DE2923217A1 - PROCEDURE FOR PROTECTING KERATINIC MATERIALS FROM KERATIN-EATING INSECTS - Google Patents

Description

CIBA-GEIGY

CLBA-GEIGY AG, CH-4002Bfisel

Case 1-11753 / = _ £, 29 2 3 2]

Method for protecting keratinic materials from attack by keratinous insects

The present invention relates to a method for protecting keratinous or keratinous Materials, especially wool, materials containing wool, Furs, furs and feathers, from attack by keratin-eating insects and from insect caused damage, in particular against infestation by moths and other keratin-eating pests, by treating those that contain keratin Substrates with certain cyclopropanecarboxylic acid esters.

It is known from the literature that various natural pyrethrins and many synthetic pyrethroids have been investigated with regard to their suitability as moth repellants, but offer these because of their relative instability to light and air usually a very limited protection. A synthetic one Pyrethroid, namely the 3-phenoxybenzyl ester of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid is described as a useful moth repellent. See J. Text. Inst. 1976 Vol. 67 No. 3, 77-81, Man. Chem. & Aerosol News October 1977, 39-40 and Japanese patent specification 1 133 600. Furthermore, from the German Offen-

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Legungsschrift 27 42 546 known that various esters of 2,2-dimethyl-3- (1 ¹ , 2 ', 2 ^! 2'-tetrahalogen) ethylcyclopropanecarboxylic acid are effective as insecticides, especially as field insecticides.

It has now surprisingly been found that a certain group of cyclopropanecarboxylic acid esters, namely those of the formula

(1) X ₁ X, 0

I I II

X ₇ -C-CH-GH-CH-CO-CH

r \ / t

X »C R

CH ₃ R ₁
wherein

X ₁ and X "independently of one another are each methyl, fluorine, chlorine or bromine,

X "and X, independently of one another, in each case chlorine or bromine, R, hydrogen, methyl or ethyl,

R _{2 is} hydrogen, methyl, cyano, -C = CH or -CH = CH ₂ and Y, and Y _2, independently of one another, are each hydrogen, fluorine, chlorine, bromine, methyl or Tr i fluorine thy I, are particularly excellent as a protective agent against Keratin-eating insects such as moths are suitable.

The present invention therefore relates to a method for protecting keratin or keratin-containing materials from infestation by keratin-eating insects and from insect caused damage, which is characterized by the fact that one has the treated material to be protected with compounds of formula (1). The invention further relates to the use of Compounds of the formula (1) as protective agents for keratinic or keratin-containing material against keratin-eating Insects and the material protected or equipped with the aid of compounds of the formula (1).

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Are preferred in the inventive method as Compounds of the formula (1) those of the formula

(2) X ¹ Br 0

Il Il

X ^ - C - CH - CH - CH - C - 0 - CH

I \ / I

Br C R '

/ \
CH ₃ CH ₃

used, in which Xl and X 'are each independently chlorine or bromine and Rl is hydrogen, cyano, -C ^S CH or -CH-CH ₂ .

Particularly good results are obtained with compounds of the formula (2) in which R ^ is hydrogen, cyano or -C ³ CH and Xi and Xl are either both chlorine or both are bromine.

The compounds used in the process according to the invention of formula (1) have an excellent effect against keratin-eating insects, such as against keratin-eating insects Larvae of Lepidoptera, e.g. Tineola spec. And Tinea spec., As well as against keratin-eating larvae of Coleoptera, e.g. Anthrenus spec, and Attagenus spec. on. the Active ingredients of the formula (1) are particularly suitable for protecting keratinic or keratin-containing material against insect caused damage, in particular for washing and lightfast finishing against insects, in particular for moth and beetle protection of such materials. It can contain keratin or keratin-containing material both in raw and in processed state, for example raw or processed sheep wool, products made from other animal hair, Hides, furs and feathers.

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In practice, the effectiveness of the compounds used in the process according to the invention is particularly important Formula (1) against the larvae of the clothes moth (Tineola bisselliela) and fur moth (Tinea pellionella) as well against the larvae of the fur and carpet beetles (Attagenus spec. or Anthrenus spec.). That according to the invention is preferred A method for protecting textiles made of wool, e.g. woolen blankets, woolen carpets, woolen linen, woolen clothes and knitwear or textiles containing wool, such as blended fabrics, one component of which is wool, e.g. blended fabrics made of wool and other natural fibers, preferably cotton or wool and synthetic fibers, on the other hand also for It is used to protect fur and pelts from infestation by the pests mentioned.

The compounds of the formula (1) are applied to the substrates mentioned above, in particular to woolen and wool-containing substrates Textiles, preferably with the help of methods known from dyeing practice, such as exhaust dyeing processes and pad application upset. For this purpose, an aqueous dispersion (or emulsion or suspension) of the respective Active ingredient made. The active ingredient is previously preferred in organic solvents such as aliphatic and alicyclic solvents Alcohols, ketones, hydrocarbons such as benzene, xylenes, toluene, benzines, also chlorinated and fluorinated Hydrocarbons, especially dissolved in propylene glycol, methoxyethanol, ethoxyethanol or dimethylformamide and then added to the application bath, the additional auxiliaries customary in dyeing practice, e.g. dispersants may contain, it being possible for such auxiliaries to be contained in the organic stock formulation.

The aqueous dispersions contain, for example, surfactants, for example anionic compounds such as soaps and other carboxylates (e.g. alkali salts of higher fatty acids),

Derivatives of sulfur-oxygen acids (e.g. sodium salt of dodecylbenzenesulfonic acid, water-soluble salts of sulfuric acid monoesters of higher molecular weight alcohols or their polyglycol ethers, such as soluble salts of dodecyl alcohol sulfate or of dodecyl alcohol polyglycol ether sulfate acids (e.g. derivatives of phosphorous acid with oxygen), phosphates derivatives of phosphorus derivatives acidic (electrophilic) nitrogen in the hydrophilic group (eg disulfine salts), cationic surfactants such as amines and their salts (eg lauryl diethylenetriamine), onium compounds, amine oxides or nonionic surfactants such as polyhydroxy compounds, surfactants based on mono- or polysaccharides, higher molecular weight acetylene glycols, polyglycol ethers (e.g. polyglycol ethers of higher fatty alcohols, polyglycol ethers of higher molecular alkylated phenols). In addition, the liquor can also contain customary auxiliaries such as water-soluble perborates, polyphosphates, carbonates, silicates, optical brighteners, plasticizers, acidic salts such as ammonium or zinc silicone fluoride, or certain organic acids such as oxalic acid, acetic acid or especially formic acid, and also antimicrobials and Finishing agents _r example, those based on synthetic resins or starch.

The textile materials can e.g. by hot or cold aqueous dyeing, bleaching, chroming or post-treatment Baths are impregnated with the active ingredients using various textile finishing processes, such as the Padding or exhaust process, come into question.

The treatment is expediently carried out at temperatures of 10 to 10O ⁰ C, for example at 10 to 70 ⁰ C, preferably about room temperature.

Because of their good solubility in organic solvents, the active compound compounds of the formula (1) can also very good from not-whats fresh media on the to be protected Substrates are applied (solvent application). as

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Solvents come for this, among other things, trichlorethylene, Methylene chloride, hydrocarbons, propylene glycol, methoxyethanol, ethoxyethanol, dimethylformamide in question, which nor distribution agents (e.g. emulsifiers such as sulfated castor oil, fatty alcohol sulfates, etc.) and / or other auxiliaries can be added. The materials to be protected are usually simply impregnated with these solutions.

The finishing of the materials to be protected can also be combined with a dry cleaning process. The active ingredient compounds are used for this purpose in the cleaning agent (e.g. lower halogenated alkanes, e.g. trichlorethylene etc.) and the cleaning process is carried out as usual.

The active ingredient compounds can, however, also be dissolved in highly volatile organic solvents and these The solution can then be sprayed onto the substrate to be protected (spray application). For this type of application Textiles containing wool, furs and feathers are particularly suitable. The advantage of spray application is that because of the Recovery of the solvent avoids pollution of the wastewater.

In the process according to the invention, the compounds of formula (1) also in combination with others against keratin-eating Effective insect repellants are used, e.g. in combination with urine derivatives, benzimidazoles ^ aromatic sulfonamides and phosphoric and phosphonic acid esters.

The amount of active substance of the formula (1) used in each case depends on the particular substrate and the application method. However, it is usually dimensioned so that after being drawn onto the material to be protected, the latter is approximately 100 to 2000 ppm, preferably 200 to 1000

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Contains ppm of active substance. This results e.g. for the exhaust process at a liquor ratio of 1:20, concentrations of 0.005 to 1 g / l treatment bath, depending on achievable degree of exhaustion. Concentrations of up to 2 g / l are possible with the padding process.

The active ingredient compounds which can be used in the process according to the invention of the formula (1) can be obtained by known production methods. See also DE-OS 27 42 546, 28 05 226, 28 05 193 and 28 05312.

The compounds of the formula (1) can be used both as pure optical isomers and in the process according to the invention are used as isomer mixtures. When in the making If the active ingredient compounds are assumed to be pure optically active compounds, pure optical compounds can be used Isomers obtained. If you use isomer mixtures as a starting compound indications used are usually recovered Mixtures of isomers which, if desired, are converted into diastereomers and these into the optical antipodes by customary methods can be separated. By the formula (1) and all other formulas and terms of according to the invention Compounds which can be used are in each case included both the individual isomers and mixtures thereof.

Preparation example for the active ingredient compounds

12.5 g of 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic acid cc-cyano-3'-phenoxybenzyl ester are dissolved in 100 ml of carbon tetrachloride. At 20 to 30 ° G, 4.76 g of B ^ is added dropwise to this solution. The reaction mixture becomes two Stirred for hours. After the carbon tetrachloride has been distilled off, the compound of the formula is obtained

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- y- 43

Cl

Cl-C-CH-CH-CH-C-O-CH

CH ₃ CH ₃

with a refraction of n ~ = 1.5800. Mixture of isomers (60% trans; 40% cis)

The compounds of the formula listed in the table below are also prepared in an analogous manner

manufactured.

TABEL

Ver
am
manure
No. ^X l X ₂ ^R l R ₂ Y ₁ H 40
¹¹ D isomer 11 Cl Cl CH ₃ CN H 1.5751 * Cis 12th Cl Cl CH ₃ CN H 1.5768 - Trans 13th Cl Cl GH ₃ H H 1.5820
t 20.
(= n _D ) Mixture of isomers
(607o Trans
40% Cis) 14th Cl Cl CH ₃ H H 1.5766 * Cis 15th Cl Cl GH ₃ H 1.5773 - Trans

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Ver
am
manure
No. ^X l X ₂ ^R l R ₂ ^Y l H 4 ° isomer 16 CH ₃ CH ₃ CH ₃ CN H 1.5675 Mixture of isomers 17th CH ₃ CH ₃ CH ₃ H H 1.5605 I s otner closely emi sch 18th Br Br CH ₃ CN H 1.5950 Mixture of isomers 19th Br Br CH ₃ H H 1.5929 Mixture of isomers 20th Cl Cl H H H 1.5828 Mixture of isomers 21st Cl Cl H CN H 1.5776 22nd Br Br CH ₃ C ^ CH H 1.5942 Mixture of isomers 23 Br Br CH ₃ CH ₃ H 1.5825 Mixture of isomers 24 Cl Cl CH ₃ CH ₃ H 1.5680 Mixture of isomers 25th Cl Cl CH ₃ CHo H 1.5713 t Cis 26th Cl Cl CH ₃ CH ₃ H 1.5707 * Trans 27 Cl Cl CH ₃ CN H 1.5688 Mixture of isomers 28 Cl Cl CH ₃ C = CH H 1.5753 Isomer mixture s ch 29 Cl Cl CH ₃ C = CH H 1.5796 * Cis 30th Cl Cl CH ₃ C = CH PF
H 1.5760 - Trans 31
32 Cl
Cl Cl
Cl CH ₃
CH ₃ CN
CH = CH ₂ H ^D 1.5693 Is omerengemi s ch 33 Cl Cl C ₂ H ₅ CN P-CH ₃ 1.5639 Mixture of isomers 34 Cl Cl CH ₃ CN m-CF ₃ 1.5689 Mixture of isomers 35 Cl Cl CH ₃ CN 1.5823 Mixture of isomers

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The following examples serve to explain the process according to the invention in more detail, without going into it restrict. Percentages and parts therein mean percent or parts by weight.

Example 1 (extraction method)

In each case a 0.4% stock solution of one of the compounds of the formulas (10) to (15) and (18) to (33) is prepared in Glycolnrancnethyläther. An aqueous application liquor is then prepared at room temperature which contains 0.12 ml of a wetting and dispersing agent, 0.6 ml of formic acid 1:10 and 0.75 ml of the respective 0.4% stock solution in 120 ml of distilled water. Then 3 g of wool flannel fabric are wetted through with hot water and entered at room temperature. Under constant Relocate the wool pattern, the bath temperature is heated over 20 minutes at 60 ⁰ C and treated for 30 minutes at 60 ° C. It is then cooled, the wool swatch rinsed twice for 3 minutes with distilled water, squeezed off by hand and air-dried. The active ingredient concentration is 1000 ppm, calculated on the weight of the wool.

The sample dried in this way is used for the test of moth fastness (Eating protection against clothes moth Tineola biselliella Hum.), According to the regulations of the Swiss Association of Standards SNV 195901, as well as the authenticity test against larvae of the catfish beetle (Attagenus piceus 01.) and carpet beetles (Anthrenus vorax Wat.), Subject to SNV 195902.

In each case, larvae of Anthrenus vorax and 6 to 7 week old larvae of Attagenus piceus are used for the test. Pieces of the same size are cut out of the treated wool flannel samples and exposed to attack (frass) by 15 larvae of the corresponding pestilent each for ^{14 days at constant temperature (28 ° C.) and constant relative humidity (65%).} The assessment takes place.

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on the one hand according to the relative weight loss of the test object and on the other hand according to the number of still living organisms.

The tested compounds of the formulas (10) to (15) and (18) to (33) show a very good action against the 3 used Pests.

Example 2 (padding method)

In each case, a 0.4% stock solution of one of the compounds of the formulas (10) to (15) and (18) to (33) is prepared in glycol monomethyl ether. 12.5 ml of the respective stock solution are _{diluted to 50 ml with glycol monomethyl ether, which contains O f} 65 g / l of a wetting and dispersing agent (= solution no. 1). 25 ml of solution no. 1 are diluted to 50 ml with glycol monomethyl ether, which contains 0.5 g / l of a wetting and dispersing agent (= solution no. 2). 25 ml of solution no. 2 are again diluted to 50 ml with glycol monomethyl ether, which contains 0.5 g / l of a wetting and dispersing agent (= solution no. 3).

Solution No. 1, 2 and 3 are each 3 ml in Crystallizing bowls emptied and a baited rondelle made of wool flannel is wetted in them for 3 seconds. The damp ones Rondelles are then padded between aluminum foils in such a way that the squeezed rondelles each took up 50% of the fleet. The concentrations of active ingredient are then in sequence 500 ppm, 250 ppm and 125 ppm for treated discs from solutions no. 1, 2 and

The moist rondelles are air-dried and subjected to the same biological tests as in Example 1 described.

The tested compounds of the formulas (10) to (15) and (18) to (33) show a very good effect against all 3 Pests, even at the lowest concentration of 125 ppm.

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Example 3

A 10% solution of 3- (2,2-dichloro-1,2-dibromoethyl) -2,2-dimethylcyclopropanecarboxylic acid 3-phenoxybenzyl ester is obtained made in glycol monomethyl ether. A part of it this solution is mixed with 200 parts by volume of a solvent suitable for dry cleaning, e.g. a suitable Gasoline fraction or perchlorethylene, diluted. If so desired Cleaning-promoting additives can also be added. Wool items are now in this cleaning liquid as usual treated and then centrifuged to a solvent content of approx. 100% of the wool weight. After drying, they prove to be moth and beetle-proof.

If 3- (2,2-dichloro-1 _s 2-dibromoethyl) -2,2-dimethylcyclopropanecarboxylic acid-S-phenoxybenzyl ester is replaced by a compound of the formula (10) to (12), (14), (15) or (18) to (33) and otherwise works according to the above rule, one also obtains a tissue that is suitable for moths and beetles ^

Similar mixtures can also be used for spraying or spraying wool in every processing state will.

Example 4

A 0.5% solution of the active ingredient of the formula (10) in methylene chloride, trichlorethylene or a low-boiling gasoline fraction is made up. A wool article becomes using a conventional spray device with this solution

2
sprayed so that 2 15 g / m 2 of active ingredient solution are applied. With a utilization effect of 30% of the aerosol, about 400 ppm of active ingredient are then on the material. The wool fabric finished in this way proves to be moth- and beet-proof «

If the active ingredient of the formula (10) is replaced by one of the formulas (11) to (15) or (18) to (33) and the procedure is followed As just described, one also comes to moth and beetle-proof fabric.

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Claims (17)

Claims 1. Process for protecting keratinous or keratinous Materials against attack by keratinous insects and against insect caused damage, characterized in that the material to be protected with compounds of the formula X ₁ X ₄ ο ι r H X ₂ -C-CH-CH-CH-CO-CH X ₃ C CH ₃ R ₁ treated, wherein X ₁ and X "independently of one another are each methyl, fluorine, chlorine or bromine, X ₃ and Χ, independently of one another in each case chlorine or erum, Rj hydrogen, methyl or ethyl, R ₂ hydrogen, methyl, cyano, -C ³ CH or -CH = GL, and Y-, and Y ₂ independently of one another are each hydrogen, fluorine , Chlorine, bromine, methyl or trifluoromethyl mean. 2. The method according to claim 1, characterized in that that you can protect the material with compounds of the formula Br
I. CH -CH- O
Il -O - CH CH - \ / C. I. S. C.
\ R ₂ CH ₃ CH ₃ C - I. Br 909850/0869 -} * ■ <• 292321? treated, wherein Xl and Xl are each independently chlorine or bromine and Ri is hydrogen, cyano, -C = CR or -CH = CH ₂ . 3. The method according to claim 2, characterized in that the material to be protected with compounds of formula Br 0 I Il (Br) ₃ C - CH - CH - CH - C - 0 - CH "^ xT ⁰ R " CH ₃ CH ₃ treated, wherein R «is hydrogen, cyano or -C = CH. 4. The method according to claim 2, characterized in that the material to be protected with a compound of formula Br Br 0 I I Il (Cl) ₂ C - CH - CH - CH - C - 0 - CH-r ^ Jr-0 ~ f ^> j CR ₂ ' CH ₃ CH ₃ treated, where RL ^{1 is} hydrogen, cyano or -C = CH. 5. The method according to claim 4, characterized in that the material to be protected with a compound of formula 909850/0869 ■ r-3 92321? Br Br O Ii Il (Cl) ₂ C-CH-CH-CH-C-O-CH-r <^> r-O C CN treated. CH ₃ CH ₃ 6. The method according to claim 4, characterized in that that you can protect the material with a compound of the formula Br Br 0 I I Il (Cl) ₂ C-CH-CH-CH-C-O-CH C HC ^ C / \ treated .. CH ₃ CH ₃ 7. "The method according to claim 4, characterized in that that you can protect the material with a compound of the formula Br Br 0 I I Il (Cl) ₂ C-CH-CH-CH-C-O- _{CH 2 -J ^} treated. CH ₃ CH ₃ 8. The method according to claim 1, characterized in that that on the materials to be protected, the active ingredients in an amount of 100 to 2000 ppm, preferably 200 to 1000 ppm, based on the material to be protected. 909860/0869 9. Procedure ger-vlcs a-sn of the expressions 1 to 8 for Protect voxi raw cc'er processed wool, containing wool Textiles, filings and rocks. 10. The method genäse claim 9 for washable and lightfast Equipment against moths and beetles. 11. The method according to any one of claims 1 to 10, characterized characterized in that wool fiber-containing textiles are treated in an aqueous liquor after Ausziehverfaliren, the the active ingredient compound (s) and optionally one or several dispersants or others in the dyeing application Contains common aids. 12. The method according to any one of claims 1 to 10, characterized characterized in that textiles containing wool fibers are impregnated with an aqueous liquor using the padding method, the active ingredient compound (s) and optionally one or more dispersants or others in the pad application Contains common aids. 13. The method according to any one of claims 1 to 8, characterized in that the material to be protected with a Treated organic cleaning fluid containing one or more of the active ingredients defined in claims 1 to 7 contains. 14. The method according to any one of claims 1 to 10, characterized in that the material to be protected with a Sprayed organic solvent which contains one or more of the active ingredients defined in claims 1 to 7. 909850/0869 BAD ORIGINA! 2823217 15. Use of compounds defined in claims 1 to 7 for protecting keratin-containing material the infestation by harmful insects and insect caused damage, 16. Use according to claim 15 for protecting wool containing textiles, hides and furs before the Infestation by moth and beetle larva. 17. Means for finishing materials containing wool, Furs and hides, characterized in that they contain one or more of the claims defined in claims 1 to 7 Links. 909850/0869