CZ129196A3 - Improved preparations for intestinal worm extermination - 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

Improved pesticides

QfcLaat.-, Lg.chni.ky

The present invention relates to unexpectedly improved novel compositions comprising a compound which acts on the leaves in the upper systemic control of plant pests, i.e. parasitic nematodes, insects and mites. The composition is a compound, especially as disclosed in U.S. Patent Application No. 07 / 827,231, filed February 3, 1992, which is a continuation of Application No. 07 / 663,218, filed March 1, 1991, which is incorporated herein by reference. published in PCT / US92 / 1474, in combination with an adjuvant selected from conventional wetting, dispersing or emulsifying agents used in agricultural preparations. The invention also relates to a method for controlling nematodes, insects and mites and to the use of the new compositions.

Prior art

The use of wetting, dispersing and emulsifying agents in formulations containing fluorinated alkenes is well known. For example, the aforementioned U.S. patent application discloses the use of a mixture of dodecylbenzenesulfonate calcium with a nonionic six molar condensation product of ethylene oxide and nonylphenol, a mixture of dodecylbenzenesulfonate calcium with a nonionic thirty molar condensation product of ethylene oxide and nonylphenol,

See also the aforementioned patent application, U.S. Pat. U.S. Patent 4,950,666 and U.S. Pat. 4,876,285 for other typical surfactant wetting, dispersing and emulsifying agents used in agricultural formulations. Examples of such agents are alkyl and alkylarylsulfonates and sulfates and their sodium salts; alkyl amide sulfonates including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and ethylene oxide addition products of such esters; and addition products of long chain mercaptans and ethylene oxide.

Further, U.S. Pat. U.S. Patent Nos. 5,237,100, 5,236,933 and 5,232,949 disclose nematicides in compositions with adjuvants, including co-agents such as piperonyl butoxide or sesamex.

However, there is still a need for nematicides, insecticides and acaricides (mite control agents) that are better absorbed by plants, have better systemic mobility and, if possible, low effective doses of use.

The essence 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 a compound of composition I having the structure

X \ -c- (ch ₂ ) „- o / I *

Y Z where: η = 1, 3, 5, 7, 9, or 11;

q is ch ₂ nhr _s , ch ₂ no ₂ , ch ₂ n = chr ₂ , ch ₂ n = c = o, ch ₂ n * r ₃ r ₄ r ₌ w-, or (C = O) -R _xx ;

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 _xx then each of X, Y and Z is F;

W— is an agriculturally acceptable anion;

R ₂ is an aromatic group;

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

R _g is hydrogen; an aliphatic group optionally substituted by at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; amino acid amide Q; (C = O) -R 2; C _{X X 2} -C aliphatic amines, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, phenyl; C ₂ -C _{x 2} aliphatic carboxylic acids, their esters, thioesters and amides, all optionally substituted by at least one group selected from hydroxy, alkoxy, halo, 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 _g considered with nitrogen from Q is guanidine; hydrazine; alkyl or arylhydrazine, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; or an alkyl or aryl sulfonamide, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl;

R is a (C = O) -R; C 1 -C aliphatic group optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; C ₂ -C _i2 aliphatic carboxylic acid, esters, thioesters 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 an N, O or S group such that when considered with a carboxamide it is a urea, semicarbazide, carbamate or thiocarbamate group, all optionally substituted by an alkyl or aryl group optionally substituted by at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl;

R is -OR. -SR 1, halogen, -NHOH, or -NR 1, R 2, wherein each X XX 2 X 2 3- 2 X 3 of RR is independently hydrogen; an aliphatic or aromatic group optionally substituted by at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; A C _x -C _x aliphatic amine optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; C ₂ -C _x aliphatic carboxylic acid, its esters, thioesters or amides, all optionally substituted by at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl - and phenyl-; or, ¾

R _xa and R _X3 taken together with N of R _xx are a protein amino acid or cyclic group selected from morpholine, piperidine, piperazine or pyrrolidine optionally substituted by at least one group selected from hydroxy-, alkoxy-, halo-, nitro-, amino-, thio-, alkylthio-, carboxy. alkoxycarbonyl and phenyl;

R _X4 is OH, alkoxy, NH _a or NHNH _a ; or any agriculturally acceptable salt thereof;

together with or in combination with an activity-enhancing amount of adjuvants according to (a) of formula II, which are alkyl glycosides, wherein the alkyl group is a mixture of about eight to fourteen carbon atoms and the number of glycosidic groups present in the formula is from one to six, but preferably one or two more preferably APG 325 or APG 225, wherein the alkyl group is a mixture of nine to eleven carbons or Atplus 258 or also Rhodonate LMO, which is a coconut oil saccharoglyceride or Rhodonate MLP 704, which is a modified LMO saccharoglyceride;

(b) Formula III, which is a quaternized fatty aminoethoxylate, wherein the lipid amine is an alkylamine, wherein the alkyl group is a mixture of from about eight to twenty carbon atoms, more preferably a mixture of from eight to twelve carbon atoms, as found in cocomethylammonium chloride, and most preferably Ethoquad C / 12 (quaternised lipid aminoethoxylate, which may be represented by the formula (EO) xH (EO) yH Z

Λ where:

_And R is a mixture of alkyl groups having from about eight to twenty two carbon atoms after purchasing;

R _2x is alkyl of one to four carbons inclusive;

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

Z 'is an agriculturally acceptable anion;

(c) of formula IV, which is a mixture of lipid aminoethoxylate and ethoxylated alkylphenol, preferably Improve ^R (lipid aminoethoxylate may be represented by formula

R ₂₂ N ^ (EO) nH (EO) mH where:

R ₂₂ represents a mixture of alkyls from about six to thirty carbons inclusive, but preferably from twelve to twenty carbons inclusive,

ΕΟ is 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, but preferably from five to fifteen, and the ethoxylated alkylphenol may be represented by the formula * 23 ~

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

(EO) q (ÉO) p is the number of carbons, which indicates 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 numbers that indicate the number of moles of ethylene oxide monomer in the formula and are 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 Tergitol ^R 15-S-7, Tergitol ^R 15-S-9 or Tergitol ^R 15-S-12 and preferably Tergitol ^R 15-S-12 (formula VI can be represented as follows:

Rut

CH

CH, h ₃ / CH.

CH, Xdl

AND

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, but preferably from nine to twelve inclusive, and C 'represents the ends of the carbon chain so that together the chain forms a mixture of carbons having a total of from eleven to fifteen carbons inclusive, but preferably from twelve to fourteen carbons inclusive);

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

0 'R'

R25 (CHCHiOV-H (CH ₂ O1-H

J.

where

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

R 1 is hydrogen or methyl; and after ζ _χ denote the numbers of moles of alkoxylation or, in particular, 101.0 ethoxylation in the formula and are in the sum of from one to fifty, but preferably from five to fifteen);

(g) of formula VIII, which is alkydimethylamine oxide, preferably Empigen OB (alkyldimethyloxide may be represented by formula

0 '

AND

R ₃₅ -N ⁺ -CH ₃ ch ₃ where

R _2e 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 lipid alcoholic polyglycol ether, preferably Genapol T250 or Neodol (the lipid alcoholic polyglycol ether may be represented by formula

R '

R _{; 7} -O (CHCH _; t-OH 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 1 represents alkyl from about one to two carbons inclusive;

Z ₂ indicates the number of moles of ethoxylation in the formula and is a sum of from one to fifty, preferably from five to fifteen) (i) of formula X, which is a fatty acid esterified polyethoxyecher, preferably Kaomul 230, or stearic acid polyethoxylate, preferably Simusol M52 (esterified coconut polyethoxyether and stearic acid polyethoxylate can be represented by the formula

R ₂₃ -CO ₂ - (EO 2 -H where

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

EO represents ethoxylation in formula and ₃ is from one to fifty, preferably from five to fifteen); or (j) formula XI, which is quaternary ammonium, preferably

Dodigen 226 (quaternary ammonium can be represented by the formula

R ₂₉ -N "(CH ₃ ) ₂ (CH ₂ (C ₆ H ₅ )) Q 'wherein R ₂₉ represents alkyl from C 8 to C 20, preferably C 10 to

C16 and Q is an agriculturally acceptable anion;

(k) formula XII, which is a quaternary ammonium, preferably Dodigen 4022 (quaternary ammonium may be represented by the formula * 30 * 3ΐ * 32Ν ⁺ (ΕΟ) _ηι (ΡΟ) _η2 Q · a

!

wherein R _and R ₃₁ and R ₃₂ are independently alkyl having from one to three carbons, which in total from two to seven carbons, preferably all methyl, or one of R _3o, R _31, ^R 32 is ((EO ) (PO) _n2 ); EO is ethylene oxide; PO is propylene oxide; her

n 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);

(l) formula XIII, which is a diamine ethoxylate, preferably a

Ethoduomeen (diamine ethoxylate can be represented by the formula j * 33

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

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

R CXPO) ^ wherein _R34 represents alkyl from C8 to C18, particularly 'then C13 to C15; EO is ethylene oxide; PO represents propylene oxide; n _e is an integer from 6 to 50, but preferably from 6 to 9; is an integer from 4 to 8, preferably from 4.5 to 6; and (n) mixtures of the foregoing.

The most suitable adjuvant is in the composition represented by Improve ^R and Tergitol ^R 15-S-12.

A suitable compound of formula I is an agriculturally acceptable salt of 3,4,4-trifluoro-3-buten-1-amine, especially its monochloride; furthermore N- (3,4,4-trifluoro-3-butenyl) glycine, in particular its monochloride; further 2-amino-N- (3,4,4-trifluoro-2-butenyl) propanamide, in particular its monochloride; furthermore (S) -2-amino-4- (methylthio) -N- (3,4,4-trifluoro-3-butenyl) butanamide, in particular its monochloride; further 4,4-difluoro-3-buten-1-amine, in particular its monohydrochloride; 3,4,45-trifluoro-3-butenoic acid and in particular its sodium salt; a combination of 3,4,4-trifluoro-3-butenoic acid and 3,4,4-trifluoro-3-buten-1-amine in a ratio of one to one (1: 1); furthermore (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 ratio of one to one (1: 1); further N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine; 2 - [(3,4,4-trifluoro-3-butenyl) amino] acetamide, especially its monochloride; 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 especially its monohydrochloride salt; or N- (30,4-trifluoro-1-oxo-3-butenyl) glycine and the most suitable active ingredient is N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine.

Surprisingly, the combination of a compound of formula I and an auxiliary active ingredient of formulas II, III, IV, V, VI in amounts of 0.05% to 20%, but less than an amount toxic to the infested plant, or mixtures thereof increase the efficacy of the compound. according to formula I against parasitic, especially nematode, infestation when applied to the foliage of infested plants, by an unexpected difference compared to the compound of formula I with other known surfactant wetting, dispersing and emulsifying agents, which are commonly used in agricultural preparations. One of ordinary skill in the art should be able to find the percentage of adjuvant effective for a particular compound of a given formula. The percentage is expressed by volume.

Therefore, the present invention is also a method for controlling nematodes, insects and acarides and for using these novel compositions for controlling nematodes, insects and acarides comprising an action against nematode, insect and mite infestation either on the leaves of infested plants or in soil with a compound of formula I. with an activity-enhancing amount of an adjuvant of formula II, which is an alkyl glycoside, preferably APG ^R 325 or Atplus 258 in an amount of from 0.25 to 1%; further with an adjuvant according to formula III, which is ethoxylated cocomethylammonium chloride, in particular Ethoquad C / 12 in an amount of from 0.25 to 1%; further with an adjuvant of formula IV, which is a fatty aminoethoxylate, preferably Improve ^R in an amount of from 0.25 to 2%; further with an adjuvant according to formula V, which is acetylene diolethoxylate, 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-7 in an amount of about 0.5%. 12 in an amount of 0.5%.

Exemplary embodiments of the invention

The novel compositions of this invention are useful as unexpectedly effective systemic compositions for removing nematode, insect and mite infestation of a plant. These preparations can be used in a lower effective ratio of the compound of formula I to the foliage area, while maintaining the effectiveness of removing nematode, insect and mite infestations. That is, when applied to the foliage or stems of a plant, they penetrate the bast (phloem) and xylem of the plant and kill nematodes, insects or mites elsewhere in the plant.

These present methods for the systemic removal of nematodes, insects and mites utilize the compositions of the present invention with unexpected penetration through 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 bovine tissue penetration, whereby the compound of formula I is moved down the plant without losing the elimination activity of the compound of formula I against nematodes, insects or mites.

In order to effectively systemically control nematodes and other pests by spraying the above-ground surfaces of the plant, the present compositions can improve the ability of the active ingredient to penetrate the cuticle of the plant's foliage or stem, penetrate the bast tissue and remain there long enough to be transported by the plant to untreated parts including roots. There, such a plant of formula I may be released or in some way come into contact with the pest to the extent that it kills or repels the pest, and the damage that the pest would cause to the plant is limited or completely ruled out. During this process through the plant, 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 may be designed so that when a compound is placed on and prior to absorption into a plant, it may undergo reactions that provide a compound that is readily absorbable, transportable, and effective in preventing pest damage. These are, for example, those compounds having UV-labile protecting groups which, when exposed to natural light, react and give active and mobile derivatives of the compounds of formula I. Another example is silylated amino derivatives.

Thus, what is placed on the leaves or stems of a plant need not be a preparation in which what is currently being transported or is currently killing the pest is a compound of formula

I. The methods of the present invention provide compositions that can be transformed by chemical and biological reactions to have the appropriate polarity for systemic activity.

Although the methods of the present invention involving the application of a composition to a plant locus, preferably to leaves, are known, the present compositions are surprising combinations of compounds of formula I as defined above and selected adjuvants of formulas II, III, IV, V, VI or mixtures thereof. These combinations are for those adjuvants that cannot be predicted from those commonly used in agriculture.

From the point of view of nematode control, preference is given among the compounds of formula I to those where n is 1 and X, Y and Z i are all F, and Q 1 is then CH ₂ NH ₃ + W-, i.e. the salt 3,4,4-trifluoro- 3-buten-1-amine. When Q 1 is CH ₂ NHR ₆ , R ₆ is preferably a peptide-linked alpha-amino acid, more preferably a protein amino acid. When Q 1 is (C = O) -R _XX , R _xx is preferably hydroxyl and thus the compound is 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 is 3,4,4-trifluoro 3-buten-1-amine-3,4,4-trifluoro-3-butenoate.

W- can be any agriculturally acceptable anion. This includes, but is not limited to, chloride, iodide, bromide, oxalate, sulfate, phosphate, citrate, acetate, or fluoroalkenecarboxylate, for example, F ₂ C = CFCH ₂ COO-.

In addition to the compounds specifically described above, all agriculturally acceptable salts of the compounds that fall within the scope of this invention are included. For example, a compound of the invention having a free amino group may also exist as a protonated form that may associate with various anions, such as (but not limited to) chloride, bromide, iodide, phosphate, oxalate, sulfate, citrate, and acetate. In addition, a fluoroalkenecarboxylate 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, alkaline earth metals such as sodium, calcium and potassium; magnesium; or quaternary ammonium ions such as ammonium, mono-, di-, or trialkylammonium, for example isopropyl ammonium, or pyridinium. Moreover also fluoralkenylammoniový ion, such as F ₂ C = CFCH ₂ CH ₂ NH _ _3j may be cat) risen. All such compounds and others having similar agriculturally acceptable characteristics are provided by the present invention.

The term halo, halide or halogen as used herein means fluorine, chlorine, iodine or bromine or compounds thereof.

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

The term alkoxy means a lower alkyl group attached through an oxygen atom. The term alkylthio means a lower alkyl group attached through 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, its esters, thioesters and amides means an aliphatic group wherein at least one carbon is a carboxyl group, -COOH, or is a lower alkyl ester, lower alkylthioester or amide thereof.

The term aromatic means phenyl, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl. It should be clear to one of ordinary skill in the art that heterocycles may also be used as aromatic groups, for example, thiadiazole, pyridine, thiazole, isothiazole, oxazole, pyrazole, triazole, benzothiazole, thiophene, furan, and the like, all of which may be also optionally substituted.

For purposes herein, the phrase amide Q of amino acid (or Q 2) means that R _e is an amino acid linked by a peptide bond to N of CH ₂ NHR _S. This amino acid may be natural, i.e. proteinaceous, or non-naturally occurring. The amino group of an 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 lower alkyl or phenyl, which may be optionally substituted. The term alkyl or arylsulfonamide means a sulfonamide group substituted with lower alkyl or phenyl, which may be optionally substituted optionally.

SYNTHESIS OF THE COMPOUND

Methods for preparing the compounds of formula I of this invention are described in PCT Application No. PCT / US92 / 1474, which is therefore incorporated herein by reference.

PREPARATIONS

In normal use, the prepared substances are not usually used alone without further additives or dilutions, but are usually used in a suitably formulated preparation compatible with the method of use and containing an effective amount of the prepared substance. The formulations of the present invention may be mixed with additional agriculturally acceptable surfactants and carriers normally used to facilitate dispersion of the active ingredients, confirming the recognized fact that the final formulation and method of application may affect the activity of the formulation. The present preparation can be used, for example, in the form of sprays, powders or granules for areas where extermination of pests is desired, the type of application varying according to the type of pest and the surroundings. Thus, the compositions of the present invention can be prepared as large diameter granules, as dusts, as wettable powders, as emulsifiable concentrates, as a solution, 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 granule particles are relatively large, with a typical diameter of about 400-2500 microns. The particles are either impregnated / from the solution with a substance prepared according to the invention or coated with this substance, the adhesive sometimes being used. The granules generally contain 0.05-10%, but preferably 0.5-5% of active ingredient.

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

The compositions of the present invention may be prepared in the form of liquid concentrates by dissolving or emulsifying in suitable liquids and in the form of solid concentrates as additives in talc, clays and other known solid carriers used in agricultural chemistry. Concentrates are preparations containing about 5-50% of 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 which includes surfactant dispersing, emulsifying and wetting agents which fall outside the scope of the term adjuvant as defined herein, but even higher concentrations of the active ingredient or its excipient may be used experimentally. For practical use in the form of sprays, the concentrates are diluted with water or other liquids, or solid carriers are added for use as powders.

A typical formulation in the form of a 50% wettable powder consists of 50.0% (w / w) of the prepared substance, 22.0% attapulgite diluent, 22.0% kaolin diluent and 6.0% sodium salts of sulfonated Kraft lignin emulsifier

Typical carriers for solid concentrates (also called wettable powders) include rolling clay, clays, silicates and other highly absorbent 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 active compound and 72 parts of attapulgite clay.

The production of concentrates is useful for transporting the low melting products of this 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 emulsifying other concentrates which are homogeneous liquids or pasty preparations easily dispersed in water or other liquid carriers. They may consist only of the active ingredient with a liquid or solid emulsifier or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isoforms or other relatively non-volatile organic solvents. These concentrates are dispersed in water or other liquid carriers for use and are normally used as sprays on the areas to be treated.

A typical emulsifiable concentrate formulation of 50 grams per liter consists of 5.9% by weight of the substance prepared according to the invention and contains as emulsifiers 1.80% of a mixture of dodecylbenzenesulfonate calcium salt and nonionic

A 6 molar condensation product of ethylene oxide and nonylphenol, 2.70% of a mixture of dodecylbenzenesulfonate calcium salt and a nonionic 30 molar condensation product of ethylene oxide and nonylphenol, 1.50% of a nonionic polyalkylene glycol ether paste and 88.10% of a purified xylene solvent.

Typical surfactant wetting, dispersing and emulsifying agents for use in the adjuvant formulations of the present invention are other agricultural formulations which include, 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; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated kerosene; fatty acid esters of polyhydric alcohols and ethylene oxide addition products of these esters; and addition products of long chain mercaptans and ethylene oxide. The surfactant normally contains about 1-15% by weight of active compound. Thus, in the present compositions, the surfactant together with the adjuvant of the present invention may reduce the percentage of other surfactants used to prepare the composition.

Other useful formulations include simple solutions of a substance of the invention in a solvent in which the substance is completely soluble at the desired concentration, such as water, acetone or other organic solvents. The preferred formulation for use on foliage is an aqueous solution, more preferably containing a sufficient amount of adjuvant to provide an increased parasitically active compound of formula I and also to provide the desired concentration. However, glycerol and other surfactants such as Tween ^R 20, most preferably 1% glycerol and 0.1% Tween ^R 20 may also be included in the formulation.

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

METHODS OF USE

The present invention provides methods for controlling and repelling various pests which parasitize agricultural crops, in particular nematodes, insects and mites. Infestation of a plant with any of these pests can be prevented by applying an effective amount of any of the compounds of this invention to a particular site in the plant. The application can be carried out in various ways, including applying the compound or a preparation containing the compound to the soil before or under the planted plants or in case of danger to the seeds or parts thereof before and / or during sowing and to the leaves, stems or trunks of plants or trees. The treatment can be performed several times during the growth season with one or two days between applications. The appropriate schedule of applications will depend on the life cycle of the pest, 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 performed on a variety of crops. Their list 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 this invention can be used against any of the phytopathogenic nematodes. The list of insects that can be exterminated or repelled by the methods of this patent includes, but is not limited to, leaf pests of green peach aphid and soil pests such as southern corn rootworm. Mites that can be controlled by the methods of the present invention include, but are not limited to, two spotted arachnid mites. Although no specific tests using the above formulations have been performed, tests performed with several antiparasitic active compounds of the present invention have shown no significant effect against tobacco bud worm or Colorado potato beetle.

It has been found that a suitable amount when applying a preparation where Compound I is enhanced by combination with the active adjuvant by 0.25 to 2% by weight according to formula II is, for example, in this combination of about 28 to 56 mg / m ² to achieve such a level of extinction. (80-100%), which is comparable to 112 mg / m ² Triton CS7 for root nematode control.

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 applications, a continuous sprayer was used to specify the application procedures and volumes used in the field (233 liters per hectare). Twenty milliliters of each test solution was prepared in water estimating that 10 ml was currently used on 5 plants in one treatment (five or six inch pots, soil mixture: 50% Metromix, 25% fine sand, 25% medium coarse sand, with 136 g Osmocot 14-145-14 per cubic foot, one three to four week old Rutger 's tomato per pot). Plants were often transplanted into five- or six-inch pots; at least one day was left between transplanting and treatment. The pots were placed along a 5 foot long central belt of a continuous sprayer. One 8001E nozzle tip was placed in the arm directly above the plants and adjusted to a position 6 to 9 inches above λ

foliage. The pressure was set at 15 psi so that the nozzle flow was 4.2-4.5 ml / sec. The spray rate was adjusted to about 95 on the dial so that the LCD rate was read 1.75-1.85. Tests were usually based on 20 treatments and a control treatment 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 excavated in close proximity to the plant stem for the application of Meloidogyne incognita nematode eggs. Using a large syringe, 30 ml of egg suspension (720 eggs / ml, 21,000 eggs per plant) was distributed between all the holes in the pot. Prior to inoculation, the plants were randomly distributed and then transferred to either greenhouse 16 or 21 for 3-4 weeks of incubation. The daily temperatures in the greenhouse were 25-30 ° C and the additional light from above simulated the length of the day 12 hours. During the evaluation, the leaves were examined for phytotoxic effects and then the stems were cut at a height of +2 inches above soil level. Excess soil was shaken from the root ball and the soil was washed well from the roots with water using a high pressure nozzle. The roots were visually evaluated for the intensity of proliferation and the frequency of cecidia, and each replicate was assigned a value of 0-100% expressing the severity of the disease. This data was entered into the SAS program and the results were compared with the 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 below with their active ingredient Λ and percentage:

Table 1 Adjuvant % a., p. Active folder NH3SO4 100 ammonium sulfate APG® 225 70 alkyl glycoside APG® 300 50 alkyl glycoside APG® 325 70 alkyl glycoside Arquad T 127W 27 trimethyl 1. ammonium chloride Buffercide 1 0 orthophosphoric acid Cayuse 42.5 polyglycol ether phosphate> + 16.5 ammonium salts Improve® 64 fatty amine methoxylate + 14 ethoxylated nonylphenol

CropOil 1 7 polyoxoethylated polyol fatty acid ester + polyol fatty acid ester Ethoquad C / 25 100 cocomomethylammonium chloride 15EO Ethoquad C / 12 100 cocomomethylammonium chloride 2EO EaicoI® CC9 100 propoxylated quaternary am; Glycerine 100 glycerine MON 0818 1 5 polyoxyethylene alkylamine Nitrogen 28 28% nitrogen nonylpheno! 4EO 100 , .. ... ..I - nonylphenol 4EO nonylphenol 6EO 100 nonylphenol 6EO nonylphenol 8EO 100 nonylphenol 8EO nonylphenol 10EO 100 ^: nonylphenol ÍOEO nonylphenol 12EO 100 nonylphenol 12EO R-11 90 octylphenoxyethano1 Silwet L77 100 organosilicon ethoxylate Surfynol 465 100 10 moles of acetylated EO diolethoxylate Surfynol 485 100 30 moles of acetylated EO diolethoxylate Tergitol® 15-S-3 100 C _1x -C ₁₅ secondary alcohol EO Tergitol® 15-S-5 100 ^c xx ^-c xSecondary alcohol EO Tergitol® 15-S-7 100 ^c xx ”C _X3 secondary alcohol EO Tergitol® 15-S-9 100 ^C xx ^C xs. ^secondary alcohol EO

Tergitol® 15-S-12 100 ^c 11 ~ C _{is the} secondary alcohol EO Tergitol® 15-S-15 100 C _{i; L is} -C seconds alcohol EO Tween 20 1 00 polyoxyethylene (20) sorbitan monolaurate Triton® CS-7 60 alkylaryl polyethoxylate and sodium alkylate sulfonated with alkyl Varion CDG-K 28 lauryl betaine

Following! results using the above methods show the compounds of formula I, i.e. 2-amino-N- (3,4,4-trifluoro-2-butenyl) propanamide, monochloride salt (designated A below), (S) - 2-amino-4- (methylthio) -N- (3,4,4-trifluoro-3-butenyl) butanamide monochloride (designated B below), 3,4,4-trifluoro-3-butenoic acid, sodium salt (designated C below), N- (3,4,4-trifluoro-oxo-3-butenyl) glycine (designated D below),

2 - [(3,4,4-trifluoro-3-butenyl) amino] acetamide monohydrochloride (designated E below), 3,4,4-trifluoro-3-butenoic acid 2-aminoethyl ester monohydrochloride (designated F v hereinafter), with which the selected adjuvants of the present invention provide an unexpected potentiation of the compound of formula I. (* FOR I)

Table 2 continuation FOR 1 * Adjuvant Adj% 1 6 8 4 2 B none 35 38 B none 29 1 9 B none 28 13 B none 35 22 B none 38 24 B none 24 9 B and none 1 9 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 (ai) 88 49 B APG® 300 .25 37 1 6 B APG® 300 .25 (ai) 58 7 B APG® 300 .5 73 1 9 B APG® 300 1 67 40 · “ B APG® 300 1 (aí) 92 55 B APG® 325 .25 88 49 B APG® 325 .25 (ai) 64 9 B APG® 325 .5 74 6 9 B APG® 325 1 70 29 B APG® 325 1 (ai) 96 47 B Arquad T .25 (ai) 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 7 B CS7 .5 98 33 3 B CS7 .5 81 28 13 B CS7 .5 81 24 1 1 B CS7 .5 92 62 21 B CS7 .5 51 1 8 9

Β CS7 .5 (ai) 95 58 21 Β CS7 -5 (ai) 93 63 54 Β CS7 • 5 (ai) 100 81 21 Β CS7 .5 (ai) 50 1 1 Β CS7 .5 (ai) 55 1 5 Β CS7 .5 (ai) 55 13 Β CS7 + NH ₃ SO ₄ .5 + 2 23 1 4 Β CS7 + 28% N .5 + 2 1 7 8 Β CS7 .5 90 40 Β Emcol® CC9 1 5 5 Β Emcol® CC9 5 1 8 5 Β Ethoquad C / 12 .25 91 Β Ethoquad C / 12 .25 (ai) 67 1 6 Β Ethoquad C / 12 .5 91 Β Ethoquad C / 12 1 98 Β Ethoquad C / 12 1 (ai) 79 50 B Β Ethoquad C / 25 1 21 8 Β Ethoquad C / 25 5 38p 28 Β Ethoquad C / 25 2.5 (ai) 36 1 1 Β Ethoquad C / 25 1 + Surfynol 465 .5 (ai) 62 26 C Glycerine 1 (ai) 32 4 0 D Glycerine Sludge) 61 27 Β Improve® .25 7 3 1 0 Β Improve® .25 1 00 7 3 1 5 Β improve® • 5 80 23 Β Improve® .5 93 30 Β Improve® .5 100 98 28 Β Improve® • 5 (ai) 94 56 Β Improve® • 5 (ai) 96 62 Β Improve® • 5 (ai) 93 34 Β Improve® 1 80 20 Β Improve® 1 100 91 28 Β Improve® 1 (ai) 99 74 Β Improve® 2 9 1 46 Β Improve® 2 83 38 Β Improve® 2 100 88 48 Β Improve® .5 (ai)

♦ glycerin 1 (ai) 73 3 7 Ε Improve® • 5 (ai) 97 93 Ε Improve® .5 (ai) 97 8 6 54 C Improve® • 5 (ai) 100 9 9 93 C Imorove® .5 (ai) 97 97 C Improve® .5 {ai) 100 8 3 38 C Improve® .5 (ai) ♦ glycerin 1 (ai) 68 44 D Improve® .5 [ai) 100 99 92 Table 2 continuation * FOR 1 Adjuvant A d j% 1 6 8 4 2 D Improve® .5 (ai) 100 96 D Improve® .5 (ai) 92 37 21 D Improve® • 5 (ai) ♦ glycerin 1 (ai) 88 80 51 AND Improve® 5fai) 97 8 8 59 with ......... j F Improve® .5 100 8 7 F Improve® • 5 (ai) 19 F Improve® .5 (ai) 76 46 F Improve® 1 100 9 4 B MON 0818 .25 42 26 B MON 0818 .25 6 9 22 B MON 0818 1 35 13 B 28% N 42 6 B 28% N 2 5 6 12 B nonvlphenol 4EO .5 (ai) 1 1 9 B nonylphenol 6EO -5 (ai) 20 1 8 B nonylphenol 8EO .5 (ai) 29 4 B nonylphenol IOEO • 5 (ai) 1 8 8 B nonylphenol 12EO • 5 (ai) 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 1 8 23 B Silwet L77 2 23p 9p

β Silwet L77 5 62p 26p 8 Silwet L77 5 48p 32p Β Silwet L77 .25

Table continue-in 2 ánl * FOR 1 Adjuvant Adj % 1 6 8 4 2 + MON 0818 .25 5 4 22 B Silwet L77 .5 + MON 0818 .25 4 7 18 B Surfynol 455 1 1 8 1 5 B Surfynol 465 5 33p 5p B Surfynol 485 .25 (ai) 6 7 1 1 B Surfynol 485 , 25 (ai) 5 7 1 4 B Surfynol 485 .5 (ai) 8 3 13 B Surfynol 485 1 (ai) 7 1 30 B Surfynol 485 1 (ai) 92 51 B Tergitol® 15-S-3 .5 (ai) 49 7 B Tergitol® 15-S-5 .5 (ai) 51 21 B Tergitol® 15-S-5 • 5 (ai) 40 0 B Tergitol® 15-S-7 • 5 (ai) 86 49 B Tergitol® 15-S-7 • 5 (ai) 74 26 F Tergitol® 15-S-7 5 (ai) 35 B. Tergitol® 15-S-9 .5 (ai) 90 23 B Tergitol® 15-S-9 • 5 (ai) 91 58 B Tergitol® 15-S-12 .5 (ai) 8 8 9 B Tergitol® 15-S-12 .5 (ai) 100 78 B Tergitol® 15-S-12 • 5 (ai) 96 58 B Tergitol® 15-S-12 .5 (ai) 96 60 B Tergitol® 15-S-12 .5 (ai) 83 54 C Tergitol® 15-S-12 .5 (ai) 97 76 C Tergitol® 15-S-12 .5 (ai) 97 80 37

C Tergitol® 15-S-12 .5 (a <) + glycerin 1 (ai) 91 68 29

I Table 2 continuation ‘FOR 1 Adjuvant Adj % 1 6 8 4 2 D Tergitol® 15-S-12 .5 (ai) 99 88 D Tergitol® 15-S-12 .5 (ai) 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 (ai) 7 4 5 B Tween 20 .25 36 7 B Varion .25 (ai) 47 0

p = phytotoxicity recorded on leaves

Bold% efficacy indicates 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 1, except that (ai) in the column% Adj means the volume of adjuvant from Table 1 is adjusted to the concentration of the auxiliary active ingredient.

The surfactants or wetting agents listed above are sold under the following names: APG ^R is sold by Henkel APG, Arquad is sold by Akzo, Chemical Division, Buffercide is sold by Custom Chemicals. Cayuse ^R is sold by Wilbur-Ellis Co. Improve ^R is sold by Dow-Elanco. Cropoil is available from a variety of sources. Ethoquad is sold by Akzo, Chemical Division,

Emcol is available from Witco Corp. Organics Div., 28% nitrogen can be prepared from common nitrogen-containing compounds. Nonylphenol is sold, for example, by Witco S.A. R-1 + is available from Wilbur-Ellis Co. Silwet is from Union Carbide Corp., Special Chemicals Div. Surfynol is from 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 were also used to evaluate the effectiveness of the root-knot nematode control in the evaluation of the adjuvants which are combined with the compound of formula I, specifically for example N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine. on tomato roots when a mixture of adjuvant and compound is applied to the foliage of young plants.

Tomato plants (Rutgers cultivar) were grown one plant at a time in 6 cm diameter plastic pots containing a mixture of equal parts of fine sand, coarse sand, alluvial soil and commercial flower soil.

Mixtures of adjuvanted compound were prepared by adding the compound to water to 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 on the leaves and stems using a continuous sprayer that simulates the application procedures used in the field. 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. For each treatment, three plants were sprayed and then air-dried and left under fluorescent lamps for 15-18 hours before cultivation. All plants were then inoculated with mature root-knot nematode eggs containing JI larvae, 8,000 eggs per plant were applied 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 inside 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 signs of phytotoxicity and assigned a ratio of 0 to 3, where 0 = no damage, 1 = mild spotting or chlorosis, 2 = mild damage, but no growth inhibition, 3 = severe damage and stunting. After three weeks of incubation as described above, the plant roots were washed and examined for the severity of nematode disease. Each root system was evaluated individually - a visual estimate of the percentage of root system damaged by nematode growth was determined and assigned values of 0, 3, 5, 10, 25, 50, 75 or 100% root damage.

Tested adjuvant business name chemical name of the concentration Atplus 258 alkyl polyglucoside 62% a.s. CS-7 alkylaryl polyethoxylate and Na salt alkyl sulfonated with an alkyl 60% a.s. Dodigen 226 cocoalkyldimethylbenzyl- Dodigen 4022 ammonium chloride 50% a.s. Emcol XE 1656 alkoxylated fatty amine oxide 7 0% a.s. Build OB alkyldimethylamine oxide 30% a.s. Ethvlan CPG 945 modified alcohol alkoxylate 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. + ethyxylated nonylphenol 14% a.s. Kaomul 230 esterified coconut polyethoxyether 10 0% a.s. piperonyl butoxide 100% a.s. Rhodonate LMO coconut oil based saccharoglyceride 100% a.s. Rhodonate MLP704 modified LMO saccharoglyceride 100% a.s. Simusol M52 polyethoxylated stearic acid 100% a.s. Ethoduomeen ethoxylated alkylamine 100% a.s. Ethomeen C-15 ethoxylated alkylamindiamine 100% a.s.

Manufacturers of tested adjuvants

Atplus 258 Imperial Chemical Industries Triton CS-7 Rohm & Haas Co. Dodigen 226 Hoechst AG Dodigen 4022 Hoechst AG Emcol XE 1656 Witco Corp. Build OB Albright & Wilsons Ethylan CPG 94 Harcros Chemicals lne. Flo-Mo 3153 Witco Corp. Genapol T250 Hoechst AG Improve DowElanco Kaomul 230 KAO Spain piperonyl butoxide Fluka Chemika Rhodonate LMO Rhone-Poulenc Rhodonate MLP704 Rhone-Poulenc Simusol M52 Seppic France Ethoduomeen AKZO Corp. Ethomeen C-15 ALZO Corp.

Table 3. Mean percentage of root damage due to nematode growth (% disease), standard deviation of this mean,% removal of root damage and evaluation of leaf phytotoxicity (0 = none, 3 = severe) after treatment of tomatoes with MON (700700) mixed with marked adjuvants.

Adjuvant 0.5 X I / O if no recording. D aai / ha % of disease % removal average j phytotoxicity prCměr standard deviation CS-7 560 33.33 11.79 50.00 1.67 280 66.67 11.79 0.00 1.00 Improva 560 20.00 7.07 70.00 2.00 280 23.33 16.50 57.50 1.00 140 53.33 11.79 12.50 0.67 Witco C5367 560 20.00 7.07 70.00 1.33 280 50.00 20.41 25.00 0.67 1 40 50.00 0.00 25.00 1.33 Oodigen 226 560 20.00 7.07 70.00 2.67 280 41.67 11.79 37.50 2.67 1 40 33.33 11.79 50.00 2.33 Neoccl 25-9 560 20.00 7.07 70.00 1.67 230 53.33 11.79 12.50 1.33 1 40 53.33 11.79 12.50 0.57 Stepwst QF-3G 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 ΧΞ 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 65.57 11.79 0.00 0.33 1 40 56.67 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 550 13.33 8.50 80.00 3.00 280 41.67 11.79 37.50 2.33 140 53.33 11.79 12.50 2.00 Rhodonate MLP704 560 8.33 2.35 37.50 2.67 230 33.33 11.79 50.00 1.33 140 53.33 11.79 12.50 0.67

Adjuvant 0.5 X v / v if not recorded D oai / ha X illness X removal average phytotoxicity diameter standard deviation Rhodonate LMO 560 33.33 11.79 50.00 1.33 280 58.33 11.79 12.50 0.67 140 65.67 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 580 5.00 0.00 92.50 = 5.67 280 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. Or 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 C15 0.3% + 560 0.33 0.47 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 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 C15 0.18% + 560 11.67 9.43 82.50 2.57 Tergitol 15S12 0.12% + Tergitol 15S9 0.2% 280 0.00 0.00 100.00 3.00 140 0.00 0.00 100.00 3.00 Tergitol 15S9 230 0.00 0.00 100.00 3.00 140 0.00 0.00 100.00 3.00 Build 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

Adjuvant 3.5 X I / O if no recording D oai / ha X illness X removed average phytotoxicity diameter standard deviation Improve 560 0.33 0.47 99.33 2.00 280 6.67 2.36 86.67 1.33 140 15.00 7.07 70.00 1.00 Atplus 253 0.4% + 560 1.33 1.25 97.33 0.67 piperonyl butoxide 0.1% 230 5.00 0.00 90.00 0.33 140 6.67 2.36 86.67 1.00 Atplus 253 0.5% + 560 0.00 0.00 100.00 1.33 ammonium sulfate 2.0% 230 2.33 0.94 95.33 0.67 140 15.00 7.07 70.00 0.67 Atplus 258 0.5% 560 0.33 0.47 99.33 1.33 280 3.00 0.00 94.00 1.00 140 20.Q0 7.07 60.00 0.33 Improve 0.5% + ammonium 560 1.33 1.25 97.33 2.33 sulfate 2.0% 280 3.33 2.36 93.33 1.33 140 25.00 0.00 50.00 1.00 Improve 0.5% + piperonyl 560 3.67 0.94 92.67 1.67 butoxide 0.1% 230 8.33 2.36 83.33 2.0.0 140 41.67 11.79 16.67 1.00 CS-7 0.5% -r 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-7 550 6.67 2.89 87.00 2.33 230 28.33 20.21 43.00 1.33 Improve 560 6.00 3.61 83.00 1.67 280 15.00 8.66 70.00 1.33 140 41.67 14.43 17.00 0.67 Oodigen 4022 5S0 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 Oodigen 4022 0.4% ♦ Tween 560 5.00 0.00 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 not recorded *) D aai / ha X disease X removal average; phytotoxicity reasonable standard deviation 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 1.33 140 58.33 14.43 -17.00 1.00 Tergitol 15-S-9 0.2% 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 2.00 Ethomeen C15 0.15 ^ o + 560 5.00 0.00 90.00 1.67 Tergitol 15-S-9 0.1% 280 15.00 8.66 70.00 1.33 140 41.67 14.43 17.00 1.00 Crop Life 5.0% 560 8.33 2.89 83.00 1.67 280 25.00 0.00 50.00 0.67 1 * 0 50.00 -tUiQ- 0.00 1.00

Ai7

PATENT CLAIMS J A composition comprising a combination of a compound of formula ííblMíSVIA ’ Y avy o, \ i and _z cc- (ch ₂ ) „- o 9 6 8.2 '8.2 Y z J - 1 Ol ^ Oa, » 1 AND _ _ - i 9 l í- L Ϊ 0 wherein: n = 1, 3, 5, 7, 9, or 11; • C2

Claims (15)

Ai7 PATENT Claims A composition comprising a combination of a compound of the formula ííblMÍSVIA ’ Y avy o, \ i and _from cc- (ch ₂ ) '- o 8.2 Y of J - 1 Ol ^ Oa, »» 1 AND _ _ - i 9 l - L Ϊ 0 wherein: n = 1, 3, 5, 7, 9, or 11; • C2 Q is CH NHR, CH NO, CHN = CHR, CHN = C = O, CHN * R R RW-, * 2 6 '2 2 2 2 2' 2 345 'or (C = O) -R; X, Y and Y are independently H or F, and provided that at least one of X and Y is F, and further provided that when Q is (C = O) -R _; ; W - is an agriculturally acceptable anion; R _a is an aromatic group; each of R _3, R ₄ and R _s is independently hydrogen; a lower alkyl group, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; _and one of R, R₁, and R ₌ is hydroxy and the other two are hydrogen; or R _3, R ₄ and R _s taken together with the nitrogen of Q form a cyclic quaternary ammonium group; R _e is hydrogen; an aliphatic group, optionally substituted with at least one group selected from hydroxy-, alkoxy-, halo-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl-, and phenyl; amino acid Q amide; (C = O) -R _v ; C _t -C aliphatic amines, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, phenyl and alkoxykarbonyl43 · ^c 3 ^"c 12 aliphatic carboxylic acids, esters, thioesters, and amides thereof, all optionally substituted with at least one group selected from hydroxy, alkoxy, halo, 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 _e considered with nitrogen from Q is guanidine; hydrazine; alkyl or arylhydrazine, optionally substituted with at least one group selected from hydroxy-, alkoxy-, halo-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl-, and phenyl-; or an alkyl- or aryl-sulfonamide _f optionally substituted with at least one group selected from hydroxy-, alkoxy-, halo-, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl-, and phenyl-; _R is (C = O) -R _x ^; C _i -C _{i and} aliphatic optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxy -, alkoxycarbonyl- and phenyl-; _C -C _i2 aliphatic carboxylic acid, esters, thioesters 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 N, O or a group such that, when considered with carboxamide, it is a urea, semicarbazide, carbamate or thiocarbamate group, all optionally substituted with alkyl or aryl, optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro-, amino-, thio-, alkylthio-, carboxy-, alkoxycarbonyl- and phenyl-? R. is -OR, -SR, halogen, -NHOH, or -NR R, wherein each of R Y is independently hydrogen? an aliphatic or aromatic Z 2 A 3 - group optionally substituted by at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl and phenyl; C ₁ -C _xa aliphatic amine optionally substituted with at least one group selected from hydroxy, alkoxy, halo, nitro, amino, thio, alkylthio, carboxy, alkoxycarbonyl, and phenyl; C ₂ -C _x2 aliphatic carboxylic acid, esters, thioesters 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 R _x2 and R _xa taken together with N of R _xx 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, 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 the compound of formula (a), 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) formula III which is a quaternary fatty amine ethoxylate 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 a about fourteen moles of ethoxylation; i (c) of 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 one to | about fifty moles of ethoxylation; and (ii) ethoxylated alkylphenol, wherein the alkyl is from zero to about twenty carbons inclusive, ethyxylate is an ethylene oxide monomer of from two to twenty moles of ethoxylation; (d) Formula V, which are ethoxylated acetylated diols. wherein the number of carbons in the acetylated chain is from ten to twelve inclusive, and the 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 ethoxylate is from seven to fifteen ethylene oxide monomers and the alkyl in the secondary alcohol or ethoxylate has from seven to fifteen carbons inclusive; (f) Formula VII, 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 fifty; (g) formula VIII 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 from about one to fifty; (i) formula X which is an esterified coconut polyethoxyether, wherein the coconut ster is a mixture of alkyls of from about six to about thirty; (j) Formula XI which is a quaternary ammonium comprising an alkyl of C8 to C20 and an agriculturally acceptable anion; (k) of formula XII, which is a quaternary ammonium having groups which are independently alkyl of one to three carbons and together from two to seven carbons; and from three to fifteen ethylene oxide and propylene oxide groups and an agriculturally acceptable anion; (1) formula XIII which is a diaminethoxylate 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. The composition of claim 1, wherein the compound of Formula I is an agriculturally acceptable salt of such compounds; 3,4,4-trifluoro-3-buten-1-amine or a monochloride salt thereof; N- (3,4,4-trifluoro-3-butenyl) glycine, or a monochloride thereof; 2-amino-N- (3,4,4-trifluoro-2-butenyl) propanamide, or a monochloride thereof; (S) -2-amino-4- (methylthio) -N- (3,4,4-trifluoro-3-butenyl) butanamide, or a monochloride thereof; further 4,4-difluoro-3-buten-1-amine, or its monohydrochloride; 3,4,45-trifluoro-3-butenoic acid or its sodium salt; a one to one combination of 3,4,4-trifluoro-3-butenoic acid and 3,4,4-trifluoro-3-buten-1-amine (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-3-butenyl) amino] acetamide or its monochloride; or 3,4,4-trifluoro-3-butenoic acid 2-aminoethyl ester or its monohydrochloride. The composition of claim 1, wherein the adjuvant is (a) the alkyl glycosides of formula II, wherein the alkyl group is a mixture of from about nine to eleven carbons including the α-glycoside groups present in the formula is from one to two; (b) a quaternary fatty amine ethoxylate according to Formula III, wherein the alkyl group of the fatty amine is a mixture of from eight to sixteen carbons and the number of moles of ethoxylates is two; (c) the mixture of formula IV is (i) a fatty amine ethoxylate of formula (E) nH (EO) mH wherein: R ₃₃ 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 sample and together gives about five to fifteen, and (ii) the ethoxylated alkylphenol is of the formula wherein: R _a3 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 (EO) q (EO) p wherein * is the number of carbons that indicates 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) the secondary alcohol ethoxylate of Formula VI is R ₂₄ a CH ·, C * —r-CH CH, where R _a4e represents hydroxy or ethylene oxide monomer, where 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 together they are a chain of carbon mixtures 49 having a total of from 12 to 14 carbons inclusive; (f) a formula of villas that 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 ₂₅ N- (CHCH ₂ O 4 -H) (CHCH ₂ O 1 -H where _And R 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 for ζ _χ represent the number of moles of alkoxylation or preferably ethoxylation in the formula and are in the sum of one to fifty, preferably five to fifteen); (g) Formula VIII, which is an alkyldimethylamine oxide, preferably Empigen OB (the alkyldimethylamine oxide may be represented by the formula 0 '^ 26 -N CH, CH, wherein it is an alkyl mixture of from about six to thirty carbons inclusive, 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 ’ RtT-O (CHCH ₂ to ₂ -OH 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 ¹ 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 is in the sum of one to fifty, preferably five to fifteen) (i) formula X, which is a polyethoxyether fatty acid esterified, preferably Kaomul 230, or stearic acid polyethoxylate, preferably Simusol M52 (esterified coconut polyethoxyether and stearic acid polyethoxylate may be represented by the formula R ₂₈ -CO ₂ - (EO 2 -H where R _2a represents a mixture of alkyls having from about twelve to twenty carbons inclusive; EO represents ethoxylation in formula az _and is from five to fifteen; (j) formula XI, which is a quaternary ammonium, which may be represented by formula R ₂₉ -N * (CH ₃ ) ₂ (CH ₂ (C ₆ H ₃ )) Q 'wherein R _g is alkyl from C 10 to C 16 and Q is an agriculturally acceptable anion; (k) formula XII, which is a quaternary ammonium, which may be represented by formula RjoRjiRnNqEOJn / PO ^ · Q where R, R, and R are all methyl or one of R, ^R 3 R '32 ^{R E0} ethylene oxide; PO is propylene oxide; η _χ is an integer from one to two; _and n is an integer from six to ten; and Q is an agriculturally acceptable anion); (1) formula XIII which is a diaminethoxylate represented by the formula wherein R ₃₃ represents alkyl from C 10 to C 16; and n ₃ , n ₄ , n _s represent the number of moles of ethoxylation in the formula and together give five to fifteen; (m) formula XIV which is an alkoxylated primary fatty alcohol represented by the formula wherein R ₃₄ represents alkyl from C 13 to C 15; EO is ethylene oxide; PO represents propylene oxide; n _e is an integer from 6 to 9; n _? is an integer from 4.5 to 6; and (n) mixtures thereof. The composition of claim 2, wherein (a) the composition is an alkyl glycoside that 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) the quaternary fatty aminoethoxylate is cocomethylammonium chloride or ethoquad C / 12; (c) a mixture that is Improve ^R ; (e) the secondary alcohol ethoxylate is Tergitol 15-S-9 or Tergitol 15-S-12, or (f) mixtures thereof. The composition of claim 4, wherein the adjuvants are alkyl glycosides of formula II, wherein the alkyl group is a mixture of from about nine to eleven carbons inclusive, and the number of glycoside groups in the sample is from one to two. The composition of claim 5, wherein Formula I is N- (3,4,4-trifluoro-3-butenyl) glycine or a monohydrochloride salt thereof. The composition of claim 5, wherein Formula I is 3,4,4-trifluoro-3-buten-1-amine or a monohydrochloride salt thereof. A composition for controlling infestation of plants by nematodes, insects or mites comprising an effective amount of the composition of claim 1 in an agriculturally acceptable carrier. A composition for controlling infestation of plants by nematodes, insects or mites comprising an effective amount of the composition of claim 5 in an agriculturally acceptable carrier. A composition for controlling infestation of plants by nematodes, insects or mites, comprising an effective amount of the composition of claim 6 in an agriculturally acceptable carrier. 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. A method of controlling infestation of plants by nematodes, insects, and mites comprising applying an effective amount of the preparations of claim 1 to a plant locus. A method of systemically controlling infestations of helminth, insect or mite infestations comprising applying an effective amount of a composition according to claim 9 which has been or is transformed after application to have the polarity required for mobility through the phloem without compromising helminth disposal efficiency. The process of claim 12, wherein the compound of formula I in the formulation is N- (3,4,4-trifluoro-3-butenyl) glycine or a monohydrochloride salt thereof. The process of claim 12, wherein the compound of Formula I in the formulation is 3,4,4-trifluoro-3-buten-1-amine or a monohydrochloride salt thereof.