FR2715272A1 - Insecticidal composition. - Google Patents

Abstract

The insecticidal composition according to the invention comprises a compound represented by formula (I): (CF DRAWING IN BOPI) as active ingredient and 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), acrylate of 2-t-butyl-6- (3-t-butyl-2- hydroxy-5-methylbenzyl) -4-methylphenyl, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, bis (2,2,6,6-tetramethyl -4-piperidyl) and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]. It allows the release of an annoying odor by the compound (I) which sometimes occurs in use or in storage under severe conditions.

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

Cz-CH COOCH

C H C = CHC H

3 2C = HC (I)

CH3

CH3 CH

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

not reviewed JP-A-56-90004.

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

  stringent light such as strong scattered light or

  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 1-ethynyl-2-methyl-2-pentynyl chrysanthemate, which does not emit a troublesome odor when used or stored for a

  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-butyl-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 agent 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'-methylenebis (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 from group (II) or depositing them on a support, auxiliary agents such as organic solvents, synergists, surfactants,

  flavors and bactericidal and fungicidal agents.

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

  are octachlorodipropyl oxide (S-4219), c-r2- (2-butoxy-

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

  piperonyl) and N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-

dicarboximide (MGK-264E).

  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-63-122608 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 the 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 method described in Japanese Patent Application JP-B-5542045. Although the compounds of formula (I) include the optically active isomers due to the asymmetric carbon atoms of the remainder of the alcohol and the remainder of the acid as well as the geometric isomers due to the residue cyclopropane 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 not limiting 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 O n Chemical name Structure [I] - A (1R) -cis, trans-chrysan- CH3, - CH (RS) -1- I-, ethynyl-2-methyl-2- = CC2H pentenyl CH3 H3 CH3

15.OH OH

  CII] -A 2,2-methylenebis (4- (CH3) 3C CH2 C (CH3) 3

methyl-6-t-butyl-

phenol) CH3 CH3

HE HO

  CII] -B 2,2'-Methylenhebis (4- (CH3) 3C CH2 C (CH3) 3 ethyl-6-t-butylphenol)

C2H6 C2H6

  [II] -C 2-t-butyl-6-yl (3-t-butyl-2-hydroxy-5-OH-OC-CH = CH 2 methylbenzyl) -4-methyl- (CH 3) 3 CH 2 C acrylate ( CH3) 3 phenyl

CH3 CH3

  [II] -D 3,5-di-t-butyl-4-hydroxy- (CH3h)

2,4-di-t-butyl benzoate

phenyl HO C-O C (CH3) 3

(CH3C C (CH3) 3

  Table 1 (cont.) Compound n Chemical Name Structure [II] -E Bis (2,2,6,6-tetramethyl-4-piperidyl) bis (2,2-bis (tetramethyl) -4-piperidyl sebacate TetrakisE3- (3,5-di-t- (CH 3) 3 butyl-4-hydroxyphenyl) - HO O CH 2 CH 2 COOCH 2

propionate] of penta-

erythritol C (CH3) 3 4 N

NOT

CIII] -A Benzotriazole N H

HN N

HN CIII] -B 1H-Tetrazole

N N

N H

CIII] -D 3-mercapto-4-methyl-5-

  trifluoromethyl-4H-CH3 I 1,2,4-triazole N N CF3 EIII] -E 5-chlorobenzotriazole ci N CN oN H

Table 2

Compound n Chemical name Structure

OH

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

  phenol (CH 3) 3 C C (CH 3) 3 CH 3 b 4, 4'-butylidenebis (3-C (CH 3) 3 CH 3 methyl-6-t-butylphenol)

HO H OH

*. H C (CH3) 3

c Alkylated diphenylamine

R R

NH

Tetrakis (3-laurylthio)

  propionate) pentaery- (HuC12SCH2CH2COOCH2) 4C thritol CgHlg9 e Trisnonylphenylphosphate Tris (2,4-di- (CH3) 3C-P-butylphenylphosphate)

(CH3) 3C

HO C (CH3) 3

2- (2-hydroxy-3-t-butyl) -5-C N

methylphenyl) -5-chloro-

benzotriazole N

H CH3

  Note: Nonylated diphenylamine produced by Sumitomo Chemical Co., Ltd., sold under the brand name "Sumilizer"

9 (A.).

  Test Example 1 To 4 mg of the compound [I] -A, 0.4 mg of a compound indicated in Table 3 below was added each time and the mixture was dissolved in acetone. The resulting acetone solution was applied to a 1 cm × 1 cm filter paper and air dried. The filter paper was placed in a 1 ml screwed tube and covered with aluminum foil. After keeping the tube in a thermostat at 800 C for 72 h, the filter paper was removed and the odor level was evaluated by a

  three-member jury according to the following scale.

  Scale of evaluation: 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 At 100 mg of compound [I] -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 odor level 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

CII] -B O 0

[II] -C O 1

[II] -D O 0

CIIJ-E 0 1

EIIJ-F 1 1

  a 2 2 b 2 1 c 2 2 d 2 2 e 1 2 f 2 2 g 2 0

CIII] -A 2 2

  none 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 it is exposed to rigorous conditions, that is to say by heating at 800 C during

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

  Test Example 3 To 4 mg of the compound [I] -A was added 0.4 mg of the compound [II] -B or [II] -D and 0.4 mg of the compound [III] -A or [III ] -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 stored in a 60 C thermostat for 72 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.

Table 4

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

EII] -B + CIII] -A O O O

CII] -B + [III] -B 1 0 0

EII] -D + [III] -A OO 0

CII] -D + [III] -B O 0 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.

R E V E NDICATIONS

  A method for preventing the release of an annoying odor by an insecticidal compound represented by formula (I):

CH C - CH

C-CH COOCH

CH3 C = CHC2H I)

CH3

CH3 CH3

  characterized in that it consists in using an insecticidal composition containing said compound of formula (I) as active ingredient and at least one compound selected from group (II) consisting of

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

  methylenebis (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 tetrakisC3-

  Pentaerythritol (3,5-di-t-butyl-4-hydroxyphenyl) propionate].

  Process according to Claim 1, 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