FR2533416A1 - NOVEL PESTICIDE COMPOSITIONS COMPRISING A PHOTOSTABILIZER - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS PESTICIDE COMPOSITIONS CONTAINING A PESTICIDE PRODUCT OF THE PYRETHRINOID SERIES AND A PRODUCT INTENDED TO PROTECT THE PESTICIDE AGAINST SOLAR RADIATION AND IN PARTICULAR THOSE FROM THE ULTRAVIOLET. THE COMPOSITIONS OF THE INVENTION MAY BE USED TO CONTROLL AGAINST PLANT PARASITES, PREMISES AND ANIMAL PARASITES.

Description

The present invention relates to novel compositions

  ticides containing a light stabilizer.

  The subject of the invention is pesticide conpositions containing a product

  pesticide of the pyethrinoid series and a product intended to protect the pesti-

  against solar radiation and in particular against the ultraviolet. As the pesticide product of the pyrethrinoid series, there may be mentioned for example the compounds of general formula I. YL-OR in which Y represents: a group YA

H 3 C CH 3

w

H H

in which W represents:

X 1 "H

  or an X 2 CC group in which X 1 x 3 X 3 represents a hydrogen, fluorine, chlorine or bromine atom, X 2, which is identical to or different from X 1, represents a fluorine, chlorine or bromine, X 3 represents a chlorine, bromine or iodine atom

X 4 \ '_ 1

  or else a group C C in which X represents x 5

  a halogen atom, and X 5 represents a halogen atom,

  possibly of that represented by X 4), the group YA being able to exist under any of its stereoisomeric forms

  (1 R, cis, 1S, cis, 1R, trans, 1S, trans) or in the form of

  The mixture of these stereoisomers and the tetrahalogen group that may exist in one of its diastereoisomeric forms resulted from the existence of asymmetric carbon at the 1 'position of the ethyl chain, ie a YB z group eCH (Ys) (Y) n in which Z represents a linear or branched lower alkyl radical having from 1 to 6 carbon atoms, Y 'represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl radical containing from 1 to at 4 carbon atoms, an alkoxyl radical having 1

  to 4 carbon atoms, and N represents a number equal to 0, 1, 2 or

  3, and R represents: or a benzyl radical optionally substituted with one or

  several radicals selected from the group consisting of the radicals

  alkylcars having 1 to 4 carbon atoms, alkenyl radicals having 2 to 6 carbon atoms, alkenyloxy radicals having 2 to 6 carbon atoms, alkadienyl radicals having 4 to 8 carbon atoms, the radical

  methylene dioxyl, the benzyl radical and the halogen atoms.

  or a group -CH 2 g LC 2 R 2 in which the substituent R 1 represents a hydrogen atom or a methyl radical and the substituent R 2 a monocyclic aryl or a group -CH 2-C-CH and in particular a group 5-benzyl 3-furyl methyl, or a CH 3 group

  in which R 3 represents a combined aliphatic organic radical

  carrying 2 to 6 carbon atoms and one or more unsaturated

  carbon-carbon and in particular the vinyl radical, propen-1-

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  yl, buta-1,3-dienyl or buten-1-yl, or a group:

O. / R 4

(R 5) nn -

  in which R 4 represents a hydrogen atom, a group z -C = N a grouping

-C CH

  or a group -CH 3 and R 5 represents a chlorine atom or a methyl radical and n 'represents a number equal to 0, 1 or 2 and in particular the 3-phenoxy benzyl group, a-cyano 3-phenoxy benzyl or aethynyl 3 benzylphenoxy, or a grouping: R 6 OR

| S / I | -CH 2

R 8

R 9 O

  in which the substituents R 6, R 7, R 8, R 9 represent a hydrogen atom, chlorine atom, or a methyl radical and in which the symbol S / I indicates an aromatic ring or a similar dihydro or tetrahydro ring, the R-OH alcoholic coupler which may comprise one or more asymmetric carbon atoms and exist in the form of various stereoisomers. As a pesticidal compound, mention may also be made of the so-called norpyrthric series products described and claimed in the European patent applications.

0038271 0041021 0048186 0050534.

  The invention is of course particularly aimed at pesticides products put on sale on the market or known by many publications; for example deltamethrin, cypermethrin, fenvalirate, fenpropanate, permethrin,

  tralomethrin and tralocythrin.

  As a product intended to protect the pesticide from sunlight and particularly ultraviolet radiation, it is possible to use 4'-benzophenone derivatives such as 2,4-dihydroxybenzophenone,

  2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxy benzoate

  phenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4- (3-hydroxy-ethoxy) -benzophenone, 2-hydroxy-4-methoxy-benzophenone 5-sulfonic acid, 2-hydroxy-4 - (2-acryloxyethoxy) benzophenone and polynere, phenyl 2-benzimidazolesulfon 4 -5'-acid, 3,4-dimethoxyphenylglyoxylic acid and its sodium salt, (muyy; L-4-benzylidene) -3-camphor, hydroxy Methoxy 4-benzophenone, 1-phenyl-4-benzophenone, 2-ethyl carboxylate

2-hexyl.

  We can also mention derivatives

  benzotriazole such as, for example, 2- <2-hydroxy 3,5-ditert-

  butylphenyl) 21 i ben-zotriazole, 2- (2-hydroxy 3,5-ditertamyl)

  phenyl) 2H-benzotriazole, 2- <2-hydroxy-5-methylphenyl) 2H -

  benzotriazole, or 2- (2-hydroxy-3,5-dimethylphenyl) 2-benzotriazole.

  It is also possible to mention the hindered amines, for example the products corresponding to the formula H i

HC I CH 3 H 3 C N CH 3

NIH 3 C CH 3 H 3 C CH 3

N N N <CH 2> 6-N

CH-3 CH 3

NH-C-CH 2 C -CH 3

I I

CH 3 CH 3

  n (sold under the trademark Chimassorb 944 (R) or the product corresponding to the formula Cr% X'X Ai A (sold under the trade name Tinuvin 770 (R)), the tertiobutyl phenyl salicylate, or the product corresponding to to the formula:

H 2 N-C 4 H 9

O N ii O s X

C 8 H 17 C 8 H 17

  The invention particularly relates to the compositions characterized in that they further contain an emulsifier.

  The invention also more particularly relates to

  defined above containing in addition a solvent.

  As an emulsifying product, mention may be made of tridecyl phosphates ethoxylated with 5-6.5 moles of ethylene oxide, oxyethylenated trinyl alcohols, phenylsulphonates and ethers.

polyglycolics of fatty alcohol.

  As a solvent, there may be mentioned in particular benzene, xylene, ethers such as monopropylene glycol methyl ether, ether

  nethyl Lque of dipropylene glycol, monoethyl ether of monoethylene glycol.

  The compositions of the invention are quite remarkable for their stability in the light as shown by the results

  attached tests This represents a remarkable progress

markable.

  We have realized that certain compositions and

  including emulsifiable concentrates containing pyrethrum

  noldes as active ingredients, see these degrade in the light so that the practical use of these compositions

can become impossible.

  Thanks to the new stabilized compositions of the invention, the various pyrethroid dilutions have their stability

  These stabilized compounds are then suitable for use in

  used in agricultural use, especially in the open field without loss

  activity and in the best economic conditions.

  In view of the intense insecticidal activity of the pyrethroids listed above, the invention is of great practical importance. It goes without saying that the compositions of the invention are not limited to agricultural use, they can still be used in all other uses of pesticides: domestic use, treatment of stored grains, treatment of animals to rid them of their parasites (treatment with baths, "sprays" or by brushing a small part of the body of the animal

  the so-called method "for on").

  The subject of the invention is in particular compositons for

  which the pyrethroid product corresponds to the formula A 1

0 H 3 C CH 13 CN O

I O 2 CH (A 1)

X 2 C -C

X 3 X 3

  in which X 1; X 2 and X 3 identical or different represent

each a halogen atom.

  The subject of the invention is more particularly the compounds of formula Alpour, in which X 1, X 2 and X 3 each represent a bromine atom, as well as the compositions for which X 1 and X 2 each represent a chlorine atom, X 3 representing

a bromine atom.

  The products of formula A 1 are described and claimed in

French Patent 2398714.

  The subject of the invention is also particularly

  previously defined compositions for which the product

ticide meets the formula A 2.

H 3 C CH 3

C C - \ CO B (A 2)

  In which X represents a hydrogen atom or a halogen atom and in which R 'represents either a linear, branched or cyclic alkyl radical, saturated or unsaturated, containing from 1 to 8 carbon atoms, optionally > 22 to 4 7 substituted with one or more functional groups, identical or different,

  or an aryl group containing from 6 to 14 carbon atoms

  bone, optionally substituted by one or more functional groups, which may be identical or different, or a heterocyclic radical optionally substituted with one or more functional groups, which may be identical or different, B represents the residue of an alcohol used in the synthesis of the esters of the series Pyrethroids the double bonded ethylene having the Z or E geometry. The products of formula A 2 are known products, described and claimed in the European patent applications 0038271, 0041021,

0048186, 0050534.

  Preferred compounds of formula A 2 may include those compounds for which X is hydrogen, R, methyl, ethyl or terbutyl and B is the residue of an alcohol of the formula: CN c -CH / x wherein X is a carbon atom. hydrogen and fluoride in which the forgetting moiety is Z and especially the (S) cyano-3-phenoxy benzyl (IR, cis) 2,2-dimethyl-3- (Z) -2-methoxycarbonylethenyl cyclopropane carboxylate, as well as the corresponding 2-ethoxy and 2-tert-butoxy compounds.

  The subject of the invention is in particular the compositions

  in that the product intended to protect the pesticide from solar radiation and in particular from the ultraviolet radiation is chosen from

zt r the beniaztriaoles.

  group of the following products: benzophenone derivatives, amines encumbered \

  The invention more particularly relates to composi-

  characterized in that the product, for protecting the pesticide against solar radiation and in particular against ultraviolet light, is a benzotriazole selected from the group consisting of the products of formula: OH | I / tertbutyl tertbutyl

8 2533416

OH -teraamyl N N / teramyl OH

OH CH 3

  CH 3 The invention more particularly relates to the compositions as defined above containing 0.01 to 20 g of product intended to protect the pesticide against solar radiation and in particular against ultraviolet for 5 to 50 g

of pyrethroid product.

  The following examples illustrate the invention without however

limit it.

EXAMPLES OF COMPOSITIONS

  Compositions containing: (emulsifiable concentrate) were prepared

  (1 R, cis) 2,2-dimethyl 3 (Z) -2-tert-butoxycarbonyl ethenylcyclohexyl

  (S) -cyano-3-phenoxy benzyl propane carboxylate; 30 g oxyethylenated tridecyl alcohol 100 g phosphoric acid fatty alcohol ester EMPHOS PS 400 30 g Tinuvin 326 "R" or 2- (2-hydroxy 3,5-diterbutyl phenyl) 2 H-benzotriazole 5 g Xylene 300 g Methyl ether monoethylenic glycol qs 1 1 B Preparations were prepared containing (emulsifiable concentrate) (1 R, cis) 2,2-dimethyl 3- (1,2,2,2-tetrabromoethyl) cyclopropane carboxylate (S) cyano 3-phenoxy benzyl 36 g Tridecyl alcohol oxyethylene 120 g Phosphoric acid ester of fatty alcohol Emphos PS 40 OO g Tinuvin 326 "R" or 2- (2-hydroxy 3,5-diterbutylphenyl) 2 H-benzotriazole 5 g Xylene 250 g Ethyl ether monoethylene glycol;

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  C Compositions containing (emulsifiable concentrate) were prepared

  (R, cis) 2,2-dimethyl-3 (Z) -2-tert-butoxycarbonyl ethenylcyclopro-

  S) α-cyano-3-phenoxy benzyl carboxylate 25 g Phosphoric acid ester of ethoxylated tridecyl alcohol 30 g Hostavin VP (or 2-hydroxy-4-noctoxybenzophenone 20 g Xylene 120 g Methyl ethylene glycol ether q s p 1 1

  STUDY OF THE STABILITY OF THE COMPOSITIONS OF THE INVENTION

LIGHT

  To measure the kinetics of degradation under luminous ceiling light, place 200 μl of emulsifiable concentrate containing the active ingredient at the dose of 25 g / l (ie 5 mg) in 25 ml beakers (diameter = 30 mm) while striving to spread the deposit in the form of a ring at the bottom of the beaker One thus tries to avoid the

  Irradiation surface inequalities for the various samples.

  The organic solvent is removed from the formulation with the aid of a hot air stream for approximately 20 minutes. The beakers thus prepared are placed under a luminous ceiling (150 klux, 1 hour of exposure corresponding to 14 hours of average sunlight ) and are removed at given times After light irradiation, the content of the b 6 expensive is taken up with 1 to 2 ml of methylene chloride and the determination of the compound is carried out.

  test by high performance liquid chromatography.

  The percentages of degradation as a function of time are as follows: with the composition of the example Ala degradation is 0%

after 20 hours.

  with the composition of Example B, the degradation is 4%

after 20 hours.

2533416

Claims (8)

  1 Pesticidal compositions containing a pesticide product of the Pyrethrinolde series and a product intended to protect the pesticide against solar radiation and in particular against the ultraviolet.   The compositions as defined in claim 1, characterized in that they further contain an emulsifier.   The compositions as defined in claim 1 or   2, characterized in that they further contain a solvent.   4 The compositions as defined in any of the   Claims 1 to 3 for which the pyrethroid product meets the formula A 1. H 3 C CH 3 X 3 H C X 2 XCCC (A 1) ) ç 2-u-CO C 2 CH 'A) I I X 3 X 3   in which X 1, X 2 and X 3, which are identical or different, represent each a halogen atom.   The compositions as defined in claim 4 for   which X 1 and X 2 and X 3 each represent a bromine atom.   The compositions as defined in claim 4 for which X 1 and X 2 each represent a chlorine atom, X 3 representing a bromine atom.   7 The compositions as defined in any of the   claims 1 to 3 for which the pesticide product meets in formula A 2 H 3 C / CH 3 x O XX (\ ll (A 2) C = C COB   R'OC wherein X represents a hydrogen atom or a halogen atom and wherein R 'represents either a linear, branched or cyclic, saturated or unsaturated alkyl radical containing 1 to 8 carbon atoms, optionally substituted with one or more functional groups, which are identical or different,   or an aryl group containing from 6 to 14 carbon atoms   bone, optionally substituted by one or more functional groups, which may be identical or different, or a heterocyclic radical optionally substituted with one or more functional groups, which may be identical or different, B represents the residue of an alcohol used in the synthesis of the esters of the series pyrethroid, the ethylenic double bond having the geometry Z or EO 8 The compositions as defined in claim 7 for which X represents a hydrogen atom R ', a methyl, ethyl or terbutyl radical and B the remainder of an alcohol of formula -C O   in which XI represents a hydrogen or fluorine atom and in which the geometry of the double bond is Z.   The compositions defined in one of claims 1 to 8,   characterized in that the product intended to protect the pestici-   against solar radiation and in particular against the ultraviolet, is selected from the group of products following derivatives of benzophenone, hindered amines and benzotriazoles. The compositions as defined in claim 9,   characterized in that the product intended to protect the pestici-   against solar radiation and in particular   ultraviolet, is a benzotriazole chosen from the group constituting   killed by the products of formula: OH tertbutvl A N N / tertbutyl 12 2533416 OH teramyl CN 3 N N teramyl OH C ONH 3 NOT NOT -   CH 3 11 The compositions as defined in any of the   Claims 1 to 10, containing from 0.01 to 20 g of product intended   to protect the pesticide against solar radiation and especially against the ultraviolet for 5 to 50 g of pyrethroid product.