:47 99.33 2:00 280 6.67 2:36 86.67 1:33 140 15:00 7.7 70.00 1:00 Atplus 258 0.4% + 560 1:33 1.25 97.33 0.67 piperonyl butoxide - 0.1% 280 5:00 · 00:00 90.00 00:33 140 6.67 2:36 86.67 1:00 Atplus 258 0.5% + 560 00:00 00:00 100.00 1:33 amnium sulphate 2.0¾ 280 2:33 0.94 95.33 0.67 140 15:00 7; 07 70.00 0.67 Atplus 258 0.5% 560 00:33 00:47 99.33 1:33 280 3:00 00:00 94.00 1:00 140 20:00 7.7 60.00 00:33 Improve 0.5% 560 1:33 1.25 97.33 2:33 + ammonium sulfate 2.0% 280 3:33 2:36 93.33 1:33 140 25.00 00:00 50.00 1:00 Improve 0.5% + piperonyl 560 3.67 0.94 92.67 1.67 butoxide 0.1% 280 8:33 2:36 83.33 2:00 140 41.67 11.79 16.67 1:00 CS-7 0.5% + piperonyl 560 2:33 0.94 95.33 1:00 butoxide 0.1% 280 6.67 2:36 86.67 1.67 140 41.67 11.79 16.67 0.67 CS-7 560 6.67 2.89 87.00 2:33 280 28.33 20:21 43.00 1:33 Improve 560 6:00 3.61 88.00 1.67 280 15:00 8.66 70.00 1:33 140 41.67 14:43 17:00 0.67 Dodigen 4022 560 6:00 3.61 88.00 1.67 280 13:33 10:41 73.00 1.67 140 41.67 14:43 17:00 1:00 Dodigen 4022 0.4% + Tween 560 5:00 00:00 90.00 2:00 20 0.1% 280 15:00 8.66 70.00 1:33 140 41.67 14:43 17:00 1:33

adjuvant (0.5% v / v if no comment) D ai / ha % of disease % potia- appreciate average fytotoxi- he reads average Std. Outgoing. Dodigen 4022 0.32% + 560 13:33 10:41 73.00 2:00 Tween 20 0.08% + piperonyl butoxide 0.1% 280 41.67 14:43 17:00 1:33 1 40 58.33 14:43 -1 7.00 1:00 Tergitol 15-S-9 0.1% 560 6.67 2.89 87.00 2:00 280 20:00 8.66 60.00 1:33 140 41.67 14:43 17:00 200 Ethomeen C15 0.15% + 560 5:00 00:00 90.00 1.67 Tergitol 15-S-9 0.1% 280 15:00 8.66 70.00 1:33 140 41.67 1 4Í43 17:00 1:00 Crop Life 5.0% 560 8:33 2.89 83.00 1.67 280 25.00 00:00 50.00 0.67 140 50.00 „ÍL Q Q ... 00:00 1:00

Claims (15)

PATENT CLAIMS 1. A mixture comprising a combination of a compound of formula (I) \ y / C = (j - _(CH2) "- QZ wherein: n = 1.3, 5, 7, 9 or 11; Q is CH ₂ NHR 6, CH ₂ NO ₂ , CH ₂ N = CHR ₂ , CH ₂ N = C = O, CH ₂ N ⁺ R ₃ R ₄ R ₅ - or (C = O) -R 11; 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 or (C = O) -R 11, then each X, Y and Z is F; W is an agriculturally acceptable anion; R ₂ is an aromatic group; each of R ₃ , R 5 and R 5 is independently hydrogen; a lower alkyl group optionally substituted by at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; one of R ₃ , R 4 and R 5 is hydroxyl and the other two are hydrogen; or R ₃ , R ₃ , and R 5 together with the nitrogen of Q form a cyclic quaternary ammonium group; R 6 is hydrogen; an aliphatic group, optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; amino acid Q amide; (C = O) R ?; C 1 -C ₁₂ aliphatic amines, optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; C ₂ -C ₁₂ aliphatic carboxylic acids, their esters, thioesters and amides, all optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; dihydro-3-oxo-pyrazolidinyl; or phenyl or thiophene, optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; 35 or R 8 together with the nitrogen of Q is guanidine; hydrazine; allyl or arylhydrazinyl, optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; or alkyl or aryl sulfonamide, optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; R 7 is (C = O) -R 14; A C 1-02 aliphatic group optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; A C 2 -C 12 aliphatic carboxylic acid, esters, thioesters, or amides thereof, all optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; or an N, O or S group such that when taken together with the carboxamide is a urea, semicarbazide, carbamate or thiocarbamate group, all optionally substituted by alkyl or aryl, optionally substituted by at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; R 11 is -OR 11, -SR 12, halogen, -NHOH or -NR 12 R 13, wherein each of R 12 and R 16 is independently hydrogen; an aliphatic or aromatic group optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; A C 1 -C 12 aliphatic amine optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; A C 2 -C 12 aliphatic carboxylic acid, esters, thioesters, or amides thereof, all optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; or R 12 and R 13 together with the N of R 11 are a protein amino acid or cyclic group selected from morpholine, piperidine, piperazine or pyrrolidine, optionally substituted with at least one group selected from hydroxy, alkoxy, halogen, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; R 14 is OH, alkoxy, NH ₂ or NHNH 2; or any agriculturally acceptable salt thereof; together with or in combination with the compound of the invention 36 (a) of formula Π, which are alkyl glycosides, wherein the alkyl group is a mixture of about eight to fourteen carbon atoms and the number of glycoside groups present in the formula is from one to six; (b) the formula ΠΙ, which is a quaternary fatty aminoethoxylate wherein the fatty amine is an alkylamine wherein the alkyl group is a mixture of from about eight to about twenty carbons inclusive, and the ethoxylate is an ethylene oxide monomer of 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; ii) ethoxylated alkylphenol wherein the alkyl is from zero to about twenty carbons inclusive, ethoxylate is an ethylene oxide monomer of from two to twenty moles of ethoxylation; (d) Formula V, which is ethoxylated acetylated diols, wherein the number of carbons in the acetylated chain is from ten to twelve inclusive, and ethoxylate is an ethylene oxide monomer of from ten to thirty moles of ethoxylation; (e) Formula VI, which is a secondary alcohol or ethoxylate, wherein the number of moles of ethoxylate is from seven to fifteen inclusive, including ethylene oxide monomer and alkyl in the secondary alcohol or ethoxylate has from seven to fifteen inclusive; (f) Formula VI, which is an alkoxylated fatty amine oxide, wherein the alkyls are from about six to thirty carbons inclusive; and the number of moles of alkoxylation is from about one to about fifty; (g) of formula V0, which is an alkyldimethylamine oxide, wherein the alkyls are from about six to thirty carbons; (h) Formula IX, which is a fatty alcohol polyglycol ether, wherein the fatty alcohol is a mixture of alkyls of from about six to thirty carbons inclusive; and the number of moles of ethoxylation is in total from about one to fifty; (i) Formula X, which is an esterified coconut polyethoxy ether, wherein the coconut ester is a mixture of alkyls of from about six to about thirty; (j) Formula XI, which is a quaternary ammonium, including an alkyl of C8 to C20 and an agriculturally acceptable anion; (k) the formula ΧΠ, which is quaternary ammonium, having groups which are independently alkyl of one to three carbons and together from two to seven carbons; and from - 37 three to fifteen ethylene oxide and propylene oxide groups and an agriculturally acceptable anion; (l) of the formula Π, which is a diaminoethoxylate with an alkyl of from C8 to C20 and ethoxylation of from one to fifty; (m) formula XIV which is an alkoxylated primary fatty alcohol with an alkyl of from C 13 to C 18 and from 6 to 50 propylene oxide groups; and (n) mixtures of the above compounds. A composition according to claim 1, wherein the compound of formula I is an agriculturally acceptable salt of the following compounds: 3,4,4-trifluoro-3-buten-1-amine or its monohydrochloride salt; N- (3,4,4-trifluoro-3-butenyl) glycine or its monohydrochloride; 2-amino-N- (3,4,4-trifluoro-2-butenyl) propanamide or its monohydrochloride; (S) -2-amino-4- (methylthio) -N (3,4,4-trifluoro-3-butenyl) butanamide or its monohydrochloride; 4,4-difluoro-3-buten-1-amine or its monohydrochloride; 3,4,4-trifluoro-3-butenoic acid or its sodium salt; a combination of 3,4,4-trifluoro-3-butenoic acid; and 3.4.4-trifluoro-3-buten-1-amine in a one to one ratio (1: 1); (S) -2-amino-3-hydroxy-N- (3,4,4-trifluoro-3-butenyl) butanamide or its monohydrochloride; N- (4,4-difluoro-3-butenyl) glycine methyl ester or its monohydrochloride; 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-1-oxo-3-butenyl) glycine; 2 - [(3,4,4-trifluoro-3butenyl) amino] acetamide or its monohydrochloride; or 2-aminoethyl ester 3.4.4-Trifluoro-3-butenoic acid or its monohydrochloride. The composition of claim 1, wherein the adjuvant is (a) alkyl glycosides of formula Π, 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 is from one to two; (b) a quaternary fatty amine ethoxylate according to the formula ΙΠ, wherein the alkyl group of the fatty amine is a mixture of eight to sixteen carbons and the number of moles of ethoxylation is two; (c) the mixture of formula IV is (i) a fatty amine ethoxylate of formula - 38 R 25 N (EO) n H (EO) m H where R ₂₂ represents a mixture of alkyls of from about twelve to twenty carbons inclusive; EO is an ethylene oxide monomer and amam is the number of moles of ethoxylation in the formula and, in total, gives about five to fifteen, and (u) the ethoxylated alkylphenol has the formula wherein O (EO) wH R23 is a mixture of alkyl groups of 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 six to ten; (d) the ethoxylated acetylated diols of formula V have the formula ch ₃ ch ₃ ch ₃ ch ₃ II 1 1 1 C * - + - C — C — C — C — c = c 1 1 I ^{1 1} 1 - C — C — C —cic * 1 1 1 ¹¹ (EO) q 1 (EO) p where * is the number of carbons indicating the total number of carbons in the chain, from ten to twelve carbons inclusive; EO is an ethylene oxide monomer wherein q and p represent the number of moles of ethoxylates in the formula and are added to 30; (e) a secondary alcohol ethoxylate of formula VII is wherein: R 24a represents a hydroxy or ethylene oxide monomer wherein a represents the number of moles of ethoxylates present in the formula and is from nine to twelve inclusive, and C * represents the ends of the carbon chains so that the chain together is a carbon blend having a total of 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 FloMo 3153 (the alkoxylated fatty amine oxide is represented by the formula O 'R R ₂ s - N * - (CHCH ₂ O) _Z , —H (CHCH ₂ O) _Z —H I R where R ₂ represents a mixture of alkyls of from about six to thirty carbons, preferably from about twelve to about 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 in total from one to fifty, preferably five to fifteen); (g) the formula VHI, which is an alkyldimethylamine oxide, preferably Empigen OB (the alkyldimethylamine oxide may be represented by the formula 0 ' R ₂ 6 —N * —CH ₃ ch ₃ where R ₂ 6 is a mixture of alkyls of from about six to thirty carbons, preferably from about twelve to twenty carbons, inclusive; (h) formula IX, which is a lipidic alcoholic polyglycol ether, preferably Genapol T250 or Neodol (the lipidic alcohol polyglycol ether may be represented by the formula R R ₂ -OíCHCH 7-OH - 40 where R 27 represents a mixture of alkyls having from about six to thirty carbons inclusive, preferably from about twelve to twenty carbons inclusive; R represents hydrogen or alkyl of from about one to two carbons inclusive; Z ₂ indicates the number of moles of ethoxylation in the formula and summed from one to fifty, preferably from five to fifteen) (i) formula X, which is a fatty acid esterified polyethoxyether, preferably Kaomul 230, or stearic acid polyethoxylate, preferably Simusol M52 (esterified coconut) the polyethoxy ether and the stearic acid polyethoxylate may be represented by the formula R ₂₈ - CO ₂ - (EO) _{Z 3} - H where R ₂₈ represents a mixture of alkyls having from about twelve to twenty carbons inclusive; EO represents ethoxylation in the formula and ₃ is from five to fifteen; (j) formula XI, which is a quaternary ammonium, which may be represented by formula R29 = K (CH3) (CH 2 Cl 2) Q ⁺ where R 29 represents alkyl from C 10 to C 16 and Q is an agriculturally acceptable anion; (k) the formula ΧΠ, which is the quaternary ammonium which may be represented by the formula RaoRaiRaztfOEO (IPO) ^ Q ⁺ where R 30, R 31 and R ₃₂ are all methyl or one of R _30, R ₃ and R ₃₂ is ((EO) _n and (PO) _n2); EO is ethylene oxide; PO is propylene oxide; n 1 is an integer from one to two; and n ₂ is an integer from six to ten; and Q is an agriculturally acceptable anion); (l) formula ΧΙΠ, which is the diaminoethoxylate represented by formula (EO) n ₃ (EO) n ₄ - 41 where R ₃₃ represents alkyl from C 10 to C 16; and n, ₃ , n ₄ , n ₅ represent the number of moles of ethoxylation in the formula and give a total of five to fifteen; (m) formula XIV, which is an alkoxylated primary fatty alcohol represented by formula R34-O (PO) n6 (EO) n7 wherein »R34 represents alkyl of C13 to C15; EO is ethylene oxide; PO represents propylene oxide; n 1 is an integer from 6 to 9; ηγ is an integer from 4,5 to 6; and r (n) mixtures thereof The composition of claim 2, wherein the compounds are (a) alkyl glycosides, which is APG 325, wherein the number of glycoside groups is one to two and the alkyl group is a mixture of nine to eleven carbons; (b) a quaternary fatty aminoethoxylate which is cocomethylammonium chloride or Ethoquad C / 12; (c) a mixture which is Improve®; (e) a secondary alcohol ethoxylate which is Tergitol 15-S-9 or Tergitol 15S-12; or (f) mixtures thereof. in The composition of claim 4, wherein the adjuvant is alkyl glycosides of formula Π, wherein the alkyl group is a mixture of from about nine to eleven carbons inclusive, and the number of glycoside groups in the formula is from one to two. 6. The composition of claim 5 wherein formula I is N- (3,4,4-trifluoro-3-butenyl) glycine or a monohydrochloride salt thereof. 7. The composition of claim 5 wherein formula I is 3,4,4-trifluoro-3-buten-1-amine or a monohydrochloride salt thereof. - 42 A composition for controlling infestation of plants by nematodes, insects or mites, characterized in that it comprises an effective amount of the composition according to claim 1 in an agriculturally acceptable carrier. A composition for controlling infestation of plants by nematodes, insects or mites, characterized in that it comprises an effective amount of the composition according to claim 5 in an agriculturally acceptable carrier. in A composition for controlling infestation of plants by nematodes, insects or mites, characterized in that it comprises an effective amount of the composition according to claim 6 in an agriculturally acceptable carrier. 11. A composition for controlling infestation of plants by nematodes, insects or mites, comprising an effective amount of the composition of claim 7 in an agriculturally acceptable carrier. 12. A method of controlling nematode, insect, or mite infestation of plants, comprising applying an effective amount of the composition of claim 1 to the plant locus. in A method for systemically controlling a plant infestation by nematodes, insects or mites, comprising applying an effective amount of a composition according to claim 9 which has been and / or is transformed after application to have the polarity required for mobility through the floem without the efficiency of nematode disposal was reduced. The process of claim 12 wherein the compound of formula I in the mixture is N- (3,4,4-trifluoro-3-butenyl) glycine or a monohydrochloride salt thereof. 15. The process of claim 12 wherein the compound of formula I in the mixture is 3,4,4-trifluoro-3-buten-1-amine or a monohydrochloride salt thereof.