NZ211697A - Use of 3-phenoxy-benzyl esters of (epsilon)- cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane carboxylic acid to protect keratinous material against insect attack - Google Patents

Description

211 69 PriOrity Date^}: €r. U ......

Campletg Specification Filed: ^7.4; tQ 5 Cass: .v.fiO»ffiOJOOi; D.06raiS.f2Q ' ' * > « « I I « | t I » I | | P.O. Journal, Mo: A3QC>...., "■;>v i/j, % I y i:- $ Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION PROCESS FOR PROTECTING XERATINOUS MATERIAL FROM ATTACK BY INSECTS THAT FEED ON KERATIN WE, CIBA-GEIGY AG, a Swiss Corporation of Klybeckstrasse 141, 4002 Basle, Switzerland, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement Jfellwed by lA> 211697 1-14824/- Process for protecting keratinous material from attack by insects that feed on keratin The present invention relates to a process for providing keratinous .material with a protective finish against attack by insects that feed on keratin, which process comprises treating said keratinous material with specific 3-phenoxybenzyl esters of (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid. The invention further relates to compositions containing said esters.

Synthetic pyrethroids have long been known as insecticides. Some of these synthetic pyrethroids, including 3-phenoxybenzyl esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, have also been described as insecticides against pests that feed on keratin (q.v. for example J. Text. Inst. 1976, No. 3, Vol. 67, 77; G.B. published application 2 024 625; US patent specification 4 219 593; New Zealand Patent No. 192259; US patent specification 4 283 444; European published application 105 030). These pyrethroids are very effective against the larvae of moths, as well as against the larvae of fur beetles and carpet beetles. In the cited publications, the compounds are used as mixtures of isomers as obtained in the usual synthesis but which are not more clearly defined.

Owing to their stereochemical properties, 3-phenoxybenzyl esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid are obtained as 2 geometrical isomers (cis, trans) and, depending on the substitution at the a-carbon atom of the alcohol component, as 4 or 8 different optical isomers. Various geometrical and optical isomers and mixtures of isomers are described in G.B. published ° application 1-448 228 and in Pesticide Science, 1975 (6), 537-542 and 1974 (5), 791-799. Both of these publications also teach that ^27 JUL 1987 VK specific optical isomers, namely those having the R-configuration with respect to the cyclopropane ring, have particularly pronounced insecticidal activity especially against houseflies and mustard beetles. Further, the inference is to be drawn from these publications that a specific geometrical isomer is not in all respects more effective than the other. The results show that, on the contrary, in certain cases the cis-isomer is more effective and in other cases the trans-isomer.

Some geometrical and optical isomers of specific 3-phenoxybenzyl esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid are also known from G.B. published application 1 467 579. Among these isomers, the trans-form is preferred (see formulations 1, 6 to 10, 13, 14 and 16).

Surprisingly, it has now been found that the cis-isomers (or the mixtures of cis-enantiomers) of a small group of 3-phenoxybenzyl esters of 2,2-dimethy1-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid have exceptionally good action against insects that feed on keratin. These isomers exhibit in all respects a substantially greater activity against pests that feed on keratin than the corresponding trans-isomers or the mixtures of isomers obtained in random distribution which are normally used. Accordingly, said cis-isomers are most suitable for protecting keratinous material, in particular wool, from attack by insects that feed on keratin.

The process of the present invention for providing keratinous material with a protective finish against insects that feed on keratin comprises treating the material to be protected with 3-phenoxybenzyl esters of (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropanecarboxylic acid, said esters having the formula oi 27 JUL 1987 ^ 2 1 * 6 9*V CI 0 \ II s'~\ /C=CJL ^p-0-CK~y R (1) CI ^*ScH - CH ' # = \ /"V ° ( > c / \ ch3 ch wherein R is hydrogen, -C=CH, -C=C-CH^ or CN, and is hydrogen or fluorine, or with a mixture of isomers containing at least 90% of said cis-isomers.

The invention further relates to material which has been provided with a protective finish with the aid of compounds of the formula (1) .

In the process of the present invention, there are used e.g. those compounds of formula (1) wherein R is hydrogen or CN, and R^ is hydrogen.

Preferred compounds of the formula (1) for application in the process of this invention are those wherein R is hydrogen or CN, and R^ is fluorine, or those wherein R is C=C-CH^, and R^ is hydrogen or fluorine.

The compounds of formula (1) which can be used in the process of the invention for protecting keratinous material against insects that feed on keratin are effective in particular for example against Lepidoptera larvae such as Tineola spec, and Tiena spec., and also Coleoptera larvae, e.g. Anthrenus spec. and Attagenus spec. The compounds are most suitable for protecting keratinous material against feeding damage by insects, especially for providing such material with a washfast and lightfast protective finish against insects, in particular moths and beetles. The keratinous material to be protected can be both in the raw and in the processed state, for example raw or processed sheep's wool or products made of other animal hairs;. hides, furs and feathers.

A particularly important feature is the effectiveness of the compounds of formula (1) against the larvae of the webbing clothes moth (Tineola bisselliella), the common clothes moth (Tiena pellio-nella) and of the false clothes moth (Hofmannophila pseudopretella), as well as against the larvae of fur beetles and carpet beetles (Attagenus spec, and Anthrenus spec, respectively), e.g. against larvae of Anthrenus verbasci and Anthrenus pimpinellae, of Anthrenus scrophulariae, of Anthrenus fasciatus, Attagenus pellio and, in particular, of the black fur beetle (Attagenus piceus) and of the carpet bug (Anthrenus flavipes).

The process of the present invention is therefore preferably used on the one hand for protecting woollen textiles, for example blankets, wool carpets, woollen underwear, woollen clothing, knits and wool-containing textiles such as blends, one component of which is wool, for example blends of wool and other natural fibres, preferably cotton, or of wool and synthetic fibres, and, on the other hand, also for protecting furs and hides from attack by the above-mentioned pests.

The compounds of formula (1) are applied to the above substrates, in particular to woollen textiles and wool-containing textiles, preferably by processes commonly known and employed in dyeing, such as the exhaust process and padding. To this end, an aqueous solution or dispersion (or emulsion or suspension) of the respective active ingredient is formulated. The active ingredient can be dissolved beforehand in an organic solvent, such as an aliphatic or alicyclic alcohol, a ketone, a hydrocarbon, such as benzene, a xylene, 2 1 t 6 toluene, a petroleum distillate, and also a chlorinated or fluorin-ated hydrocarbon, especially in propylene glycol, methoxyethanol, ethoxyethanol or dimethylformamide, and then added to the treatment bath, which can contain additional assistants conventionally used in dyeing, for example dispersants, wetting agents, acids, bases and/or dyes. The organic stock formulation can already contain such assistants.

The textile materials can be impregnated e.g. with hot or cold aqueous dye, bleaching, chroming or aftertreatment baths containing the active ingredients. Various textile finishing processes are possible, for example the pad or exhaust process.

The treatment is conveniently carried out in the temperature range from 10® to 100®C, in the dye bath preferably in the range from about 60® to 100®C and in the aftertreatment or wash bath preferably in the range from 10* to 70®C, preferably from 20* to 60*C.

As further assistants there may be added to the treatment baths e.g. dispersants, emulsifiers or surfactants. The liquor can additionally contain further conventional assistants, such as water-soluble perborates, polyphosphates, carbonates, silicates, fluorescent whitening agents, softeners, salts with acid reaction, such as ammonium or zinc silicofluoride, or certain organic acids such as oxalic acid, acetic acid or, in particular, formic acid, and also antimicrobial agents and finishing agents, for example those based on synthetic resins or starch. If the mothproof and beetle-resistant finishing is carried out together with the dyeing of the material (e.g. wool), the liquors additionally contain the corresponding dyes and, if appropriate, the necessary assistants, e.g. levelling agents.

The aqueous treatment baths may contain, for example, surfactants,for example anionic compounds, such as soaps and other carboxylates (e.g. alkali metal salts of higher fatty acids), derivatives of sulfur oxyacids (e.g. the sodium salt of dodec.ylhenzenesulfonic acid, water-soluble salts of sulfuric acid monoesters of higher molecular alcohols or of their polyglycoi ethers, for example soluble salts of dodecyl alcohol sulfate or of dodecyl alcohol polyglycoi ether sulfate), derivatives of phosphorus oxyacids (e.g. phosphates), derivatives with acid (electrophilic) nitrogen in the hydrophilic group (e.g. disulfine salts), cationic surfactants, such as amines and their salts (e.g. lauryldiethylenetriamine), onium compounds, amine oxides or nonionic surfactants, such as polyhydroxy compounds, surfactants based on mono- or polysaccharides, higher molecular acetylene glycols, polyglycoi ethers (e.g. polyglycoi ethers of higher fatty alcohols, polyglycoi ethers of higher molecular alkylated phenols).

If non-aqueous application is made (solvent application), an appropriate amount of a compound of formula (1) may also be added to a suitable solvent and the material to be protected may be impreg*-nated with the solution so obtained. Suitable solvents for this application are, inter alia, trichloroethylene, methylene chloride, hydrocarbons, propylene glycol, methoxyethanol, ethoxyethanol, dimethylformamide, to which dispersants (e.g. eraulsifiers, such a3 sulfated castor oil, fatty alcohol sulfates etc) and/or other assistants can be added. The material to be protected is usually simply impregnated with these solutions.

The proofing of the material to be protected may also be combined with a dry cleaning process. To this end, an appropriate amount of a compound of formula (1) is dissolved in the cleansing agent (such as a lower halogenated alkane, e.g. trichloroethylene etc.) and the cleaning process is carried out in the usual manner.

However, an amount of a compound of formula (1) may also be dissolved in a readily volatile organic solvent and the resulting solution then sprayed onto the substrate to be protected (spray application).

Textile fabrics which contain wool, furs and feathers are particularly suitable for this application. The advantage of the spray application is that pollution of the wastewaters is avoided on account of the recovery of the solvent.

In the process of the present invention, the compounds of formula (1) may also be used in combination with other protectants which act against insects that feed on keratin, for example with urea derivatives, benzimidazoles, aromatic sulfonamides and phosphoric and phosphonic acid esters and 5-phenylcarbamoyIbarbituric acid derivatives.

The amount of compound of formula (1) which is added to the treatment bath or non-aqueous solvent depends on the substrate and the method of application. However, this amount is ordinarily such that, after application to the material which it is desired to protect, the latter contains about 10 to 2000 ppra, preferably 100 to-1000 ppm, of compound of formula (1) with the upper limit being largely determined by economic considerations, whereas the lower limit depends on criteria such as the intended breadth and permanency of the protective action. This corresponds, for example, to concentrations of 0.001 to 1 g of active ingredient per litre of treatment bath using the exhaust process at a liquor to goods ratio of 1:20, depending on the degree of exhaustion attainable. In the pad process concentrations of up to 2 g of active ingredient per litre are possible.

As stated above, in the process of the present invention the pure cis-isomers of formula (1) or mixtures of isomers containing at least 90% of the cis-isomers can be used. All statements in the above detailed process description referring to compounds of formula (1) also apply to mixtures of isomers containing at least 90% of the compound of formula (1). In the process of the present invention it is preferred to use those mixtures of isomers con- 2116 9 taining at least 95% of cis-compound of formula (1), with the almost pure, cis-isomers being particularly preferred.

The 3-phenoxybenzyl (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropanecarboxylate ("cis-Permethrin") and the 3-phenoxy-a-cyano-benzyl (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate ("c.is-Cypermethrin!') are already known from Pesticide Science, 1975 (6), 537-542 and 1974 (5), 791-799.

The cis-isomers of formula (1) and the mixtures of isomers containing at least 90% of said isomers can be obtained according to various process which are known per se. One process comprises reacting (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid or a functional derivative thereof with a compound of the formula R -CH-®^ y~Ri (2) ' #='\ AN R o . . wherein R is the hydroxyl group or a halogen atom.

Suitable functional derivatives of cis-2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropanecarboxylic acid are,in addition to the salts thereof, preferably acid halides (-C0X) and esters (-COOR^), wherein X is a halogen atom, preferably chlorine or bromine, and R^ is preferably alky.l, most preferably ethyl or methyl. The process is preferably carried out as follows: a) reacting cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid with a compound of formula (2), wherein R^ is halogen, in the presence of an acid acceptor; 2116 b) reacting an acid halide (preferably the chloride or bromide) of cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid with a compound of formula (2), wherein is hydroxy, in the presence of an acid acceptor; c) reacting cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-carboxylic acid with a compound of formula (2), wherein R^ is hydroxy, in the presence of a hydrophilic agent; or d) reacting an alkyl ester of cis-2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropanecarboxylic acid with a compound of formula (2), wherein R^ is hydroxy, with removal of alcohol.

Particularly suitable acid acceptors for processes a and b are tertiary amines, such as trialkylamine and pyridine, as well as hydroxides, oxides, carbonates and bicarbonates of alkali metals, alkaline earth metals and alkali metal alcoholates, e.g. potassium tert-butylate and sodium methylate. For process c, e.g. dicyclohexyl carbodiimide can be used as hydrophilic agent. Processes a to d are carried out e.g. at a reaction temperature in the range from -10° to 120°C, usually from 20° to 80°C, under normal or increased pressure and preferably in an inert solvent or diluent. Suitable solvents or diluents are e.g. ether and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, preferably benzene, toluene, a xylene, chloroform and chlorobenzene; nitriles such as acetonitrile; dimethylsulfoxide and ketones such as acetone and methyl ethyl ketone.

The starting (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclo-propanecarboxylic acid and the derivatives thereof are known (q.v. Pesticide Science, 1974 (5), 791-799). 1&7 2t The compounds of formula (1) can also be obtained in accordance wi :h the processes described in US patent specification 4 242 278 ana British patent specification 1 598 472.

A further possibility of obtaining the cis-isomers of formula (1) comprises separating by methods known per se the mixture of cis/ trans-isomers obtained in the non-stereospecific synthesis of 3-phencxybenzyl esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclo-propanecarboxylic acid into the two geometrical isomers. This separation can be effected e.g. by fractional crystallisation in a suitable solvent (e.g. in an aliphatic or aromatic hydrocarbon such as hexane, toluene etc.) or preferably by column chromatography using suitable eluants (e.g. the solvents indicated above). In order to keep the loss of cis-isomers as low as possible in these methods, the separation can e.g. be effected only until a mixture of isomers containing up to 10% of the trans-isomers is obtained, which mixture of isomers can also be used in the process of the present invention.

The mixtures of cis/trans-isomers containing the two isomers in approximately equal amounts (e.g. cis:trans 40:60) and the preparation thereof are known from the literature (q.v. for example G.B. published applications 1,413,491 and 1,446,304 and N.Z. Patent 186580 and Canadian ADDlication 1,152,093). ^£==5- .:•/ * Finally, the present invention also relates to compositions / for providing keratinous material with a protective finish ; 27 JUL /9fi against attack by pests that feed on keratin, which compositions."^ _ contain one or more 3-phenoxybenzyl esters of (+)-cis-dimethyl-3- * (2,2-dichlorovinyl)cyclopropanecarboxylic acid as defined for formula (1) in pure form or as a mixture of isomers containing at least 90% of said cis-isomers. These compositions preferably contain as active ingredient a mixture of isomers containing at least 95% of the cis-isomers of formula (1), most preferably the 21169? almost pure cis-isomer itself.

The compositions of the present invention may, in addition to the active ingredient, contain conventional carriers and/or formulation assistants, e.g. organic solvents, water, acids, bases, wetting agents, dispersants and/or emulsifiers. The compositions of this invention may also contain assistants which are described above as assistants in the treatment bath for the proofing process of this invention. Further, the compositions of the present invention may also contain other protectants which act against insects that feed on keratin, e.g. urea derivatives, benzimidazoles, aromatic sulfonamides, phosphoric and phosphonic acid esters and/or 5-phenyl-carbamoylbarbituric acid derivatives.

The following Examples illustrate in more detail the process of the invention as well as the preparation of compounds of formula (1) used therein. It must, however, be emphasised that the invention is not restricted to these Examples.

In the following Examples, as also in the entire description and claims, parts and percentages are by weight unless otherwise stated.

Example 1: While cooling with ice and with exclusion of air (N^ flushing), 2.3 g of pyridine followed by a solution of 5.2 g of 3-phenoxy-a-propin-l-ylbenzyl alcohol in 10 ml of toluene are added dropwise to a solution of 5 g of GO-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride in 20 ml of toluene. Then a trace of 4-dimethylaminopyridine is added. The reaction mixture is stirred overnight and then diluted with about 200 ml of toluene and about 200 ml of water, extracted in succession with 2n HC1, 10% K^CO^-, 10% NaHCO^" and a saturated solution of sodium chloride, dried over MgSO^ and concentrated by rotary evaporation. The concentrated solution is filtered in a 300 g <?? collecting beaker over 200 g of silica gel and eluted with hexane/ ether 95:5. The solvent is removed, affording 8.6 g of 3-phenoxy-a-propin-l-ylbenzyl (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate of the formula CI 0 v II ^c=ch ^c-0-ch—^ y (101) ci '^^ch - ch c * = \ \ / c \ = / C I /\ ch3 ch3 ch3 in the form of a pale yellow oil with a refractive index of n^° = 1.5712.

For purposes of comparison, using (+)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride as starting material, the isomeric 3-phenoxy-a-propin-l-ylbenzyl (+)-trans-2,2-dimethy1-3-(2,2-dichlorovinyl)eyelopropanecarboxylate (compound 102) is obtained in analogous manner in the form of a yellow oil with a refractive index of n^ = 1.5687.

The mixture of cis/trans-isomers of 3-phenoxy-a-propin-l-ylbenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate (compound 103) known from Canadian application 1,152,094 has a refractive index of n^ =1.5700.

Example 2: Using 3-phenoxybenzyl alcohol or 3-phenoxy-a-cyanobenzyl alcohol and (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride as starting materials, the following compounds are obtained in a manner analogous to that of Example 1: 3-phenoxybenzyl OO-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)- ^ ^ ^ o cyclopropanecarboxylate (compound 201) with a refractive index ojf'V , li . nl n = 1.5680, and \| 27 Jut 19^7 ;:,V 21169 3-phenoxy-a-cyanobenzyl (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate (compound 202) with a refractive index of n^ = 1.5610.

For purposes of comparison, using OO-trans-2,2-dimethy1-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride, the following two isomeric trans-compounds are obtained in analogous manner: 3-phenoxybenzyl (+)-trans-2,2-dimethyl-3-(2,2-dichlorvinyl)cyclopropanecarboxylate (compound 203) with a refractive index of n^° = 1.5642, and 3-phenoxy-a-cyanobenzyl (+)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate (compound 204) with a refractive index of n^° = 1.5623.

Further, for purposes of comparison, the corresponding mixtures of €>»| cis/trans-isomers known from -German published applications 1,413,491 1 4.4fc,204 2 326 077 are referred to: 3-phenoxybenzyl (+)-cis/trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate (compound 205) known under the name of "Permethrin", ratio of cis:trans circa 40:60, and 3-phenoxy-a-cyanobenzyl (+)-cis/trans-2,2-dimethy1-3-(2,2-dichlorovinyl) cyclopropanecarboxylate (compound 206) known under the name of "Cypermethrin", ratio of cis:trans circa 40:60.

The starting (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclo-propanecarboxylic acid chloride required in Examples 1 and 2 can be obtained as follows: -.14 - a) The preparation of both (O-cis- and C+)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid is described in Pesticide Science, 1974 (5), 791-799, points 2.1 to 2.3. b) 8 g of (+)-cis-2,2-dimethyl-3~(2,2-dichlorovinyl)cyclopropane-carboxylic acid are heated in 80 ml of hexane to reflux. After the addition of one drop of dimethylformamide, a solution of 6 g of oxalic acid chloride in 10 ml of hexane is slowly added dropwise for 1 hour. After boiling at reflux for a further 3-j hours, the evolution of gas ceases. The solvent is removed by rotary evaporation and the residue is distilled in a bulb tube at 80°C and 0.1 torr. The resultant CO -cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride can be used direct for the reaction according to Example 1 or 2.

The corresponding trans-acid chloride is prepared in analogous manner.

Example 3: 11 g of the mixture of isomers 3-phenoxy-4-fluoro-a- cyanobenzyl QO-cis/trans-2,2-dimethy1-3-(2,2-dichlorovinyl)- cyclopropanecarboxylate (yellow oil, cis:trans ratio circa 40:60, 23 n^ = 1.5548) obtainable according to Example 2 of New Zealand Patent No. 186580 are chromatographed in a column of silica gel eluted with toluene/hexane 1:1 [net weight of the silica gel (40/60 mesh) 1200 g; column diameter 9 cm]. 3 fractions are eluted, the first of which contains the mixture of cis-isomers, the third the mixture of trans-isomers, and the second a mixture of cis/trans-isomers. The solvent is removed, affording from fractions 1 and 3 3.8 g of 3-phenoxy-4-fluoro-a-cyanobenzyl (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate of the formula ^ ci 0 \ 11 /c=ch ^c-o-ch-v «-f r ^ ^ l \-/ (301) ci ^ch - eft 1 —\ v cn 0 .y \ \ / \ / c / \ ch3 ch3 xn the form of a yellow oxl with a refractive index of n^ = 1.5567 and an NMR spectrum as shown in Fig. 1, as well as 4.7 g of 3-phenoxy-4-fluoro-a-cyanobenzyl (+)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate (compound 302) in the form of a yellowish wax, the NMR spectrum of which is shown in Fig.

Example 4: Treatment in the exhaust bath A stock solution of each of the test compounds 101, 102, 201, 203, 205, 301 and 302 is prepared by dissolving 50 mg of said compound in 25 ml of ethylene glycol monoethyl ether.

Thoroughly prewetted wool fabric samples of 3 g each are put into an aqueous treatment bath containing the following ingredients: x ppm, based on the weight of the wool, of each test compound (a corresponding amount of the stock solution described above is added to the treatment bath), 1%, based on the weight of the wool, of 80% acetic acid, 4%, based on the weight of the wool, of ammonium sulfate, 0.5 g of a wetting agent and dispersant per litre of treatment bath.

The bath temperature is raised to 98°c in the course of 20 minutes and treatment is carried out for 60 minutes at this temperature. 2116 The bath is then cooled and the samples are rinsed individually with water and dried at room temperature.

The dried wool samples which have been proofed with the test compounds are then subjected to the mothproofing test (protection against feeding damage caused by the webbing clothes moth Tineola bisselliella Hum.) and to the resistance test against larvae of the fur beetle (Attagenus piceus 01iv.) and carpet beetle (Anthrenus flavipes var. seminiveus) in accordance with Swiss standards.

In these tests, larvae of Tineola, larvae of Anthrenus and 6- to 7-week-old larvae of Attagenus are used.

Pieces of the same size are cut out of the wool flannel samples and subjected for 14 days at constant temperature (28°C) and constant relative humidity (65%). to attack (feeding) by 15 larvae of each of the pests. Evaluation for all 3 pests is made according to the loss in weight of the test sample.

The following Table 1 shows the concentration (in ppm, based on the weight of the wool) of each of the test compounds and the loss in weight (in mg) of the test samples caused by pest feeding: Table 1 Compound Tineola Attagenus Anthrenus Concentration Loss in weight Concentration Loss in weight Concentration Loss in weight (ppm) (mg) (ppm) (mg) (ppm) (mg) 101 (cis) 1.2 9.0 300 9.2 102 (trans) 2.6 43.4 300 51.7 201 (cis) 7.5 1.7 4.3 125 18.9 203 (trans) 7.5 26.9 54.2 125 68.3 205 (cis/ 7.5 .8 14.9 125 29.2 trans) 301 (cis) 7.5 0 7.5 11.4 125 14.9 302 (trans) 7.5 0.4 7.5 51.4 125 48.0 i O* v0 The results show that each cis-isomer has a very substantially better activity than both the trans-isomer and the tested mixture of isomers.

Example 5: The pad method 12.5 ml of a stock solution of each of the compounds 101, 102, 201;, 203, 205, 301 and 302 according to Example 4 are diluted with ethylene glycol monoethyl ether containing 1 g/1 of a wetting agent and dispersant. This dilution is made such that the concentration of each test compound in the padding liquor is so adjusted that after padding the wool fabric contains x ppm of the respective compound (q.v. Table 2). 3 ml of each resultant solution are poured into crystallisation dishes. With the aid of pincers, a disc of wool fabric is wetted for circa 3 seconds therein. The moist discs are padded between 2 aluminium sheets, and then pinched off to a liquor pick-up of 100%, based on the weight of the discs. The moist discs are then dried in the air and subjected to the same biological tests as described in Example 4. The results are shown in the following Table 2: • • • # Table 2 Compound Tineola Attagenus Anthrenus Concentration Loss in weight Concentration Loss in weight Concentration Loss m weight (ppm) (mg) (ppm) (mg) (ppm) (mg) 101 (cis) 1.0 2.0 250 1.1 102 (trans) 4.4 .3 250 27.1 | 201 (cis) 7.5 1.9 3.7 125 ■ 2 1 ± .2 | 203 (trans) 7.5 17.4 39.3 125 28.1 205 (cis/ 7.5 .5 32.5 125 11.0 trans) 301 (cis) 7.5 0.8 125 0.1 302 (trans) ——— 7.5 9.3 125 16.3 K) vj 2 Ij i • The results show that each cis-isomer has a very substantially better activity than both the trans-isomer and the tested mixture of isomers.

Example 6; A 10% solution of each of the compounds 101, 201, 202 and 301 in ethylene glycol monomethyl ether is prepared. One part by volume of this solution is diluted with 200 parts by volume of a solvent suitable for dry cleaning, e.g. a suitable petroleum fraction or perchloroethylene. If desired, cleaning promoters can be added. Woollen articles are than treated in the conventional manner in this cleaning fluid and subsequently centrifuged to a solvent pick-up of circa 100% of the weight of the wool. After drying, the articles have an excellent protective finish against the pests that feed on keratin indicated in Example 4.

Example 7: A 0.5% solution of each of the compounds 101, 201, 202 and 301 in methylene chloride, trichloroethylene or a low boiling petroleum fraction is prepared. Woollen articles are sprayed with 2 these solutions from a conventional spray device, so that 2 x 15 g/ta of active ingredient solution is applied, corresponding to a concentration of about 400 ppm of the respective compound on the material at a 30% consumption of the aerosol. The treated woollen fabrics are protected against the pests that feed on keratin indicated in Example 4.

Claims (13)

iWHAT^7WE CLAIM IS:- WhaL ia e.laiui.Mi ij;

1. A process for providing keratinous material with a protective finish against attack by insects that feed on keratin, which process comprises treating the material to be protected with a 3-phenoxyn benzyl ester of (+)-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclo-propanecarboxylic acid, said ester having the formula C / \ CH3 CH3 wherein R is hydrogen, -C=CH, -C=C-CH3 or CN, and R^ is hydrogen or fluorine, or with a mixture of isomers containing at least 90% of said cis-isomers.

2. A process according to claim 1, which comprises the use of a compound of formula (1), wherein R is hydrogen or CN, and R^ is hydrogen.

3. A process according to claim 1, which comprises the use of a compound of formula (1), wherein R is -C=C-CH3, and R^ is hydrogen or fluorine.

4. A process according to claim 1, which comprises the use of a compound of formula (1), wherein R is hydrogen or CN, and R^ is fluorine.

5. A process according to claim 1, which comprises treating the material to be protected, by the exhaust or pad process, with an (1) - 22 - aqueous liquor containing one or more of the compounds as defined in claim 1, and which aqueous liquor may contain additional conventional textile assistants such as dispersants, wetting agents, acids; bases and/or dyes.

6. A process according to claim 1, which comprises treating the material to be protected with an organic cleaning liquid containing one or more of the compounds as defined in claim 1.

7. A process according to claim 1, which comprises spraying the material to be protected with an organic solvent containing one or more of the compounds as defined in claim 1.

8. A process according to claim 1, which comprises applying a to the material to be protected -e&e» compound^ of formula (1) in an amount of 10 to 2000 ppm by weight, based on the weight of said material.

9. A process according to claim 5, which comprises treating woollen textiles in a dye bath by the exhaust process.

10. A process according to claim 9, which comprises treating the woollen textiles in the aftertreatment bath by the exhaust process. /V

11. The keratinous material finished according to claim 1. j|a> 2 7 JUL 1987-/

12. The keratinous' material according to claim 11 which v',?V\ . ^ •©• //" contains 10 to 2000 ppm by weight of compound of formula (I) based on the weight of the material.

13. A luwpusiliuu Iul pi'iruidiug Ke-uatinoua material with a pL'ute-^tive. finiah againat attack by pcato that feed on keratin, which eompooition containo one or mora 3-phonouybcnnyl ootoro CIBA-GEIGY AG By their Attorneys BALBWIN, SON & CAREY