FR2644676A1 - INSECTICIDE COMPOSITION BASED ON 1-ETHYNYL-2-METHYL-2-PENTENYL CHRYSANTHEMATE - Google Patents

Abstract

The insecticidal composition according to the invention comprises a compound represented by the formula I: (CF DRAWING IN BOPI) as an active ingredient; at least one compound selected from group II consisting of 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), l '2-t-Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4- 3,5-di-t-butyl-4-hydroxybenzoate di-t-butylphenyl, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ; and optionally at least one compound selected from group III consisting of benzotriazole, 1H-tetrazole, 1H-1,2,4-triazole, 3-mercapto-4-methyl-5-trifluoromethyl-4H-1,2 , 4-triazole and 5 chlorobenzotriazole. The offensive odor from Compound I which sometimes occurs in use or storage under harsh conditions can be avoided.

Description

The present invention relates to a novel insecticidal composition and

  more particularly an insecticidal composition does not

not giving off an uncomfortable odor.

  1-Ethynyl-2-methyl-2-pentenyl chrysanthemate represented by the formula (I):

CH3 CH

C = CH COOCH

C H C = CHC H (I)

CHH3

/ \ /

CH3 CH3

  is an insecticidal compound disclosed in Japanese Patent Application Laid-open JP-B-55-42045 and known to have an excellent inhibitory effect against insect pests for clothing, as described in published Japanese Patent Application.

not reviewed JP-A-56-90004.

  However, when the component of formula (1) is used or stored for a long time under conditions

  stringent light such as strong light scattered

  eratures, it sometimes gives off an uncomfortable odor. So we have

  sought to take action against this annoying odor.

  An object of the present invention is to provide an insecticidal composition comprising as active ingredient the ethynyl-2-methyl-2-pentynyl chrysanthemate, which does not emit a troublesome odor when it is used or stored for a long time.

  long life in harsh conditions.

  It has now been found that the above object of the invention is achieved by adding to the active compound of formula (I) at least one compound selected from the group (II) consisting of

  2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis-

  (4-ethyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl) -2-acrylate

  hydroxy-5-methylbenzyl) -4-methylphenyl, 3,5-di-t-butyt-4-

  2,4-di-t-butylphenylhydroxybenzoate, bis (2,2,6-

  6-tetramethyl-4-piperidyl) and tetrakis [3- (3,5-di-t-butyl) -4-

  hydroxyphenyl) propionate] pentaerythritol.

  The present invention provides an insecticidal composition containing a compound represented by formula (I) as an ingredient

  Active bone and at least one compound selected from group (II).

  From the point of view of the preventive effect against the release

  odorants, the preferred compounds of group (II) are 2,2'-

  methylenebis (4-ethyl-6-t-butylphenol) and 3,5-di-t-butyl-4-

  2,4-di-t-butylphenyl hydroxybenzoate. From a point of view

  In general, 2,2'-methylenbis (4-ethyl-6-t)

  butylphenol). The mixing ratio of the active compound of formula (I) to the compound selected from group (II) in the insecticidal composition is ordinarily from 1: 1 to 100: 1, preferably from 5: 1 to

100: 1, by weight.

  By mixing the active compound and the compound selected in

  group (II) or depositing them on a support, we can use

  if desired, auxiliary agents such as organic solvents, synergistic agents, surfactants,

  flavors and bactericidal and fungicidal agents.

  Examples of suitable organic solvents are kerosene and alcohols. Examples of suitable synergists

  are octachlorodipropyl oxide (S-421E), c-r2- (2-butoxy-

  ethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene (butoxide

  piperonyl) and N- (2-ethylhexyl) -bicycloF2.2.1] hept-5-ene-2,3-

dicarboximide (MGK-264)).

  In addition, the addition of the benzotriazole derivatives described in Japanese Patent Application JP-A-61-30505 or the compounds described in Japanese Patent Applications JP-A-63-122603 and JP-A-63 126808 to insecticide composition according to the invention is effective to prevent the color change of the compound of formula (I) in areas in contact with copper, the alloys

  of copper or dyes containing copper.

  These additives to avoid the color change due to copper are chosen from group (III) constituted by the

  benzotriazole, 1H-tetrazole, 1H-1,2,4-triazole, 3-

  mercapto-4-methyl-5-trifluoromethyl-4H-1,2,4-triazole and 5-

  chlorobenzotriazole. From the point of view of the preventive effect against the color change due to copper, the preferred compounds of group (III) are benzotriazole and 1H-tetrazole. From one point

  In general, benzotriazole is particularly preferred.

  The compound selected from group (III) is ordinarily used in a weight ratio of 1/100 to 1, preferably

  1/100 to 1/5, relative to the active compound of formula (I).

  According to the present invention, it is safe to inhibit the release of a troublesome odor by the active compound of formula (I) which sometimes occurs depending on the storage conditions. In addition, it is also possible to avoid, by addition of the compound chosen from group (III), the color change of the compound of formula (I) in the zones in contact with copper, copper alloys or dyes containing copper, which himself

  produced sometimes depending on the conditions of conservation.

  The compound of formula (I) can be synthesized by known methods such as the process described in Japanese Patent Application JP-B-55-42045. Although the compounds of formula (I) include the optically active isomers due to atoms of asymmetric carbon from the rest of the alcohol and the rest of the acid as well as the geometric isomers due to cycloDropane from the remainder of the acid, the present invention applies to effective isomers such as

  insecticidal agents and mixtures thereof.

  The composition of the present invention can be used, for example, as an insecticide for clothing. In this case, although the composition of the present invention can be applied directly, for example in furniture containing clothes such as wardrobes, credenzas and dressers, it is usually formulated into various preparations such as a plate preparation using a suitable support, and then put into operation. The content of the composition of the invention in this preparation is ordinarily from 0.1 to 80%

in weight.

  The present invention is now illustrated in greater detail by means of the following Test Examples, but it is understood

  that these are in no way limitative of the present invention.

  The compounds used in the Test Examples are shown in Table 1 below and the compounds used for the tests

  comparatives or controls are shown in Table 2 below.

Table 1

  Compound on Chemical Name Structure 11i [I] -A (1R) -cis, trans-chrysan- CH3 = - CH C = CH COO H H (RS) -1-CH C CH ethynyl-2-methyl-2- - CC2H5 pentenyl H3 H3 CH3

OH OH

(CH3) 3C (CHH2)

  EII-A 2,2-methylenebis (4- (CH3) 3C CH2 C ((H3) 3

methyl-6-t-butyl-

phenol)

OH3 CH-3

OH OH

  [II] B 2,2'-R-ethylenebis (4- (CH) 3 C CH 2 (CH 3) 3 ethyl-6-t-butylphenol) C) C2H 5 C 2 H 5 [II] -C 2-t-butyl-6-acrylate ( 3-t-butyl-2-hydroxy-5-OHCH 2 CH 2 metyl L-benzyl L) -4-methyl L- (CH 3) 3 C 1 CH 2 0 C (O 3) 3 phenyl

CH3 CH3

  EII] -D 3,5-di-t-butyl-4-hydroxy- (CH 3) 3

2,4-di-t-butyl benzoate

phenyl HO C-O C (CH3) 3

(CH3) 3C C (CH3) 3

  Table 1 (continued) Compound o n Chemical name Structure

[III-E bis (2,2,6,6-

  tetramethyl-4-piperidyl) HN (H2) C NH [II] -F Tetrakis [3- (3,5-di-t- (CH3) 3 butyl-4-hydroxyphenyl) -OH CH2 2COOCH2 propionate] penta-CH2C2COCH2 Erythritol C (CH3) 3 4 N t9N III] -A Benzotriazole NH

HN N

EIII] -B 1H-tetrazole

N N

N EIII] -C 1H-1,2,4-triazole N N -H

[III] -D 3-mercapto-4-methyl-5-

  trifluoromethyl-4H-CH3 1,2,4-triazole N N CF3 [III] -E 5chlorobenzotriazole cN N N H

Table 2

  Compound n Chemical name OH structure

has 2,6-di-t-butyl-4-methyl-

  phenol (CH 3) 3 C C (CHI 3) 3 CH 3 b 4,4'-butylidenebis (3- C (CH 3) 3 CH 3 methyl-6-butylphenol)

HO- H OH

Ha

* CH3 C (CH3) 3

c alkylated diphenylamine R

R R

Tetrakis (3-laurylthio)

  propionate) pentaeryl- (H25ClzSCH2CH2COOCH2) 4C thritol 2G CgHig e Trisnonyl- (p phenyl) phosphate 3 Tris (2,4-di- (CH 3) 3 t-butylphenyl) phosphate

(CH3) 3C

HO C (CH3) 3

  2- (2-hydroxy-3-t-butyl-5-chloro-N-methylphenyl) -5-chloro-benzotriazole

H CH3

  Note: Nonylated diphenylamine produced by Sumitomo Chemical Co., Ltd., sold under the brand name "Sumilizer Test Example 1 At 4 mg of the compound [I] -A, 0.4 mg of a compound was added each time. As shown in Table 3 below and the mixture was dissolved in acetone, the resulting acetone solution was applied to a 1 cm × 1 cm filter paper and air dried. put the filter paper in a screwed tube with a volume of ml and covered the tube with an aluminum foil After having kept the tube in a thermostat at 80 ° C. for 72 hours, the filter paper was removed and the degree of odor was assessed by a

  three-member jury according to the following scale.

  Scale of assessment: O ... no smell 1 ... slight odor 2 ... odor The results of the organoleptic test by the three members of the jury were added and divided by three and the quotient was rounded to the number nearest integer. The results

  obtained are shown in Table 3.

  Test Example 2 To 100 mg of Compound II-A, 10 mg of the compounds listed in Table 3 were added each time and the mixture was dissolved in acetone. The acetone solution was applied to a 5 cm x 5 cm filter paper and then air dried. The filter paper was placed in a 9 cm diameter Petri dish and exposed to the light of a xenon lamp (9,000 to 10,000 lux) for 24 hours without protection. The filter paper was removed and the degree of odor evolved was evaluated in the same manner as in the test example

  1. The results obtained are shown in Table 3.

Table 3

  Compound Added Odor Level Test Example 1 Sample Test 2

[II] -A 0 1

[II] -B 0 0

[II] -C 0 1

[II-D 0 0

[EII] -E 0 1

[II] -F I 1

  a 2 2 b 2 1 c 2 2 d 2 2 e 1 2 r 2 2 g 2 0 EIIIt-A 2 2 none 2 2 As can be seen from Table 3, the addition of the compound selected from group (II) produces important preventive effects against the release of troublesome odor by the insecticidal composition containing the compound of formula (I) when exposed to rigorous conditions, that is to say by heating at 80 C during

  72 hours or exposure to a xenon lamp 9,000 to 10,000 lux.

  Test Example 3 To 4 mg of compound [I] -A, 0.4 mg of compound [II] -B or [II] -D and 0.4 mg of compound [III] -A or [III] were added. ] -B, and the mixture was dissolved in acetone. The resulting acetonic solution was applied to a 1 cm x 1 cm filter paper and air dried. The filter paper was treated by heating or exposure to light in the same manner as in Test Example 1 or 2 and odor clearance was evaluated in the same manner as in Test Example 1. In addition, the impregnated filter paper was sandwiched between two cm x 5 cm copper plates, the edges of both plates being sealed with a "Cellophane" tape and the plates were kept in a 60 C thermostat for 72 hours. h. The color change of the paper

  filter was then observed and evaluated according to the following scale.

  Scale of evaluation: O ... No change of color 1 ... One observes a slight change of color

  2 ... There is a change of color.

  The observation was made by a jury of three members.

  The results were added and the sum divided by three and the quotient was rounded to the nearest whole number. The

  The results obtained are shown in Table 4 below.

Board.

  Degree of odor Compound Heating Exposure to Degree of added light staining

[II] -B + [III] -A O 0 0

[II] -B + [III] -B 1 O O

[II] -D + [III] -A OO O

[II] -D + [III] -B O O O

  none 2 2 2 It can be seen from Table 4 that the presence of the compound selected from group (III) in addition to the compound selected from group (II) not only causes a preventive effect against odor, but also a preventive effect against the change of

color due to copper.

Claims (28)

  1. An insecticidal composition characterized in that it comprises a compound represented by the formula (I) CH3 CCH   / C - CH C = CH COOCH CH3 / C = CHC2H5 I) CH3 CH3   as an active ingredient; and at least one compound selected from   group (II) consisting of: 2,2'-Methylenbis (4-methyl-6-t-)   butylphenol), 2,2'-ethylenebis (4-ethyl-6-t-butylphenol),   2-t-Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) acrylate   methylphenyl, 2,4-di-t-3,5-di-t-butyl-4-hydroxybenzoate   Butylphenyl, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and tetrakisE3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] pentaerythritol.   2. Insecticidal composition characterized in that it comprises a compound represented by the formula (I): CH3 \ / C-CH C = CH COOCH H3 / C = CHC 2H5 I) CH3 253 CH CH3 CH3   as an active ingredient; at least one compound selected from group (II) consisting of 2,2'-methylenebis (4-methyl-6-t-butylphenol),   2,2'-Methylenbis (4-ethyl-6-t-butylphenol), 2-t-acrylate,   butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl, the   2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, sebacetate   bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate and tetrakisC3-   Pentaerythritol (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; and at least one compound selected from group (III) consisting of   benzotriazole, 1H-tetrazole, 1H-1,2,4-triazole, 3-   mercapto-4-methyl-6-trifluoromethyl-4H-1,2,4-triazole and 5- chlorobenzotriazole.   3. Insecticidal composition according to claim 1, characterized in that the compound or compounds selected in the   group (II) is or are 2,2'-methylenebis (4-ethyl-6-butyl)   phenol), 2,4-di-t-butyl-3,5-di-t-butyl-4-hydroxybenzoate phenyl or mixtures thereof.   4. Insecticidal composition according to claim 1, characterized in that said compound chosen from group (II) is   2,2'-methylenebis (4-ethyl-6-t-butylphenol).   5. Insecticidal composition according to claim 1, characterized in that said compound chosen from group (II) is   2,4-Di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate.   6. Insecticidal composition according to claim 2, characterized in that the one or more compounds selected in the   group (II) is or are 2,2'-methylenbis (4-ethyl-6-t-butyl)   phenol), 2,4-di-t-butyl-3,5-di-t-butyl-4-hydroxybenzoate phenyl or mixtures thereof.   7. Insecticidal composition according to claim 2, characterized in that said compound chosen from group (II) is   2,2'-Methylenbis (4-ethyl-6-t-butylphenol).   8. Insecticidal composition according to claim 2, characterized in that said compound chosen from group (II) is   2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate.   9. Insecticidal composition according to claim 2, characterized in that the compound or compounds selected from group (III) is or are benzotriazole, 1H-tetrazole or their mixtures.   10. Insecticidal composition according to claim 2, characterized in that said compound chosen from group (III) is benzotriazole.   11. Insecticidal composition according to claim 2, characterized in that said selected in Group (III) is 1H-tetrazole. 12. Insecticidal composition according to claim 2, characterized in that the one or more compounds selected in the   Group (II) is or are 2,2'-methylenbis (4-ethyl-6-t-butyl)   phenol), 2,4-di-t-butyl-3,5-di-t-butyl-4-hydroxybenzoate   phenyl or mixtures thereof and the one or more compounds selected from group (III) is benzotriazole, 1H-tetrazol or their mixtures.   13. Insecticidal composition according to claim 2, characterized in that the compound or compounds selected in the   group (II) is or are 2,2'-methylenebis (4-ethyl-6-t-butyl)   phenol), 2,4-di-t-butyl-3,5-di-t-butyl-4-hydroxybenzoate   phenyl or mixtures thereof and the compound selected from group (III) is benzotriazole.   14. Insecticidal composition according to claim 2, characterized in that the compound or compounds selected in the   group CII) is or are 2,2'-methylenbis (4-ethyl-6-t-butyl-   phenol), 2,4-di-t-butyl-3,5-di-t-butyl-4-hydroxybenzoate   phenyl or mixtures thereof and said compound selected from the group (III) is 1H-tetrazole.   15. An insecticidal composition according to claim 2, characterized in that said compound selected from group (II) is 2,2'-methylenbis (4-ethyl-6-t-butylphenol) and the one or more compounds selected from group (III). ) is or are it   benzotriazole, 1H-tetrazole or mixtures thereof.   16. An insecticidal composition according to claim 2, characterized in that said compound selected from group (II) is 2,4-t-butylphenyl 3,5-t-butyl-4-hydroxybenzoate and said compound (s) chosen from the group (III) is or are the   benzotriazole, 1H-tetrazole or mixtures thereof.   17. An insecticidal composition according to claim 2, characterized in that said compound chosen from group (II) is 2,2'-methylenebis (4-ethyl-6-t-butylphenol) and said compound   selected from group (III) is benzotriazole.   18. An insecticidal composition according to claim 2, characterized in that said compound selected from group (II) is 2,2'-methylenebis (4-ethyl-6-t-butylphenol) and the compound selected from group (III) is 1H-Tetrazole 19. An insecticidal composition according to claim 2, characterized in that said compound selected from group (II) is 2,4-di-t-3,5-di-t-butyl-4-hydroxybenzoate. butylphenyl and   said compound selected from group (III) is benzotriazole.   20. Insecticidal composition according to claim 2, characterized in that said compound selected from group (II) is 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate and   said compound selected from the group is 1H-tetrazole.   21. A method for preventing harmful insects, characterized in that it consists in using an insecticidal comoositioc comprising a compound represented by the formula (I): CH3 -CH C = CH COOCH CH3 / / (C I) 3 / C = CHC2H5 3 2 5 CH3 CH3 CH3   as an active ingredient; and at least one compound selected from   group (II) consisting of 2,2'-methylenebis (4-methyl-6-t-butyl)   phenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), acrylate   2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methyl-   phenyl, 2,4-di-t-butyl-3,5-di-t-butyl-4-hydroxybenzoate   phenyl bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the   tetrakisE3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] of penta   erythritol. 22. A method for preventing harmful insects, characterized in that it consists in using an insecticidal composition comprising a compound represented by formula (I): CH3 -C-CH C = CH COOCH 3 v / C = CHC2H5 () CH3 CH3 CH3   as an active ingredient; at least one compound selected from the group (II) consisting of 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-- butylphenol), 2-t-butyl-6- (3-tbutyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 3,5-di-t-butyl-4-hydroxybenzoate di-t-butylphenyl, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and   tetrakisE3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] of penta   erythritol; and at least one compound selected from group (III)   consisting of benzotriazole, 1H-tetrazole, 1H-1,2,4-   triazole, 3-mercapto-4-methyl-5-trifluoromethyl-4H-1,2,4-   triazole and 5-chlorobenzotriazole.   23. A method for preventing harmful insects according to claim 21, characterized in that the one or more compounds   selected from group (II) is or are 2,2-methylenbis (4-   ethyl-6-t-butylphenol), 3,5-di-t-butyl-4-hydroxybenzoate of 2,4-   di-t-butylphenyl or mixtures thereof.   24. A method for preventing harmful insects according to claim 22, characterized in that said selected compounds   in group (II) is or are 2,2'-methylenbis (4-ethyl-6-   t-butyl-phenol), 2,4-di-t-butyl-4-hydroxy-2,4-di-t-butyl-4-hydroxybenzoate butylphenyl or their mixtures.   25. A method for preventing harmful insects according to claim 22, characterized in that said compound (s)   chosen from group (III) is benzotriazole, 1H- Tetrazole or their mixtures.   26. A method for preventing the release of an annoying odor by an insecticidal compound represented by the formula (I): CH C-CH C-CH COOCH CH3 / C = CHC2H5 (I) CH3 CH3 CH3   characterized by using an insecticidal composition containing said compound of formula (I) as an active ingredient; and at least one compound chcisi in the group (II) constituted   2,2'-Methylenbis (4-methyl-6-t-butylphenol), 2,2'-   Methylenbis (4-ethyl-6-t-butylphenol), 2-t-butyl acrylate   6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl,   2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, sebacetate   bis (2,2,6,6-tetramethyl-4-piperidyl) and tetrakisE3-   Pentaerythritol (3,5-di-t-butyl-4-hydroxypenyl) propionate].   27. A method for preventing the release of an annoying odor by an insecticidal compound represented by the formula (I): CH3 CCH C-CH 3 COOCH C X CZCHC2H5 () 3 25 CH 3 CH3 CH3   and preventing its color change due to copper, characterized in that it consists in using an insecticidal composition containing said compound of formula (I) as an active ingredient; at least one compound selected from Group (II) consisting of   2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylbenzene   (4-ethyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl) acrylate   2-hydroxy-5-methylbenzyl) -4-methylphenyl, 3,5-di-t-butyl-   2,4-di-t-butylphenyl 4-hydroxybenzoate, bis (2, -   2,6,6-tetramethyl-4-piperidyl) and tetrakisE3- (3,5-di-t-butyl)   4-hydroxyphenyl) propionate] pentaerythritol; and at least one 2.644676   compound selected from group (III) consisting of benzotriazole,   1H-Tetrazole, 1H-1,2,4-triazole, 3-mercapto-4-methyl-5-   trifluoromethyl-4H-1,2,4-triazole and 5-chlorobenzotriazole.   28. Process according to claim 26, characterized in that the compound or compounds chosen from group (II) is or are   2,2'-Methylenbis (4-ethyl-6-t-butylphenol), 3,5-t-butyl-4-   2,4-t-butylphenyl hydroxybenzoate or mixtures thereof.   29. The method according to claim 27, characterized in that the compound or compounds chosen from group (II) is or are   2,2'-Methylenbis (4-ethyl-6-t-butylphenol), 3,5-t-butyl-4-   2,4-di-t-butulphenyl hydroxybenzoate or mixtures thereof.   30. Process according to claim 27, characterized in that the compound or compounds chosen from group (III) is   are benzotriazole, 1H-tetrazole or their mixtures.