DE4009142A1 - New insecticidal compsns. - comprising a chrysanthemic acid ester, an odour-preventing cpd. and opt. an azole cpd. to prevent colour change - Google Patents

Abstract

New insecticided compsns. comprise a chrysanthemic acid ester (I), one or more odour-preventing cpds. (II) and optionally one or more azole cpds. (III): cpds. (II) : 2,2'-methylenebis(4-methyl- 6-tert.-butylphenol) (IIA); 2,2'-methylenebis(4-ethyl- 6-tert.-butylphenol (IIB); 2-tert-butyl-6-(3-tert. -butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (IIC); 2,4-di-tert.-butylphenyl 3,5-di-tert.-butyl-4-hydroxybenzoate (IID); bis(2,2,6,6-tetramethyl- piperidin-4-yl) sebacate (IIE) and tetrakis (3-(3,5-di-tert.-butyl-4-hydroxyphenyl) -propionic acid) pentaerythritol ester (IIF).

Description

The invention relates to new insecticidal compositions and especially insecticidal compositions that are not obnoxious Give off smell.

Chrysanthemic acid 4-methyl-3-yl-4-hepten-1-in-ester of Formula I.

is an insecticidal compound described in JP-B-55- 42 045, which from JP-A-56-90 004 for excellent inhibitory properties is known to clothing pests (the Expression "JP-B" means a verified, published Japanese Patent application and the term "JP-A" means an unexamined published Japanese patent application).  

However, if the compound I under for a long time unfavorable conditions are used or kept, such as e.g. B. under strong, diffuse light or at high temperatures, sometimes gives off a nasty smell. So existed a need countermeasures against this disgusting Smell to hit.

The object of the present invention is insecticidal compositions with chrysanthemic acid-4-methyl-3-yl-4-heptene 1-in-ester as an active substance that is used or stored under unfavorable conditions over a longer period of time do not give off a foul smell.

The above object is achieved in that for the active compound of formula I at least one compound from the group 2,2′-methylenebis (4-methyl-6-tert-butylphenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), Acrylic acid 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) - 4-methylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, sebacic acid bis (2,2,6,6-tetramethyl-4-yl-piperidine) ester or tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, [henceforth Group II] is added.

The present invention provides insecticidal compositions available that a compound of formula I as Active ingredient and at least one compound from group II includes. From the point of view, making a return To prevent odor are from the compounds of the Group II 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) and 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester-r prefers. 2,2′-Methylenebis is particularly preferred (4-ethyl-6-tert-butylphenol).

The mixing ratio is in the insecticidal compositions on a weight basis of active compound of formula I.  I to the compounds from group II usually from 1: 1 to 100: 1, preferably from 5: 1 to 100: 1.

When mixing the active compound and the connections of the Group II or when expanding it with a carrier can optionally Adjuvants, such as organic solvents, Synergists, surfactants, flavors or bacteriocidal or fungicidal agents are used.

Examples of suitable organic solvents are petroleum or alcohols. Examples of suitable synergists are octachlorodipropyl ether (S-421 ^R ), α - [2- (2-butoxyethoxy) ethoxy] - 4,5-methylenedioxy-2-propyltoluene (piperonyl butoxide) or N- (2-ethylhexyl) bicyclo [2.2. 1] hept-5-ene-2,3-dicarboxyimide (MGK-264 ^R ).

The addition of benzotriazole derivatives is also described in JP-A-61-30 505 or in JP-A-63-122 608 and JP-A-63- 126 808 described compounds to the invention insecticidal compositions effective in preventing a change in color of compound I upon contact with surfaces made of copper, copper alloys or containing copper Dyes.

Such additives to protect against color change due to Contact with copper is e.g. B. benzotriazole, 1H-tetrazole, 1H- 1,2,4-triazole, 3-mercapto-4-methyl-5-trifluoromethyl-4H- 1,2,4-triazole or 5-chlorobenzotriazole (henceforth group III). From the point of view of protection from color changes due to of contact with copper are from the connections of the Group III benzotriazole and 1H-tetrazole preferred. Especially benzotriazole is preferred.

The group III compounds are usually described in a weight ratio of 1/100 to 1, preferably of 1/100 to 1/5, based on the active compound I used.  

According to the present invention, the delivery of a disgusting Odor from the active compound I who sometimes occur depending on storage conditions can be reliably prevented. Furthermore, with addition of group III compounds a color change of the compound I on surfaces in contact with copper, copper alloys or copper-containing dyes, the sometimes depending on the storage conditions can occur can be prevented.

The compounds of formula I can by known methods are produced such. B. after in JP-B-55-42 045 described method. While the compounds of formula I optically active isomers with asymmetric carbon atoms in the alcohol residue and in the acid residue and geometric isomers with different spatial arrangement of the substituents on the cyclopropane ring relates to the present invention those isomers that act as insecticidal agents are and their mixtures.

The compositions of the present invention can e.g. B. can be used as insecticides for clothes. In this case are the compositions of the present invention, though them directly in z. B. furniture containing clothes, such as Cloakrooms, dressing tables or dressers can be used can, usually in various dressings, such as tabular Formulations formulated using suitable carrier substances used and then applied. The salary of the composition according to the invention in such dressings is usually from 0.1 to 80% by weight.

The present invention is hereinafter described in more detail in the test examples described, Table I the compounds shows which were used as test examples and Table II shows the connections for comparative or Control attempts were used.  

Table I

Table II

Test example 1

To 4 mg of compound [I] -A, 0.4 mg of the in Compounds shown in Table III below and the mixture was dissolved in acetone. The acetone solution obtained was on a filter paper on an area of 1 cm x 1 cm applied and air dried. The filter paper was placed in a 5 ml screw tube and the tube was covered with aluminum foil. After thermostatting The filter paper was removed from the tube for 72 hours at 80 ° C taken. Three test subjects checked and rated the escaping Odor according to the following criteria.

Assessment criteria:
0. . . no smell
1 . . . slight smell
2nd . . odor

The results of the organoleptic tests of the three test subjects was added up and divided by three. The quotient was rounded to the nearest whole number. Table III shows the results obtained.

Test example 2

To 100 mg of compound [I] -A was added 10 mg each added to the compounds listed in Table III and the mixture was dissolved in acetone. The acetone solution was applied to a filter paper on an area of 5 cm × 5 cm and air dried. The filter paper thus obtained was placed in a petri dish (9 cm in diameter) and 24 hours without being covered with the light of a xenon lamp (9000 to 10,000 lux) irradiated. After that the escaping smell in the same way as in test example 1 checked and rated. Table III shows the ones obtained Results.  

Table III

According to Table III, the addition of a compound generates Group II in the insecticidal compositions which contain a compound of formula I, a significant Effect in preventing the delivery of an obnoxious Odor even under unfavorable conditions, e.g. B. at 72 hours Warm to 80 ° C or when irradiated with a Xenon lamp from 9000 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 added and the mixture was dissolved in acetone. The acetone solution obtained was applied to a filter paper applied an area of 1 cm × 1 cm and air dried. The filter paper was made in the same way as in test examples 1 or 2 heat-treated or with light irradiated and the smell was checked and as in test example 1 determined. Next was the impregnated filter paper placed between copper plates of 5 cm × 5 cm and the edges of the two plates were sealed with cellophane tape. The Plates were kept in a thermostat at 60 ° C for 72 hours. The color change of the filter paper was as follows Assessment basis examined and determined.

Basis for assessment:
0. . . no color change
1 . . . slight color change
2nd . . Color change.

The evaluation was carried out by three test subjects. The results were added up and divided by three. The quotient was rounded to the nearest whole number. The Table IV below shows the results obtained.  

Table IV

Table IV teaches that in the presence of a compound from the Group III in addition to a compound from Group II not only smell but also a color change due to from contact with copper is prevented.

Claims (24)

1. Insecticidal compositions comprising a compound of formula I. as active ingredient and at least one compound from group II consisting of 2,2'-methylenebis (4-methyl-6-tert.-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert.-butylphenol), Acrylic acid 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4 -di-tert-butylphenyl ester, sebacic acid bis (2,2,6,6-tetramethyl-4-yl-piperidine) ester or tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) - propionic acid] pentaerythritol ester. 2. Insecticidal compositions comprising a compound of formula I. as active ingredient and at least one compound from group II consisting of 2,2, '- methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) , Acrylic acid-2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester, bis (2,2,6,6-tetramethyl-4-yl-piperidine) sebacic acid ester or tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl ) - propionic acid] pentaerythritol ester and at least one compound from group III, consisting of benzotriazole, 1H-tetrazole, 1H-1,2,4-triazole, 3-mercapto-4-methyl-5-trifluoromethyl-4H-1,2,4 -triazole or 5-chlorobenzotriazole. 3. Insecticidal compositions according to claim 1 or 2, where the compound of group II 2,2'-methylenebis (4- ethyl 6-tert-butylphenol) and / or 3,5-di-tert-butyl 2,4-di-tert-butylphenyl 4-hydroxybenzoate. 4. Insecticidal compositions according to claim 1 or 2, where the compound of group II 2,2'-methylenebis (4- ethyl-6-tert-butylphenol). 5. Insecticidal compositions according to claim 1 or 2, the Group II compound being 3,5-di-tert-butyl-4- 2,4-di-tert-butylphenyl hydroxybenzoate. 6. Insecticidal compositions according to claim 2, wherein the group III compound benzotriazole and / or 1H-tetrazole is. 7. Insecticidal compositions according to claim 2, wherein the Group III compound is benzotriazole. 8. Insecticidal compositions according to claim 2, wherein the group III compound is 1H-tetrazole. 9. Insecticidal compositions according to claim 2, wherein the compound of group II 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and / or 3,5-di-tert-butyl-4-hydroxybenzoic acid  2,4-di-tert-butylphenyl ester and Group III compound: benzotriazole and / or 1H-tetrazole is. 10. Insecticidal compositions according to claim 2, wherein the compound of group II 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and / or 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and Group III compound is bezontriazole. 11. Insecticidal compositions according to claim 2, wherein the compound of group II 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and / or 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and Group III compound is 1H-tetrazole. 12. Insecticidal compositions according to claim 2, wherein the compound of group II 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and the compound of group III Is benzotriazole and / or 1H-tetrazole. 13. Insecticidal compositions according to claim 2, in which the compound of group II 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and Group III compound: benzotriazole and / or 1H-tetrazole is. 14. Insecticidal compositions according to claim 2, in which the compound of group II 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and the compound of group III Is benzotriazole. 15. Insecticidal compositions according to claim 2, in which the compound of group II 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and the compound of group III Is 1H-tetrazole.   16. Insecticidal compositions according to claim 2, in which the compound of group II 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and Group III compound is benzotriazole. 17. Insecticidal compositions according to claim 2, in which the compound of group II 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and Group III compound is benzotriazole. 18. Procedures for controlling insect pests, comprehensive the use of insecticidal compositions according to one of claims 1 or 2. 19. The method according to claim 18, wherein the connection of the Group II 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) and / or 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di- tert-butylphenyl ester. 20. The method according to claim 18 or 19, wherein the compound Group III benzotriazole and / or 1H-tetrazole is. 21. A method of preventing the delivery of an obnoxious Odor from an insecticidal compound of the Formula I, the use of insecticidal compositions according to claim 1. 22. A method of preventing the release of an offensive odor and / or undergoing a color change due to contact with copper in an insecticidal compound of the formula I, which comprises the use of insecticidal compositions according to claim 2. 23. The method according to any one of claims 21 or 22, wherein the compound of group II 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and / or 3,5-di-tert-butyl-4-hydroxybenzoic acid Is 2,4-di-tert-butylphenyl ester. 24. The method of claim 23, wherein the compound of Group III is benzotriazole and / or 1H-tetrazole.