SE444313B - M-PHENOXIBENZYL AND ALFA-CYANO-M-PHENOXYBENZYL ESTERS OF 2-HALOGEN-ALKYL (OXI, THIO, SULFINYL OR SULPHONYL) PHENYLALKANIC ACIDS, PREPARATION AND USE OF DEMEDIC DOMESTIC DEMEDIC DOMESTIC DEMEDIC DEMEDIC DEMEDIC DEMEDIC DIMESIDE - Google Patents

Description

7902467-5 wherein RCF2X-, Y and Z are all in the meta or para position to the carbon atom to which the alkanoic acid ester group is attached and X represents O, S, SO or SO2; Y and Z each represent H, Cl, F, Br, NO 2, CH 3 or OCH 3; R represents H, F, Cl, CHF 2 or CF 3; R 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl; R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 'or OCH 3.

Preferred compounds have the structure: "z Rs ncrzo \ I I __ Rq cn-co-o-cxx Û o Ü wherein RCF2O- is in the meta or para position to the carbon atom to which the alkanoic acid ester group is attached; R represents H or F; R 2 represents ethyl, n-propyl or isopropyl; R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 or OCH 3. The most preferred compounds are illustrated by compounds of the preferred structure, wherein R represents H or F, R 2 isopropyl, R 3 CN and R 4 H or F. The present invention also relates to a sweet to control insects and acarids by the insects and acarids, their find, stall and / or food storage are brought into contact with an insecticidal or acaricidally effective amount of an m-phenoxybenzyl ester of 2-haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl) phenylalkanoic acid. The invention also includes a method of protecting agronomic crops, either growing or harvested and homothermic animals from infestation by insects and / or acarids by treating the crops and / or animals with an insecticidal or acaridically effective amount of the above-identified m-phenoxybenzyl esters of the 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) phenylalkanoic acids.

The invention also includes the 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) phenylalkanoic acids of the formula: RCF X 2 \ - ÉHCOOH YZ R 2 wherein RCFZX-, Y and Z are all in meta or para-position to the carbon atom to which the alkanoic acid group is bonded, R represents H, F, Cl, CHF 2 or CF 3, X represents O, S, SO or SO 2, R 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl and Y and Z represent H, Cl , F, Br, NO 2, CH 3 or OCH 3. Preferred compounds of the invention are those compounds wherein X represents S or O. The compounds can be used as intermediates for the preparation of the m-phenoxybenzyl and the α-cyano-m-phenoxybenzyl esters.

The most closely related technique known is described in South African patent application 73/4462, which relates to phenylacetic acid (CH) CO (CO). including alkoxyphenylacetic acids, which are useful intermediates derivatives of the formula: for the preparation of insecticidally active phenylacetic acid esters. See also Belgian Patent 650,701. The acids VIII of the invention shown in the flow chart below, wherein R 2 represents ethyl, n-propyl or isopropyl can be prepared using the corresponding toluene (IV) as starting material. The process for the preparation comprises four steps, wherein the first is halogenation of the toluene (IV) with bromine, chlorine, N-bromosuccinimide (NBS) or the like. This reaction preferably takes place in the presence of an inert organic solvent such as carbon tetrachloride and a radical initiator such as light, benzoyl peroxide or azo-bis-isobutyronitrile to produce the benzyl halide (V). The benzyl halide of formula V was then converted to the corresponding phenylacetonitrile (VI) by reaction with sodium or potassium cyanide in the presence of dimethyl sulfoxide (DMSO), ethanol or the like at elevated temperature. Alternatively, the benzyl halide may be reacted with sodium or potassium cyanide in an aqueous toluene mixture using a quaternary ammonium salt such as benzyltriethylammonium chloride or tricaprylmethylammonium chloride or a tertiary amine such as tri-n-hexene phenylamine or a substituent of phenylamine. acetonitrile (V) is then soldered to a solder before being treated with an alkyl halide in the presence of a base and an inert organic solvent; the crown ethers have been found to be useful catalysts in this reaction: α-Alkyl (substituted phenyl) acetonitrile formed in the above reaction is carried out in formula VII and hydrolysis of this α-alkyl (substituted phenyl) acetonitrile of formula VII using an alkali metal hydroxide in the presence of alkylene glycol and water gives alpha-alkyl (substituted phenyl) acetic acid of formula VIII. the acid of formula VIII with thionyl chloride, thionyl bromide, or the like, preferably in the presence of an aromatic solvents such as benzene or toluene then give alpha-alkyl (substituted phenyl) acotyl halides (II), which are reacted with m-phenoxybenzyl alcohol (III, R 3 = H) or alpha- "cyano-m-phenoxybenzyl alcohol (III, R 3 = CN) to the desired m-phenoxybenzyl esters or the alpha-cyano-m-phenoxybenzyl esters of 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) -phenylalkanoic acids (I) which are useful insecticides.

Various optical isomers of the acids of the invention are obtained by the methods described. For example, it has been found that when α-isopropyl-4-trifluoromethoxyphenylacetic acid is mixed with about 0.5-1.0 molar equivalents of (-) - α-phenylethylamine in a suitable solvent such as ethanol or aqueous ethanol, the salt of (+) - syran. Upon acidification, this salt releases the acid, which is generally in excess of 85% of the (+) - isomer. Higher redissolution can be achieved by recrystallization of the (-) - α-phenylethylamine salt or by repeating the redissolution procedure with freshly prepared (-) - α-phenylethylamine. The m-phenoxybenzyl or α-phenoxybenzyl or α-cyano-m-phenoxybenzyl esters of the completely redissolving (+) - α-isopropyl-4-trifluoromethoxyphenylacetic acids have been found to be about twice as effective against insects as the esters prepared from the racemic acid. As for the α-cyano-m-phenoxybenzyl ester, a further increase in activity is obtained when active α-cyano-m-phenoxybenzyl alcohol is used in the ester-forming step.

Preferably, the m-phenoxybenzyl esters of the 2-haloalkyl (pxy-, thio-, sulfinyl- or sulfonyl) phenylalkanoic acids, illustrated by formula I, can be prepared by an alpha-substituted 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) phenylacetyl halide (II), preferably the chloride is reacted with an m-phenoxybenzyl alcohol (III). The reaction is generally carried out in the presence of a solvent such as diethyl ether, benzene or toluene at a temperature between about 10 ° C and 30 ° C. presence of an acid acceptor.

The acid acceptors that can be used are tertiary organic amines, trimethylamine, triethylamine and pyridine. This reaction can be illustrated as follows: 7902467-5 CH-COA + 'in 0 X CH-Qá-,. '. RRR crzx 2 \\ 3 L (II) (III) «acid- '- acceptor CH-CO-O-CH -OII RCFZX R2 R3t-' (I) wherein RCFZX is in the meta or para position to the carbon atom of which alkanoic acid group is attached or wherein X represents O, S, SO or SO 2 and wherein R represents H, F, Cl, CHF 2 or CF 3; R 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl; R 3 represents H or CN and A represents halogen, preferably chlorine.

With respect to the compounds of the present invention illustrated by formula I, it should also be understood that various optical isomers of the above compounds result from the methods described.

For example, in the synthesis of the esters of formula I, wherein R 3 represents hydrogen, a chiral center is present at R 2 and d and 1 isomeric pairs are formed. Also α-cyano substitution at R3 gives an additional chiral center which allows an additional D, 1-pair.

For example, it has been found that when α-isopropyl-4-trifluoromethoxyphenyl acetic acid is mixed with about 0.5 - 1 molar equivalents of (-) - α-phenylethylamine in a suitable solvent such as ethanol or aqueous ethanol, the salt of the (+) - acid precipitates. When acidifying 7902467-5, this salt releases the acid, which is generally in excess of 85% of the (+) - isomer. Higher redissolution can be achieved by recrystallization of the (-) - α-phenylethylamine salt or by repeating the redissolution process with newly produced (-) - α-phenylethylamine. The m-phenoxybenzyl or α-cyano-m-phenoxybenzyl esters of the completely redissolved (+) - α-isopropyl-4-trifluoromethoxyphenylacetic acid have been found to be twice as effective insecticides as the respective ester produced from the racemic acid. In the case of the α-cyano-m-phenoxybenzyl ester, a further increase in activity is obtained when the optically active α-cyano-m-phenoxybenzyl alcohol is used in the ester-forming step.

The α-substituted 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) phenylacetyl halides (II) wherein R 2 represents ethyl, n-propyl or isopropyl can be prepared by using suitable toluene (IV) as starting material. The process for the preparation comprises five steps, the first of which is halogenation of the toluene (IV) with bromine, chlorine, N-bromosuccinimide (NBS) or the like.

This reaction preferably takes place in the presence of an inert organic solvent such as carbon tetrachloride and a radical initiator such as light, benzoyl peroxide or azo-bis-isobutyronitrile to give the benzyl halide (V). The benzyl halide of formula V is then converted to the corresponding phenylacetonitrile (IV) by reaction with sodium or potassium cyanide in the presence of dimethyl sulfoxide (DMSO), ethanol or the like at elevated temperature. This (substituted phenyl) acetonitrile (VI) is then easily alkylated when treated with an alkyl halide in the presence of a base and an inert organic solvent; crown ethers have been found to be useful catalysts in this reaction. The α-alkyl (substituted phenyl) ocetonitrile formed in the above reaction is illustrated by formula VII and hydrolysis of this α-alkyl (substituted phenyl) -aetonitrile of formula VII using alkali metal hydroxide in the presence of ulkylene glycol and water. the α-alkyl (substituted phenyl) acetic acid shown as formula VIII. Treatment of the acid of formula VIII with thionyl chloride, thionyl bromide or the like, preferably in the presence of an aromatic solvent such as benzene or toluene then gives the α-alkyl (substituted phenyl) uceryl halogen (II) which is reacted with m-phenoxybenzyl alkane (III) or the α-cyano-m-phenoxybenzyl alcohol fills the desired m-phenoxybenzyl ester of the α-cyano-m-phenoxybenzyl ester of the 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) phenylalkanoic acids (I).

These reactions are graphically illustrated by flow chart I below. 7902467-5 FLOW DIAGRAM I Initialization of m-phenoxybenzyl esters of 2-hologenulkyl (oxy-, fio-, sulfinyl- or sulfonyl) Phenylulonic acids.

- ~ Q RCFZX or RcFzx (NES) (IV) _ (V) DMSO RCFZX _ RCFZX (V) I (VI) Benzene, CHZCN + R X CHCN - Kroneter | RCFZX RCFZX R2 (VU <> (vn) H20 R '' RcFyx .2 RCFZX Rz WII) (VIII) benzene R _ - (v1II) (n) çHCOCl + HOçH 0 + Rcrzx H2 R3 - (II) i (III) cu ~ co-o-cn 0 I _ Bßfße fl I »| Rcrzx R; 33 - (I) 7902467-5 As an alternative to the benzyl bromide (V) shown in the flow chart I in which the products are limited to para-substitution, the haloalkyl (oxy- or thio-) benzene (IX) can be chloromethylated using of a mixture of para-formaldehyde or trioxane with zinc chloride and dry hydrochloric acid to benzyl chloride (X) which can then be used instead of V to complete the synthesis to I. This modification is illustrated by the following sweet: RCFZY _ + (cuzmn + Hclšflíä RcF2-Y1 / (c) (HXC1 (IX) - Y: H0 or 5 (X) Preparation of m-phenoxybenzyl and the α-cyano-m-phenoxybenzyl ester of α-alkyl-3- (or 4) -trifluoromethoxyphenylacetic acid can also provide - occurs according to a sequence beginning with alkylation of m- or p-methoxyphenylacetonitrile, using an alkyl halide in the presence of a crown ether and a base. When the m-methoxyphenylacetonitrile is used in this reaction, the α-alkyl-3-methoxyphenylacetonitrile and when the β-isomer is used, α-alkyl-4-methoxyphene is obtained ylaceto-nitrile. As will be seen below, the location of the methoxy group on this phenylacetonitrile starting material determines the position of the trifluoromethoxy substituent in the final product. The α-alkyl-3 (or 4) -methoxyphenylacetonitrile indicated above is converted to the α-alkyl-3 (or 4) -hydroxyphenylacetonitrile by treatment with boron tribromide, preferably in the presence of a solvent such as methylene chloride. The treatment of the phenol thus formed with thiophosgene and the base in the presence of a solvent such as chloroform then gives the chlorothioester of O- [m- or p- (1-cyano-2-methylpropyl) phenyl] formic acid. This ester is converted to α-alkyl-3 (or 4) -trifluoromethoxyphenylacetonitrile with molybdenum hexafluoride and this compound is then hydrolyzed to the corresponding α-alkyl-Sf (or 4) -trifluoromethoxyphenyl acetic acid by reaction with ethylene glycol an alkali metal hydroxide and water.

Treatment of the α-alkyl-3- (or 4) -trifluoromethoxyphenyl acetic acid with thionyl chloride in the presence of an aromatic solvent such as benzene or toluene gives the corresponding acid chloride which reacts with m-phenoxybenzyl alcohol or α-cyano-m-phenoxybenzyl alcohol to the desired m-phenoxy -cyano-m4phenoxybenzyl-alkyl-3- (or 4) -trifluoromethoxyphenyl acetate.

This reaction is graphically illustrated in Flow Diagram II below. 79ø2467-5 12 FLOW DIAGRAM II I / \\ kroneter Ä E C fl zc "" Rzß "* fi ïïaör fl“ EWN __ R v CH3O '_ cnao 2 cn c1 ^ V S :: 3> -cwcN + -mn3_¿LJL. mwNV I | cuao R2 ao R2 / \ cHc13 / \ _ í: ï * _Ü> »- çn-CN + csc12 Nao fl I S çn-cn no * *" "*“ 2 c; ~ co 'Å2. S í <::: 3> - »ca-cm + MOFG cn-cm 1 u I 'I cl-co R2 cF3o R2 f š :::::> - cn-cN + nocnzcnzo fl S03 CH-cdon å 2 å .cF3o V 2 V 'crso V2 _ §:; :::> - ca-coon + soclz --- cn-cocl II, V n _ R cF3o 2 cF3o 2 í :::::> - cu-cocl + ou-cn o - II cr o R2 Ra 3. cu-co-o-CH o Pyrid in I Û cF3o R2 R3 B 7902467-s In the reactions according to flow chart II, R2 represents ethyl, n-propyl or isopropyl and R3 represents hydrogen or cyano.

Although Flowchart I can generally be used to prepare many compounds of the invention, it has been found that upon alkaline hydrolysis of the nitriles, the HCF2 radical may be lost in the examples in which RCF2X is HCFZO- or HCɧ ~. However, it has been found that it can be reintroduced by reacting the phenol or thiophenyl in question with chlorodifluoromethane in a mixture of aqueous alkali and dioxane.

The actual synthesis of the examples comprising the HCF 2 O group is best illustrated by Flow Diagram III in which the α-alkyl-3- (or 4) -methoxyphenylacetonitrile (according to Flow Diagram II) was converted to the α-alkyl-3 (4) -hydroxyphenylacetic acid using hydrobromic acid. Treatment with chlorodifluoromethane in aqueous alkali and dioxane gives the α-alkyl-3 (4) -difluoromethoxyphenyl acetic acids. These acids were converted to the desired m-phenoxybenzyl or α-cyano-m-phenoxybenzyl esters as illustrated in Flowchart III. 7902467-s 14 FLOW DIAGRAM III CH_CN ɧÄ_ fl ÉE_. CH-00 I Û CH 0 R2 HO R 2H 2 ca-co H + ncclr Ei9X fl H. It should also be noted that although the procedure shown in the Flowchart I is suitable for the preparation of most of the examples in which X is:,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, -S- or -å-, it is often better to prepare the O final acids (VIII) or esters (I) wherein X = -S- and then oxidize the sulfur atom to the desired 0 u 9 in -S- or ëñ the analogues using suitable oxidizing agents such as m-chloroperbenzoic acid, sodium periodate or hydrogen peroxide.

For the preparation of such Compounds of structure I wherein R 2 is t-butyl, the following reaction sequence starting from the meta- or para-substituted aldehyde was used: (1) reaction with t-butylmagnesium chloride; (2) conversion of the neopentyl alcohol to the chloride using thionyl chloride; (3) preparing the Grignard reagent from the chloride using magnesium in tetrahydrofuran; and (4) carboxylation with carbon dioxide.

The sequence is further illustrated by the synthesis of α-t-butyl-3- (or 4) -trifluoromethoxyphenylacetic acid as illustrated in Flow Diagram IV. The acids can be transferred to the corresponding esters in the manner shown in Flowchart I. 7902467-5 16 FLOW DIAGRAM Iv cno + ¿¿ßumgc1 en-ou “2, I; _ _ 'c (cn) i CF30 cF3o 3 3 \ I / \ cH-o fl + soclz ___-_.- cH-cl.

I | cF3o C (C “3) 3, 'cr3o C (° 33) 3 _ 1. Mg,' when Én cl 2. C02 cr o“ gull 3 'E + o __ C (C ".3) 3: i Ä CF3 For those compounds of structure I in which R 2 is isopropenyl, the compound of the α-isopropenyl group can be prepared according to the following reaction sequence using the meta- or pura-substituted phenylacetic acid: (1) reaction with two equivalents of isopropylmcgionium chloride; transferring the hydroxy acid to the sphere, and (3) dehydrating the hydroxy ester with P 2 O 5.

The synthesis is further illustrated by the preparation of phenoxybenzyl-α-isopropenyl-4 (or 3) -trifluoromethoxyphenylucephute according to flow diagram V. FLOW DIAGRAM V cn coon ÄL-åïfrmgcl 2 2. cu "' cF3o _ C330 / CH3 CH3 í :::::> - en-coon + Brcnz-¶ ::::: í-o + Et3N I c-on CF o ß / \ cH3 cH3 I _ --- ca-co -o-cH2 “- I c-on cF o - ß / \ CH3 CH3> I» P o ca-co-o-cH2 * I :::;] - 0 _2 = É_.

I, - c-on »cr o 3 / \ Ä cH3 CH3 I c cr o cH-co-o-CH2" ï ::::: [- o_1:; ::] ß / \ en cn 3 2 7902467- In the formation of the α-cyano-m-phenoxybenzyl ester products according to the procedures illustrated in either Flow Diagrams I or II, it is not necessary to isolate the α-cyano-m-phenoxybenzyl alcohol starting compound, it is equally convenient or even more convenient to allow a mixture of m-phenoxybenzaldehyde, an alkali metal cyanide such as sodium cyanide and the α-substituted 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) phenylacetyl halide react together in one step to form the final α-cyanoate.

Flow diagram VI illustrates the preparation of the mano- and disubstituted haloalkyl (oxy-, thio-, sulfinyl- and sulfonyl-) alkanoic acid m-phenoxy-m-phenoxybenzyl esters of the invention illustrated in Examples 40-68 below.

/ N W 7902467-5 FLOW DIAGRAM VI ROÖ-çlx-cooxa + ßrz or C12 gfíß, HQQCHCOOH z | _ R “2 _ _ y W 2.

V fl rlz and Y denote H, Br or Cl no cfxxcoou + Naon + cm- * zcl- fl fëcuoßcncoøxx z R Z 1 | z 2 _ y 2 vara. Z ochY befecknor H, Br eller Cl cuaogfnlïrlcu + uBr -> nø © fflzucoou az R 2 I C113 cu3 i _ 4 HQWQCHCQUH + Naou + cxF2c1 __ >> .Fzcnoçacoou | .

R. R 2 - -. 2. ena. C113 cu3o © cu2ßr + Nacn ---> CHQQCHZCN r - F * _ cn o ca cu + n m: + Neon -__; cH o 'cucu 3 2 2 3, P - F “2 CH30 © 4EHCN + HBL -___) HO ~ ®4IJHCOOH r“ 2 r- “z MQQ-cíucuou + Naon + curzcl> Fzc fl ogizucoorx RF 2 F“ z HU CEHCUOII + HNO3 "_” “> NO (| IIICOOH R R2 2 NO2 7902467-5 N HU- CHCUOH + NaOH + CHFZCl> F7CHO (fHCOOH I s.

R 'R 2 2 N02 4 N02 V I _ _ .I' @ ~ cnzo®cxxzou + vara 5935- »© ~ cu2o®cu2ßr i ocu3 _ V ocna 'czLo- CH Br + Nacu 959» CH o crx cN .e. 2 2, 2 ß cu 3 ocu: f ”LD m_- + wirv øw fl Em-" Cl y ... f 'L __ J CH20 (EHCN + HC1 ----> HO-? HC_OOH RR (m3 2 ocn3 2 ROQfH -coou + cnrzcl + _: go fl- Qrzc fl oïncoon R 'R 2 2 OCH3 - OCH3 OH + Na0CH3 + Pyridín + A + CHO + CuClz R _ 4 Br, QOÛ cuo <114> ocH 3 Gen ZOQ-cízicu R ï, ocn 3 2 i A _ gm ÛÛÛ-enn + ncN> Û ° Ûcncr4 “4“ 4 7902467-'5 21 l + cn \ _> 2 2 Mgßr + C2H5 ° /! (Innan ¶ <V \ cacu nå _ _ ~~ - CHC13 _.____.__ è 'Ex Qçncn + csclz mon ä š I' ____ çHCN I '': ff Rz y / I ¥ L¿cx '* ZYS _ »N KOH -CHCN + HOCHZCHZOH å I H20 çxxcoo fl \ RZ CFax _ R : zyzy CFX Rcvzx 'I Benseh çucoo fl + soclz A> Rc1-'2 ç fl coc1 z “zz“ z> yv ncrzx o _ (izucocl + rio-fn: 14 + Pyrmiq z 122 Ra Y,, RCF XI. 2 CU-CO The compounds of the invention are highly effective as contact and gastrointestinal toxins for ixodide attachments and a variety of insect species, especially Dipterous, Lepidopterous, Coleopterous and Homopterous insects..................................... They are unusual among the pyrethroids in that they u has a very persistent residual insecticidal activity on plant tissue, they are effective in the soil and surprisingly effective in controlling ixodidoe and protecting animals against insect infestation 'and ixodidae when administered to the animals orally or parenterally or applied thereto as a topical insecticidal or acaricidal preparation. They do not need to be mixed with stabilizers to give insecticidal and acaricidal compositions with stabilizing effect; however, they can be used in combination with other biological chemicals; for example pyrethroid synergists such as piperonyl butoxide, sesamex or n-octyl sulfoxide of isosafrol. They can also be used in combination with conventional insecticides such as phosphates, carbamates, farmamidines, chlorinated hydrocarbons or halobenzoyl ureas. To obtain control of insects, including soil insects, which attack growing plants and / or harvested crops, including stored grains, the insecticidal compounds of the present invention may be applied to the foliage of the plants, the locus of the insects and / or the feed of the insects. In general, the active compound is applied in the form of a dilute liquid spray; however, it can also be applied as an aerosol, a dust, a granulate or a wettable powder formulation.

Liquid sprays, which are especially useful for oil sprays and emulsifier baro concentrates that can be further diluted for application.

When they are respectively prepared as a liquid concentrate, dispersed to facilitate handling and shipping, these preparations are generally in water at the site of use and are then applied as a dilute spray to the bloodstream, soil or surface of the area which, _ .. , ..._ 7902467-5 23 shall be treated.

A typical emulsifiable concentrate useful for protecting a variety of crops such as cereals, cabbage crops, cucumber bits, corn, cotton, tobacco, soybeans, ornamental plants, shrubs and the like, may comprise about 20% by weight of the active ingredient; 4% by weight of an emulsifier conventionally used in the preparation of pyrethroid preparations; 4% by weight of surfactant; % by weight of an organic solvent such as cyclohexanone and about 47% by weight of a petroleum solvent having a minimum aromatic content of about 83% by volume.

For use as animal systemic insecticidal and acaricidal agents, the compounds of the present invention may be administered to the host animal either orally or parenterally.

When administered orally, it may be in any suitable form intended for oral administration such as bolus, capsules, tablets or as an oral liquid. The active ingredient may also be incorporated into an edible animal feed such as a nutritionally balanced diet containing 0.0001-0.1%, preferably 0.001 - 0.05%, based on the weight of the feed of the active compound.

If desired, the systemic insecticidal and acaricidal agent can be incorporated into the animal's body by subcutaneous, intramuscular or intraperitoneal injection so that it can be distributed throughout the animal's body by the action of the animal's circulatory system. In practice, the systemic agent may be dissolved or dispersed in a pharmaceutically acceptable carrier such as water, propylene glycol, vegetable oils, glycerol formal or the like for administration.

Preferably, the systemic agents have a good safety margin and are effective in protecting a variety of animals, especially noscopes and domestic animals such as cattle, sheep, horses, dogs, cats and the like from attacking lice, mosquitoes, flies. , ticks and the like.

Examples of compounds of the present invention which are useful as insecticidal and acaricidal agents are: m-phenoxybenzyl-α-isopropyl-4-freefluaromethoxy-phenylucetate; α-cyano-m-phenoxybenzyl α-isopropyl-4-frifluoromethoxyphenylacetate; : wyono-m- f and axibenzyl-a-í sopropyl ~ 4-chlorodif1ucxomero fi phenylacate; m-phenoxybenzyl-α-isopropyl-4- (1,1,2,2-tetrofluoroethoxy) phenylucetate; α-cyono-m-phenoxybenzyl-α-isopropyl-4-pentafluoroethoxyphenyl acetate; m-phenoxybenzyl-α-ethyl-3-trifluoramephoxyphenylacetaph; α-cyano-n-Phenoxybenzyl-α-n-propyl-4-chlorodifluoromethoxyphenylacetaph; α-cyano-m-phenoxybenzyl-α-t-butyl-4-free fluoromethoxyphenylucetaf; α-cycno-m-phenoxybenzyl-α-isopropyl-4-difluoromethoxyphenylacetate; α-cyano-m-phenoxybenzyl-α-isopropyl-4-free fluoromethylthiophenylacetate; m-phenoxybenzyl-α-ethyl-4-free-fluoromethylsulfinyl-phenyl acetate; α-cyano-m-phenoxy-benzyl-α-isopropyl-3-difluoromethylsulfonyl-phenyl-acetate; α-cyano-m-phenoxybenzyl-α-ethyl-4-free fluoromethoxyphenyl acetate; α-cyono-m-phenoxybenzyl-α-isopropenyl-4-trifluoromethoxyphenylacetate; m-Phenoxifa-isopropyl-3-bromo-4-difluoromethoxyphenylacetate; α-cyano-m-phenoxybenzyl-α-isopropyl-3-chloro-4-difluoromethoxyphenylacetaph; m-phenoxybenzyl α-isopropyl-3-chloro-4-difluoro-methoxyphenylocetate; α-cyano-m-phenoxybenzyl-α-isopropyl-3-bromo-4-difluoromethoxyphenyl acetate; m-phenoxybenzyl α-isopropyl-3,5-dichloro-4-difluoromethoxyphenylocetate; d-cyano-m-phenoxybenzyl-α-isopropyl-3-methyl-4-difluoromephoxyphenyl-acephoph; α-cyano-m-phenoxybenzyl-α-isopropyl [3-fluoro-4-difluoromethoxyphenyl] -cephate; α-cyano-m-phenoxybenzyl-α-isopropyl-3-nitro-4-difluoromethoxylphenyl4 acetate; α-cyano-m-phenoxybenzyl-α-isopropyl-3-mephoxy-4-difluoromethoxyphenyl acetate; Α-ethynyl-m-phenoxybenzyl-α-isapropyl-4-trifluoromethoxyphenyl acetate; (+) - α-cyano-m-phenoxybenzyl - (+) - α-isopropyl-4-difluoromethoxyphenyl acetate and 0 (+) - d-cydna-m-phenoxy] benzyl +; - α-isopropyl-4-trifluoromeroxyphenyl- acetate.

The invention is further illustrated by the following examples in which the temperature refers to degrees Celsius.

EXAMPLE 1 Preparation of p- (1,1,2,2-tetrafluorophoxy) toluene For 1 hour, tetrafluoroethylene and nitrogen are bubbled into a magnetically stirred mixture of 10.8 g (0.100 mol) of p-coxol, 1.67 g ( 1.43 g of real, 0.0255 ml) of potassium hydroxide pellets and 70 ml of dried dimethylformamide (DMF), kept at 680. After dilution with 250 ml of water, the reaction mixture is extracted with 100 ml of ether. The ether solution is diluted with 200 ml of 5% sodium hydroxide and twice with 400 ml of water. The ether solution is dried, filtered and then rotafioned evaporated to 18.14 g (87%) of p- (1,1,2,2-tetrafluorofoxy) toluene. In Analysis Calculated for C 9 H 8 F 4 O: c 51.93 H 3.87 F 36.51% Found 52.06 H 3.76 F 41.52 7 EXAMPLE 2 Preparation of Qf (1,1,2,2-tetrafluoroethoxy) benzyl bromide A mechanically stirred mixture of 118.45 g (0.69 mol) of p- (1,1,2,2-tetrafluoroethoxy) toluene, 123.00 g (0.61 mol, 121 mol%) N- bromosuccinimide (NBS), 1.00 g (4.13 mol, 0.73 mol%) of benzoyl peroxide and 350 ml of carbon tetrachloride are refluxed for 2.25 hours. After cooling, the reaction mixture is diluted with 350 ml of carbon tetrachloride, filtered to remove the solids, dried over sodium sulfate, filtered and then evaporated on a rotary evaporator to 160.99 g (99%) of a clear red oil. This product was used in the subsequent reactions. Infrared and NMR show that the product is p- (1,1,2,2-tetrafluoroethoxy) benzylbramide, EXAMPLE 3 Preparation of p- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile For 40 minutes a hot solution of 75 , 1 g (1.15 ml) of potassium cyanide in 140 ml of water to a mechanically stirred mixture of 160.99 g (0.561 mol) of p- (1,1,2,2-tetrafluoroethoxy) benzyl bromide and 500 ml of anhydrous 2B alcohol at a temperature of 750. The resulting mixture is refluxed for 1.75 hours. After standing overnight, the reaction mixture was kept in 500 ml of cold water and 400 ml of ether. The combined ether solutions are washed twice with 500 ml of water, dried over sodium sulphate, filtered and then evaporated on a rotary evaporator to give 114.95 g of an oil. The vacuum distillation of this oil gives, as a distillation fraction, 37.10 g (28%) of the nifrile, boiling point at 11 DEG C. at 0.29 mm Hg.

EXAMPLE 4 Preparation of α-isogropyl-p + (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile A mixture of 39.85 g (0.11 mol) of p- (1,1,2,2-tetrafluoroethoxy) ) - phenylacetonitrile, 3.71 g (9.9 mmol, 5.8 mol%) dicyclohexyl-18-crown-6, 22.0 ml (28.8 g, 0.234 mol) 2-bromopropane, 55 ml benzene 7902467r5 27 and 55 ml of 50% sodium hydroxide are stirred for 45 minutes, during which an exothermic reaction raises the temperature from 25 to 430. The reaction mixture is then heated at 450 for 16.5 hours. After dilution with 200 ml of water, the reaction mixture is extracted with 200 ml of ether. The ether solution is washed with 400 ml of 12% hydrochloric acid, 200 ml of% hydrochloric acid and 300 ml of water. The ether solution is dried over sodium sulfate, filtered and then evaporated to give 47.13 g of an oil. This oil is vacuum distilled to give 34.83 g (7420, boiling point at 0, o5s _ o, o9o mm Hg.

Analysis calculated for C 13 H 13 F 4 NO: c 56.73 H 4.76 N 5.09 F 27.61% Found: C 56.12 H 4.85 N 4.99 F 34.07% EXAMPLE 5 Preparation of 3- Methyl 2-fp- (1,1,2,2-tetrafluoroethoxy) phenylbutyric acid A stirred mixture of 48.0 g (24.0 g actually, 0.60 mol) of 50% sodium hydroxide, 21.78 g (0.0791 mol) of α-isopropyl-β- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile and 240 ml of ethylene glycol are heated at 1350 for 12 hours. After dilution with 600 ml of water, the reaction mixture is washed twice with 100 ml of ether. The aqueous layers are acidified with concentrated hydrochloric acid and then extracted twice with 300 ml of ether. The ether solution is washed twice with 500 ml of water, dried over sodium sulphate, filtered and then evaporated to give 20.47 g (89%) of a brown solid, m.p. 92-970 (hexane).

Analysis calculated for C 13 H 14 F 4 O 3: c 53.06 H 4.80 F 25.83% Funnef c 53.04 H 4.79 F 25.93% 7902467-5 EXAMPLE 6 Preparation of 3-methyl-2-fp- (1 1,2,2-tetrafluoroethoxy) phenyl] -butyric chloride A stirred mixture of 20.00 g (0.068O mal) 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyric acid, 20.00 ml (33.2 g, 0.280 ml) of thionyl claride (Baker) and 75 ml of dried benzene are refluxed for 4 hours.

The reaction mixture is then evaporated and the resulting residue is diluted with 50 ml of benzene and evaporated again to give 22.46 a (106%; of a clear dark brown liquid. This product is used as it is in the subsequent reactions. The liquid is examined by infrared analysis and determined to be the above product: EXAMPLE 7 Preparation of m-phenoxybenzyl-α-isapropyl-4- (1,1,2,2-tetrafluoroethoxy) phenyl acetate To a stirred mixture of 6.81 g (0.034O) mol) of m-phenoxy-benzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) of dried pyridine and 20 ml of methylene chloride were sweetened over a period of 20 minutes in a 20 ml methylene chloride solution of 10.6 g ( 0.034 ml) 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyryl chloride The reaction mixture is stirred at room temperature for 66 hours and then diluted with 200 ml of ether.

The ether solution is washed with 200 ml of 20% hydrochloric acid and 200 ml of water, dried over sodium sulphate, filtered and then evaporated to give 16.24 g (100%). This product is purified on a dry silica gel column (116 x 5 cm, eluent = 1: 1 hexane-methylene chloride) by collecting a sample between 85 cm and 63 cm (solvent front = 113 cm) to give 12.60 g (78% ) of a clear slightly yellowish oil.

Analysis calculated for C 26 H 24 F 4 O 4: c 65.54 H 5.08 F 15.95% Found: C 64.99 H 4.96 F 19.10% 29 79021167-5 EXAMPLE 8 Preparation of α-cyano-m-phenoxybenzyl, α -isopropyl 4- (1,1,2,2-tetrafluoroethoxy) phenylacetate To a stirred mixture of 8.81 g (7.49 g real, 0.0333 mol) of α-cyano-mephenoxybenzyl alcohol, 3.0 ml (2 .95 g, 0.0372 mol) of dried pyridine and 20 ml of methylene chloride were added over a 20 minute period a 20 ml of methylene chloride solution of 10.6 g (0.034 mol) of 3-methyl-2- [p- (1,1,2 , 2-tetrafluoroethoxy) phenyl] butyryl chloride. The reaction mixture was stirred at room temperature for 66 hours and then saturated with 200 ml of ether, washed with 200 ml of 20% hydrochloric acid and 200 ml of water, dried over sodium sulphate, filtered and then evaporated to a dark red oil. To remove the m-phenoxy-benzaldehyde units, the oil is reacted with 0.5 g of sodium borohydride at ice bath temperature, and the resulting oil is purified on a dry silica gel column (121 cm x 5 cm, eluent = 1: 1 hexane-methylene chloride) by to collect a sample between 77 cm and 57 cm (solvent front of 113 cm) 1111 11.17 g (66%) of a clear orange 015 m.

Analysis calculated for C 27 H 23 F 4 NO 4: C 64.67 H 4.62 N 2.79 F 15.16% Found: C 65.26 H 4.81 N 2.82 F 17.94% EXAMPLE 9 Preparation of α-isopropyl-4 Methoxyphenylacetonitrile A solution of sodium hydroxide (50%, 300 ml) was added to a solution of p-methoxyphenylacetonitrile (147 g, 1 mol), dicyclohexyl-18-crane-6 (18.63 g, 5 mol%), 2 bromopropane (320 g, 2.6 mol) and benzene (300 ml). The reaction mixture is heated to 459 and kept for 4 days. The organic phase is separated, washed well with water (0 x 200 ml), dilute hydrochloric acid (1 x 200 ml), water (2 x 200 ml) and evaporated to an oil. Vacuum distillation gives the product (175.6 g, 81% real): boiling point 960-1000 (0.15 mm) nmr (CDCl 3) shows that the distilled material contains 12.5 mol% of EXAMPLE 11 was used as such in Example 12. 7902467-5 starting nitrile.

EXAMPLE 10 Preparation of α-isopropyl-4-hydroxyphenylacetonitrile Boron tribromide (51.0 g, 0.2 mol) in methylene chloride (20 ml) was added to a solution of α-isopropyl-4-methoxyphenylacetonitrile (37.8 g, 2 mol) in methylene chloride (35 ml) kept at -40 °. The red solution is allowed to warm to room temperature and stirred for 3 days.

The reaction solution is added to ice, then extruded with ether (QS X 100 ml), washed with water (2 X TOO ml) and evaporated to an oil. Vacuum distillation gives the product: isopropyl-4-hydroxyphenylccephonifril (2s, 9, s1%), boiling point 142-14s ° (0.25 mm).

Preparation of formic acid, chlorothio-, 0-fp- (1-cyano-2-methylpropyl) -phenyl] ester Thiophosgene (16.43 g, 0.143 mol) in chloroform (50 ml) was sweetened over minutes to a solution of α-isopropyl -4-hydroxyphenylaoetonitrile (25.0 g, 0.143 mol) in NaOH solution (5%, 5.72 g, 0.143 mol), using an ice bath to keep the temperature below 300. The mixture is stirred for 15 minutes and the chloroform layer is separated, washed with water and evaporated to a yellow oil (38.2 g). The product EXAMPLE 12 g Preparation of α-isopropyl-4-trifluoromethoxyphenylacetonitrile The thiocarbonate (38.2 g) from Example 11 is treated with molybdenum hexafluoride (15.8 g) at 2525 °. The thick reaction mass is then allowed to warm to room temperature and slowly heated to 1600 'using an oil bath. The mixture is cooled to room temperature and then kept in water and extracted with ether (4 x 50 ml), washed with water (1 x 50 ml) and evaporated to an oil. Vacuum distillation gives α-isopropyl-4-trifluoromethoxitenyl-acetanitrile, b.p. 78-800 (0.5 mm).

EXAMPLE 13 Alternative Preparation of α-isopropyl-4-trifluoromethoxyphenyl acetanitrile.

A. Preparation of 4-trifluoromethoxybenzyl chloride.

A mixture of trioxane (355 mg), zinc chloride (340 mg) and trifluoromethoxybenzene (600 mg) is heated at 73 ° C while bubbling hydrochloric acid gas through the reaction mixture. The reaction mixture is washed with methane sodium carbonate solution and water. When the solvents are removed, the product is obtained as a colorless liquid (1, 429).

B. Preparation of 4-trifluoromethoxyphenylacetonitrile.

The above chlorine compound is converted to the corresponding nitrile according to the procedure used in Example 3 in 93% yield.

C. Preparation of α-isopropyl-4-trifluoromethoxyphenylacetonitrile.

Alkylation of 4-trifluoroacetonitrile is carried out in 90% yield according to the procedure illustrated in Example 4.

EXAMPLE 14 Preparation of α-isobropyl-4-trifluoromethoxyphenylbutyric acid A mixture of α-isopropyl-4-trifluoromethoxyphenylacetonitrile (2.0 g), potassium hydroxide (3.0 g) in ethylene glycol (35 ml) and water (3 ml) for 8 hours. The mixture was kept in water and extracted with ether (2x10 ml). The aqueous layer is acidified with dilute hydrochloric acid and extracted with ether (3 x 10 ml), washed with water (1 x 25 ml), dried (NaSO 4) and evaporated to an oil (0.23 g); IR (oufspada) 1700 em '.

EXAMPLE 15 Preparation of α-isopropyl-4-trifluoromethoxyphenylacetyl chloride 7902467 * 5 æ A solution of α-isopropyl-4-trifluoromethoxyphenylacetic acid (1.2 g) and thionyl chloride (0.6 ml) in benzene (5 ml) reflux coconut for 4 hours. Evaporation of the solvent and excess thionyl chloride gives the acid chloride used for esterification in Examples 16 and 17.

EXAMPLE 1 § Preparation of α-cyono-m-phenoxybenzyl-α-isopropyl-4-trifluoromethoxyphenuclucutate in A solution of α-isopropyl-4-trifluoromethoxyphenylacetyl chloride (4.58 mmol) in ether (5 ml) was added to an ether ( 20 ml) solution of α-cyono-m-phenoxybenzyl alcohol (4.58 mmol) and pyridine (0.5 ml).

The mixture is stirred overnight and filtered. The filter root and wash liquor evaporate and the residual oil are purified on 5x2 mm silica gel plates using 1: 1 methylene chloride-hexone as eluent. The band with Rf = 0.55 is extracted with ether and evaporated to give the desired ester (0.85 g).

IR (open path) 1} 55 cm -1; NMR (cDc13) δ; s_7.6 (m, 1sH, Ar fi), 6.31 and 6.28 (5.1H, -CH-Ar), 3.27 (d, J = 7Hz, TH, CH CH (CH in CN - 2.0-2.6 (m, 1H, CH (CH3) 2), 0.6-1.2 (four doublets J = 7Hz, 6H, isopropyl CH3), 19F chemical shift 58, 8 relative to CFCl3.

EXAMPLE 17 Preparation of m-Phenoxybenzyl-u-isopropyl-4-trifluoromethoxyphenxlocetut. To a solution of m-phenoxybenzyl alcohol (1.89 g) and pyridine (1 ml) in methylene chloride (6 ml) was added a methylene chloride ml) solution of α-isopropyl-4-trifluoromethoxyphenylocetyl chloride, prepared from the corresponding acid (2.46 g) according to Example 15. After stirring the reaction blonde overnight, it is washed with water, dilute sulfuric acid solution, undiluted carbonyl hydroxide , Water and indunstos fill an orange-colored ølju. Purification by silica gel chromophogruphy gives the desired sphere (2.76 g).

IR (diluted) g1738 cm-1; NMR (CDCl 3) δ 6.73-7.45 (m} IBH), 5.03 (S, ZH), 3.20 (d, J; 10.5 H 2, TH), 2.26 (m, 1H ), Ö, 6Ö and 0.94 (Two d, J = 6.6 Hz, 6H).

EXAMPLE 18 Preparation of α-ethyl and α-n-propyl-4-trifluoromethoxyphenyl acetic acids and acids thereof.

Mon follows the procedure of Example 9 but replaces the 2-bromopropane with ethyl bromide and 1-bromopropane to give the acids n-ethyl-4-free fluoromepoxyphenylacetic acid and an-propyl-4-free fluoromethoxyphenylacetic acid according to the steps illustrated in Examples 12 and 11. 14. These acids are then converted into the following esters by appropriate procedures according to Examples 15, 16 and 17.

O. cF3o cH-Ö-o-cn oi I _ RR 1 2 7902467-5 34 RR C235 H 60.83 (t, J = 7.5Hz, 3H, CH3), 1.90 (m, 28, -CH2-), - I 3.49 ( t, J = 7; 5Hz, ~ cg-cH2Cn3), .04 (s, 2H, -OCH2-), 7.10 (m, l3 fl, ArH) CZHS CN 60.84 (two triplets, J = 7.6Hz, 3H, .CH3 ), 1.94 (m, zu, -ca, -), '~ I 3.55 (t, J = 7.4Hz, 1H, -C_1 ~ _i_CH2CI-i3), 6.33 (s, 1H, -C§CN-), 7.18 (m, 13H, Ar fl) 3.63 (t, J = 7.2Hz, la, -ègfc3 fl7), 7.12 (m, 13H, ArH) ï_1_-C3H7 CN 60.65-2.4 (m, 78, -CH2CH2Câl3), 3.11 (:, J = 7.3Hz, ln, -cg-c3H7), 7.20 (m, 1314, AIR) 7902467-s ee fi elæl Preparation of α-bromo-4-trifluoromethylthiotoluene Bram (20.5 g, 0.13 mol) in 20 ml carbon tetrachloride is slowly added to 4-trifluoromethylthiotoluene (29 g, 0.15 mol) in 90 ml of carbon tetrachloride which is heated to gentle reflux under a 2Z5W solar lamp. When the additive is complete, the solution is kept at reflux for one hour. Most of the solvent is removed at atmospheric pressure, and then the residue is vacuum distilled. A 15.5 g fraction with a boiling point of 64-77 ° / 0.6-0.8 mm consists of 92% monobromination by effluent chromatography (glo).

EXAMPLE 20 Preparation of 4-trifluoromethylthiophenylacetonitrile Sodium cyanide (3.9 g, 0.08 mol) is added to 40 ml of dimethyl sulfoxide at 65 ° C under N 2. The heat is removed and α-bromo-4-trifluorothiotoluene (14.3 g real, 0.053 mol) is added dropwise at such a rate that the exothermic reaction never gives a temperature above 75 ° C. The red reaction mixture is heated to 90-95 ° C for about 45 minutes, then cooled to room temperature and treated with 50-100 ml of ice water. An aqueous suspension is extracted with several portions of ether, which are combined, washed with water and dried over sodium sulfate. Evaporation in vacuo gives 9.7 g of a dark red oil, 95% pure according to glc.

EXAMPLE 21 Preparation of α-isopropyl-4-trifluoromethylthiophenylacetonitrile.

Fifty percent sodium hydroxide (13.5 ml) is added dropwise over a thirty minute period to a suspension of 4-trifluoromethylthiophenylacetonitrile (9.7 g, 0.045 mol), 2-iodopropane (9.5 g, 0.056 mol) and 18 -cron-6 (0.61 g, 0.0023 mol) in 13.5 ml of the hen and the temperature of the exothermic reaction reaches 43 ° C. After stirring for 2.5 hours at room temperature, a sample placed on a glo - mm 7902467-5 shows that none of the starting nitrile remains. The reaction is worked up by adding ice water and extracting with ether, which is washed with% HCl, water and dried over sodium sulfate. Evaporation in vacuo gave 10.2 g (86.8%) of a reddish brown oil. Comparable results are obtained by using ethyl bromide or n-propyl iodide instead of 2-iodopropane for the synthesis of α-ethyl-4-trifluoromethylthiophenyl acetonitrile resp. α-n-propyl-4-trifluoromethylthiophenylacetonitrile.

EXAMPLE 22 Preparation of α-isopropyl-4-trifluoromethylthiophenylacetic acid α-isopropyl-4-trifluoromethylthiophenylacetonitrile (6.9 g real, 0.0265 mol) and 50% sodium hydroxide (25 g, 0.312 mol) are combined in 53 ml of ethylene glycol reflux for 18 hours.

The reaction mixture was kept in ice water and extracted with ether.

The aqueous phase is acidified with concentrated HCl, then re-extracted with ether which is washed with water and dried over sodium sulfate. Evaporation in vacuo gives 2.05 g of an oil product.

Comparable results are obtained by using α-ethyl-4-trifluoromethylthiophenylacetonitrile or α-n-propyl-4-trifluoromethylthiophenylacetonitrile as starting material for the synthesis of α-ethyl-4-trifluoromethylthiophenylacetic acid resp. α-n-propyl-4-trifluoromethylthiophenyl acetic acid.

EXAMPLE 23 Preparation of α-cyano-m-Phenoxybenzyl-α-isopropyl-4-trifluoro? Methylthiophenylacetate Using isopropyl-4-trifluoromethylthiophenylacetic acid and the procedures of Examples 15, 16, the product is obtained as an oil. Analysis calculated for C 26 H 22 F 3 NO 3 S: C, 64.32%; H, 4.57%; F, 1.1, 74%; N, 2.89%; S, 6.60%. Funnett C, 64,271; H, 4.62%; Comparable results were obtained using α-ethyl-4-trifluoromethylthiophenyl acetic acid or an-propyl-4-trifluoromethylthiophenyl acetic acid for the synthesis of α-cyano-m-phenoxybenzyl-α-ethyl-4- trifluoromethylthiophenyl acetate resp. α-cyano-m-phenoxybenzyl-α-n-propyl-4-trifluoromethylthiophenyl acetate.

EXAMPLE 24 Preparation of m-phenoxybenzyl α-isopropyl-4-trifluoromethylthiophenyl acetate.

Using α-isopropyl-4-trifluoromethylthiophenyl acetic acid and the procedures of Examples 15 and 17, the product was obtained as an oil.

EXAMPLE 25 Preparation of α-isopropyl-4-mercaptophenylacetic acid A solution of α-isopropyl-4-difluoromethylthiophenylacetonitrile (15.7 g, 0.065 mol) in sodium hydroxide solution (50%, 42 g) and ethylene glycol (80 ml) is heated at reflux. for 18 hours. The reaction mixture was kept on ice water and extracted with ether. The alcoholic layer is acidified at 15 DEG-0 DEG C. using concentrated hydrochloric acid and extracted with ether. The ether extract is washed with water, saturated sodium chloride solution and evaporated to an oil (1l, 4 g, 83%). NMR and ir indicate that the -CHF 2 radical was deposited during the reaction and the product is the thiol. 79ß24e7 ~ s 38 EXAMPLE 26, / Preparation of α-isopropyl-4-difluoromethylthiophenylacetic acid Sodium hydroxide (18.4 g, 0.46 mal) in 50 ml of water and α-isopropyl-4-mercaptotenyl acetic acid A (11 g, 0.05 mol) in 40 ml of dioxane are combined and heated to a temperature of 50 ° C. Chlorodifluoromethane (Freon-22) is slowly bubbled under the surface of the liquid and immediately causes an exothermic reaction to 7500. The additive is completely sweetened until the exothermic reaction slowly begins to cease (approximately 0.5 hours). The reaction mixture is cooled to room temperature and treated with 100 ml of ice water. The aqueous layer is extracted with 3 x 200 ml of ether, then acidified at 15-2035 with concentrated HCl. The resulting oil is removed by ether extraction. The ether solution is washed with water, and saturated sodium chloride before drying over sodium sulfate and evaporation in vacuo gives 10.2 g of a dark brown gum. This was used without further purification in the final esterification step.

According to the above procedure, but using α-isopropyl-3-chloro-4-mercaptophenylacetic acid instead of α-isopropyl-4-mercaptophenyl acetic acid in the process, α-isopropyl-3-chloro-4-difluoromethylthiophenylacetic acid is obtained.

EXAMPLE 27 Preparation of α-cyano-m-phenoxybenzyl α-isopropyl-4-difluoromethylthiophenyl acetate Using α-isopropyl-4-difluoromethylthiophenylacetic acid and the procedures of Examples 15 and 16, the product was obtained as an oil. Analysis calculated for C 26 H 23 F 2 NO 3 S: C, 66.79%; H, 4.96%; F, 8.13%; N, 3.00%; s, 6.86%. Found: c, 66.5s%; H, 5.13%; F, 8.02%; N, 2.87%; S, 6.95%. 79o24e7-5 39 EXAMPLE 28 Preparation of α-isopropyl-4-hydraxyphenylacetic acid A mixture of α-isopropyl-4-methoxyphenylacetonitrile (40.0 g) and bromofuccic acid (m, zoo m1) aferfled boiling oil using 126_12s ° C 14 hours. The reaction mixture is sprayed with ice and water, extracted several times with ether, washed with water and evaporated to a solid residue. The solid residue is boiled in chlorine form (200 ml), cooled, filtered and dried: yield: 23.8 g, m.p. 172 DEG-174 DEG C .; ar (Nujol) 32504900 (width oH), 1699 ef] (c_ = o). Comparable results were obtained using α-ethyl-4-methoxyphenylacetonitrile or α-n-propyl-4-methoxyphenylacetonitrile for synthesis of α-ethyl-4-hydroxyphenylacetic acid resp. α-n-propyl-4-hydroxyphenyl acetic acid. EXAMPLE 29 Preparation of α-isopropyl-4-difluoromethoxyphenylacetic acid In a magnetically stirred mixture with a temperature of 80 ° C of .00 g (0.0515 mol) of α-isopropyl-4-hydroxyphenyl acetic acid, 65 ml of dioxane, 19.08 g (18.56 g real, 0.464 mal) sodium hydroxide and ml water water is bubbled 46 g (0.532 mal) chlorodifluoromethane over a period of Å hours. The reaction mixture was kept in 250 ml of ice water and the resulting mixture was washed with ether, acidified with concentrated hydrochloric acid to pH 3 and then extracted with 200 ml of ether. The ether solution is washed once with 100 ml of water, dried over sodium sulfate, filtered and then evaporated to a white paste. A mixture of hexane and methylene chloride is added and the resulting mixture is filtered to remove the solids which make up the starting material. The filtrate is evaporated to give 41 g of a clear brown oil. The product was judged to be at least 85% pure by nmr. NMR (CDCl 3 -d 5 pyridine), δ 7.43 (d, J = 8.2 H 2, ZH), δ 7.08 (d, J = 8.2 H 2, 2H), δ 6.57 (f, J = 74.3 H2, 1H), δ 3.63 (s, imp.), ¿3.25 (d, J = 10 Hz, 1H), (d, d = 6.5 Hz, 3H), (§ 0.78 (d, J = 6.5 H 2), δ 3.82 (S, 1H), Comparable results are obtained using α-ethyl-4-hydroxy-phenylacetic acid or α-n-propyl-4-hydroxyphenylacetic acid for synthesis of a Ethyl 4-difluoromethoxyphenylacetic acid or an-propyl-4-difluoromethoxyphenylacetic acid.

EXAMPLE 30 Preparation of m-phenoxybenzyl-α-isopropyl-4-difluoromethoxy-phenxlacetuf Using α-isopropyl-4-difluoromethoxyphenylacetic acid A and the procedures of Examples 15 and 17, the product was obtained as a light yellow oil.

Analysis calculated for C 25 H 24 F 2 O 4: C, 70.41%; H, 5.67%; F, 8.91% Found: C, 73.36%; H, 5.96%; F, 10.56%.

Comparative results were obtained using α-ethyl-4-difluoromethoxyphenylacetic acid or α-n-propyl-4-difluoromethoxyphenylacetic acid For synthesis of m-phenoxybenzyl-α-ethyl-4-difluoromethoxyphenyl-ucephut or α-n-difluoromethoxy-4.

EXAMPLE 31 i Preparation of α-cyano-m-m-Phenoxybenzyl-α-isopropyl-4-difluoromethoxyphenyllocetut By using α-isopropyl-4-difluoromethoxyphenylacetic acid M 7902467-5 and the procedures of Examples 15 and 16 the product is obtained as an oil.

NMR δ (cDc13) δ, δ, δ (four doublets, J = 6Hz, CH3), 2.30 [m, 1H, -êH_cH (cH3) 2], 3.24 [α, J_ = 10.1 Hz, 1H (hHccc (cH3) 2], 6.33 (two singlets, 1H, -CEQN), 6.45 (t, J '= 74 Hz, 1H, CEF 0-), 7.16 (m, 1sH, Arn) . Analysis calculated for C 26 H 23 F 2 NO 4: C, 69.17%; J, 5.13%; F, 8.42%; N, 3.10%. Funnef = c, 69.41%; H, 5.20 z; F, 10, 25%; N, 3.70%.

Comparable results were obtained using α-ethyl-4-difluoromethoxyphenyl acetic acid or α-propyl-4-difluoromethoxyphenyl acetic acid for the synthesis of α-cyano-m-phenoxybenzyl-α-ethyl-4-difluoromethoxy-phenylacetate and α-cyano m-phenoxybenzyl α-propyl-4-difluoromethoxyphenyl acetate.

EXAMPLE 32 Preparation of m-phenoxybenzyl α-isopropyl-4-trifluoromethylsulfinexylphenyl acetate A mixture of 10.0 g of m-phenoxybenzyl α-isopropyl-4-trifluoromethylthiophenyl acetate according to Example 24 and 4.1 g of m-chloroperbenzoic acid (85% ) was heated in 100 ml of methylene claride for several hours. The mixture was filtered and the concentrated residue was purified on a dry silica gel column using a 2: 1 methylene chloride-hexane mixture. The product was collected as a light yellow oil.

Comparable results were obtained using m-phenoxybenzyl-u-ethyl-4-trifluoromethylthiophenyl acetate or m-phenoxybenzyl α-n-propyl-4-trifluoromethylthiophenyl acetate for the synthesis of m-phenoxybenzyl α-ethyl-4-trifluoromethylsulfinylphenyl. m-phenoxybenzyl-α-n-propyl-490-trifluoromethylsulfinylphenylacetic acid.

EXAMPLE 33 Preparation of α-cyano-m-phenoxybenzyl-α-ethyl-3-difluoromethylsulfonyl] phenyl acetate A mixture of 10.0 g of α-cyano-m-Phenoxybenzyl-α-ethyl-3-diFluoromethylthiophenyl acetate and 9.0 g m-chloroperbenzoic acid (85%) was refluxed in 100 ml of ethylene dichloride overnight. The mixture was purified, after filtration and concentration by dry column chromatography on silica gel using a 2: 1 methylene chloride-hexane mixture. The product was collected as a yellow oil.

EXAMPLE 34 Preparation of 4-trifluoromethoxy-β, β-dimethylatropic acid To a solution of p-trifluoromethoxyphenylacetic acid (22, g, 0.1 ml), obtained by alkaline hydrolysis of the nitrile prepared in Example 12) in ether (50 ml) was sweetened at an ice bath temperature. commercially available isopropylmagnesium chloride solution (0.2 ml) in ether.

The reaction mixture was stirred for two hours at room temperature and dry acetone (5.8 g, 0.1 mol) was added to the reaction mixture and refluxed for 5 hours. The reaction mixture is cooled, carefully acidified with aqueous sulfuric acid and extracted with ether.

Combined organic layers are extracted with 10% sodium carbonate solution. The alkaline layer is acidified with hydrochloric acid and extracted with ether. The ether extract is dried (Na 2 SO 4) and evaporated to give 4-trifluoromethoxy-6, B-dimethylatropinic acid.

EXAMPLE 35 Preparation of m-Phenoxybenzyl 4-trifluoromethoxy-α-isopropenyl-phenyl acetate 7902467-5 43 To a solution of 4-trifluoromethoxy-5, B-dimethylatropic acid (13.9 g, 0.05 ml) and triethylamine (6.1 g, 0.06 mol) in acetone (100 ml) is added m-phenoxybenzylbramide (1.3.2 g, 0.0 ml) at ice-bath temperature and then refluxed for several hours; the eel landing was kept in cold dilute hydrochloric acid and extracted with ether. The ether layer is washed with 10% hydrochloric acid, water, dried (Na 2 SO 4) and evaporated to give the hydroxy ester, which is dehydrated with P 2 O 5 in the batch at 80 ° C for 18 hours. Filtration and removal of the solvent give the crude ester. Purification of the material by dry column chromatography on silica gel using 50:50 methylene chloride-hexane as solvent gives a product as a pale yellow gum.

EXAMPLE 36 Preparation of 4-Trifluoromethoxy-out-butylbenzylalkyl To a solution of commercially available t-butylmagnesium chloride in THF (1.0 ml) was added at 38-40 ° C a solution of 4-trifluoromethoxybenzaldehyde (56 g, 0.4 g). mal) in THF (50 ml) under a nitrogen atmosphere.

The reaction solution is stirred at room temperature overnight and carefully acidified with dilute sulfuric acid at 15-20 ° C. Ether is added and the organic phase is washed with water, dried (Na 2 SO 4) and evaporated to a gummy solid. That arena material is purified by silica gel chromatography to give the alcohol used in Example 37.

EXAMPLE 37 V Preparation of β- (1-clear-2,2-dimethylpropyl) -α, α, α-trifluoroanide 291 To freshly distilled thionyl chloride (14.87 g, 0.125 mol) cooled in a salt ice bath was sweetened in portions the neopentyl alcohol from Example A79o24e7-5 44 (12.4 g, 0.05 mol) for 13 minutes. The ice bath is removed and the slurry is allowed to stand overnight. Evaporation of the excess thionyl chloride gives a solid.

EXAMPLE 38. Preparation of at-butyl-4-trifluoromethoxyphenylacetic acid The neopentyl chloride prepared according to Example 37 is transferred to the Grignord reagent and subsequent carbonation with carbon dioxide according to the procedure of Weinstein and Morse [Journal of the Åmeri-I can Chemical Society 74, 1133 (1952)] gives the desired acid as a white solid.

EXAMPLE 39 Preparation of α-cyono-m-phenoxybenzyl-α-t-butyl-4-trifluoromethoxyphenyl acetate Using α-t-butyl-4-trifluoromethoxyphenylacetic acid and the procedures described in Examples 15 and 16, the product was obtained as an oil.

EXAMPLE 40 1 Preparation of α-isopropyl-3-bromo-4-hydroxyphenylacetic acid A mixture of α-isopropyl-4-hydroxyphenylacetic acid (20 g, 0.103 mol) in chloroform (250 ml) was cooled to 0 ° C and bromine (16.5 g, 0.103 mol) in chloroform (15 ml) is added over 30 minutes. The reaction solution is stirred at 0 ° C for 30 minutes and then allowed to warm to room temperature. The solvent is evaporated and the residue is crystallized from hexone-benzene to give the monobromo derivative (22.19); smalfpunkf 113 _ 116%. EXAMPLE 41 Preparation of α-Isopropyl-3-bromo-4-difluoromethoxyphenyl acetic acid Using the procedure of Example 29, the α-isopropyl-3-bromo-4-hydroxyphenyl acetic acid (18.0 g) is converted to the corresponding difluoromethoxy. . The desired acid is obtained by separation of unreacted starting material by chromatography on silica gel using 2.5% methanol-in chlorotorm as eluent, as a waxy solid (4.7 g). The crude acid was used as such in Examples 42 and 43.

EXAMPLE 42 Preparation of m-Phenoxybenzyl-α-isopropyl-3-bromo-4-difluoromethoxy-phenyl acetate Using α-isopropyl-3-bromo-4-difluoromethoxyphenylacetic acid and the procedures of Examples 15 and 17, the product is obtained in 1 g. NMR (cocla), δ6, s_7.7 (m, 1211, ArH), 6.45 (f, _.1 = 7. Hz, 111, oc111 = 2>, 5.10 (as, 11-1, C112 ) 3.18 (d, .1 = 911z, 111, 4 C (fCH (CH3) 2), 1.0 and 0.71 (2d, J = 6 Hz, 6H, isopropyl CH3).

EXAMPLE 43 Preparation of α-cyano-m-phenoxybenzyl-α-isopropyl-3-bromo-4-difluoromethoxyphenyl acetate Using α-isoproyl-3-bromo-4-difluoromethoxyphenylacetic acid and the procedures of Examples 15 and 16 are obtained. . NMR (coCl 3) δ 6.9_7.7 (m, 1211, ARH), 6.50 (f, 444112, 1H, OCHF 2) 6.33 and 6.36 (25, 1H, C 1 -CN), 3.25 (d, 1H, CE-CH (CH3), 0.6-1.1 (4d, 6H, isopropyl CH3). 7902467-5 '46 EXAMPLE 44 Preparation of α-isopropyl-3-chloro-4-hydroxyphenylacetic acid A mixture of α-isopropyl-4-hydroxyphenylacetic acid (30 g, 0154 mol) in chloroform (600 ml) is cooled to 0 DEG-5 DEG C. and chlorine gas (12.0 g, 0.169 mol) is slowly bubbled in. The solvent is removed and the product is obtained by crystallization from benzene-hexane: m.p. 125 ° C.

EXAMPLE 45 Preparation of α-cyano-m-phenoxybenzylphasouropyl-3-chloro-4-difluoromethoxyphenyl acetate Using α-isopropyl-3-chloro-4-hydroxyphenylacetic acid and the procedures of Examples 29, 15 and 16, the product is obtained as a gum. NMR (CDCl 3) δ 6.8 to 7.5 (m, 12H, ArH), 6.50 (t, J = 74 Hz, 1H, OCHF 2), 6.33 and 6.30 (25, 1H, - CH-CN), 3.25 (d, J = 10 Hz, 1H, c fi-cH (cH3) 2).

Analysis calculated for C 20 H 22 ClF 2 NO 4: C 64.26; H, 4.56; hL2.88; CL 7.30; E 7.82; Found: C 64.27; H, 4.70; N 2.94; Cl, 7.20; F, 7.78.

EXAMPLE 46 Preparation of m-phenoxybenzyl-deisopropyl + 3-chloro + 4-difluoro-. methoxyphenyl acetate.

Using α-isopropyl-3-chloro-4-hydroxyphenylacetic acid and the procedures of Examples 29, 15 and 17, the product is obtained as a yellow oil. NMR (CDCl 2) δ 6.8 to 7.6 (m, 12H, ArH), 6.47 (t, J = 74 Hz, OCHF 2), 5.07 (bs, 2H, CH 2). 79o2457-5 47 Analysis calculates for C 25 H 23 ClF 2 O 4: c 55.15; H 5.03; c1 7.59; F 8.24; Found: C 65.46; H 5.05; Cl 7.73; F 8.08 ~ EXAMPLE 47 V Preparation of α-isopropyl-3,5-dichloro-4-hydroxyphenyl acetic acid A mixture of α-isopropyl-4-hydroxyphenyl acetic acid (30 g, 0.155 mol) in chloroform (500 ml) is cooled in ice. ointment bath and chlorine gas (about 30-35 g) are bubbled at 0-5 ° C for 90 minutes. The solution is stirred at 0 DEG-5 DEG C. for an additional hour and allowed to warm to room temperature. The solvent is evaporated and the product is obtained by crystallization from hexane as a white solid (29.8 g); melting point 152-154 °.

EXAMPLE 48 Preparation of isopropyl-3,5-dichloro-4-difluoromethoxyphenyl acetic acid.

Using α-isopropyl-3,5-dichloro-4-hydroxyphenylacetic acid and the procedure of Example 29, the above acid is obtained as an oil. The nmr of the product shows that it contains 15 mole percent (approximately) of the starting maferial and was used as such in Example 49, EXAMPLE 49 Preparation of α-oyano-m-Phenoxybenzyl α-isopropyl-3-bromo-4-, difluoromethoxyphenyl acetate.

Using α-isopropyl-3,5-dichloro-4-difluoromephoxyphenyl-acetic acid and the procedures of Examples 15 and 16, the product is obtained as a gum, NMR (coc1) 66.94; (m, HH, ArH), 6.67 (f, 7902467-5 48 J = 74Hz, 1H, ocHF2), 6.33 and 6.40 (2s, 1H, c fi, cN), 3.23 (a, J = 10 Hz, 1H, c5, cH (cH3) 2, 0.6 f111 1.1v (4d, 6H, isopropyl cH3). 22 2 2 2 4 'c 60.01; H 4.07; N 2, 69; Analysis calculates for CH Cl F NO - mma = csan; H4æ; N2m.

EXAMPLE 50 Preparation of m-phenoxybenzyl-1-deisooropyl-3L-dichloro-4-difluoromethoxyphenylacaphate Using α-isopropyl-3,5-dichloro-4-difluoromethoxyphenyl acetic acid and the procedures of Examples 15 and 17 are obtained as a procedure. a gum.

Analysis calculated for C 25 H 22 Cl 2 F 2 O 4: c 60.61; H 4.48; c1 14.32; F 7.67; EXAMPLE 51 'Preparation of α-isopropyl-3-methyl-4-difluoromethoxyphenylacetic acid 3-methyl-4-methoxyphenylaoephonitrile is converted to the above compound using the procedures of Examples 28 and 29.

The product is contaminated with a certain amount of α-isopropyl-3-methyl-4-hydroxyphenylacetic acid as shown by nmr. However, the material as such was used for the esterification in Example 52, the final ester being purified by chromatography. EXAMPLE 52 Preparation of α-cyano-m-phenoxybenzyl α-isopropyl-3-methyl-4-difluoromethoxyphenyl acetate Using the acid of Example 51 and the procedures of Examples 15 and 16, the ester is obtained as a viscous oil. NMR (CDCl 3) δ, s, 7.5 (m, 12H, ArH), 6.45 (f, J = 74Hz, 1H, ocHF 2), 6.48 and, 53 (25, V 1 H, cH-cN), 2, (S, aH, cH3).

Analysis calculated for C97HORF2N0¿: _c69.65; H 5.41; * N 3.01; Funnef; c 70.05; H 5.86; N 2.83.

EXAMPLE 53 Preparation of 3-Fluoro-4-methoxyphenylacetonitrile A mixture of 4- (bromomethyl) -2-fluoroanisole (45.8 g, 0.21 mol), trihexylamine (1.4 g) and sodium cyanide (20.5 g, 0.42 mal) in water (50 ml) is heated at 60-65 ° C for 18 hours. The mixture is cooled and extracted into its ether, washed with water, saturated sodium claride solution and dried (Na 2 SO 4). Evaporation of the solvent gives a solid (33.2 g): mp 42-46 ° C.

EXAMPLE 54 Preparation of α-isoprapyl-3-fluoro-4-methoxyphenylacetonitrile A mixture of 3-fluoro-4-methaxiphenylacetanitrile (30 g, 0.18 ml), 2-bromopropane (27.7 g, 0.225 mal), benzyl triethylammonium chloride (2.3 g, 0.01 mol) and sodium hydroxide solution (50%, Öómli is heated at 550 for one hour and cooled. The mixture is diluted with water, extracted with ether, washed with water, 1N HCl, water and dried. -5 50 (Na 2 SO 4) Evaporation gives the product as a brown oil (30.7 g).

NMR spectra show that the benzyl proton is a doublet at 3.6%. EXAMPLE 55 Preparation of u-isopropyl-3-fluoro-4-difluoromethoxyphenylacetic acid Starting from α-isopropyl-3-fluoro-4-methociphenylacetonitrile according to the procedures in Examples 28 and 29 the product is obtained as a brown oil. NMR spectrum shows that the product is contaminated with the starting material. Therefore, this crude reaction mixture was subjected to the Freon 22 reaction twice more as described in Example 29 to give the product as a brown oil. NMR spectrum shows that the product is about 96% by weight.

EXAMPLE 56 Preparation of α-cyano-m-phenoxybenzyl-α-isopropyl-3-fluoro-4-difluoromethoxyphenyl acetate Starting from α-isopropyl-3-fluoro-4-difluoromethoxyphenylacetic acid and according to the procedures of Examples 15 and 16, the final ester is prepared a yellow oil. NMR (CDCl 3) δ 6.8 to 7.5 (m, 12H 1 ArH), 6.63 (t, J = 74 Hz, 1H, OCHF 2), 6.33 and 6.37 (2S, 1H, CH -CN).

Analysis calculated for C 26 H 22 F 3 NO 4: C 66.52; H 4.72; N 2.98; Found: C 66.27; H 4.87; N 2.99.

EXAMPLE 57 Preparation of α-isopropyl-3-nitro-4-hydroxyphenylacetic acid A mixture of α-isopropyl-4-hydroxyphenylacetic acid (18.2 g, 7942467-5 0.094 ml) in acetic acid (130 ml) is heated to 40 ° C and nitrate acid (70%, 9.56 g, 0.095 mol) is added at such a rate that the reaction temperature is maintained at 38-400 and must never exceed »45 ° C. The reaction mixture is stirred at 40-42 ° C overnight and kept in ice water. The yellow solid is collected by filtration, washed and dried (19.1 g); melting point 103-1Ö5 °.

EXAMPLE 58 Preparation of α-isopropyl-3-nitro-4-difluoromethoxyphenylacetic acid Using α-isopropyl-3-nitro-4-hydroxyphenylacetic acid and the procedure of Example 29, the above acid is prepared as a crude material containing unreacted starting material. However, by repeating the Freon 22 reaction described in Example 29 three times using the crude product obtained after each cycle, the product is finally obtained as a fine beige solid (hexane): mp 88-900.

EXAMPLE 59 Preparation of α-cyano-m-phenoxybenzyl α-isopropyl-3-nitro-4-difluoromethoxyphenyl acetate.

Using α-isopropyl-3-nitro-4-difluoromethoxyphenylacetic acid and the procedures of Examples 15 and 16, the product is obtained as a yellow oil.

Analysis calculated for C 26 H 22 F 2 N 2 O 6: C 62.90; H 4.47; N 5.64; Found: C 62.51; H 4.77; N 5.58. Preparation of α-cyano-m-phenoxybenzyl-α-isopropyl-3-methoxy-EXAMPLE 61 4-difluoromethoxyphenyl acetate Using α-isapropyl-3-methoxy-3-methoxy. 4-Difluoromethoxyphenylacetic acid In the procedures of Examples 15 and 10, the product can be prepared as a gum.

Preparation of m- (m-fluorophenoxy) benzaldehyde Sodium salt of 3-fluorophenol is prepared by mixing the 3-fluorine product as a clear liquid (6.6 g): b.p. 82-88 ° C (0.5 mm).

EXAMPLE 62 of ° 1 (15.1s 9, 0.135 mol) and nuffium methoxide (7.2o 9, 0.135 mol) in pyridine (115 ml). The reaction is heated to 110 ° C during which 34 ml of pyridine-methanol are distilled off. The reaction is cooled to 80 ° C and m-bromohensaldehyde (25.0 g, 0.135 mol) and copper (I) -E chloride (4.05 g, 0.049 mol) are added. The reaction mixture is refluxed overnight. The following day, most of the pyridine is removed by distillation and the reaction is cooled and diluted in toluene (80 ml). The solids are filtered and the filtrate is washed with 20% HCl, water, 5% NaOH and concentrated and evaporated to a dark brown oil Vacuum distillation gives Analysis calculated for C 13 H 9 FO 2: C 72.22; H 4.20; F 8.79; Found: C 72.03; H-4.80; F 8.60.

Preparation of substituted α-cyano-m-phenoxybenzyl esters of fluoroalkoxyphenylacetic acid Starting from either α-isopropyl-4-difluoromethoxyphenylacetic acid or 15 and 16 the following esters are prepared: Rcrzo - <::: >> cH-coo-çn 0 »'ßí _ I CN. R4 cH (cu3) 2 7902467-5 54 ^ mmu .mn .mv o «. ~ ~ @. ~ Z H @ .mz. ^ Zu | mu_.mH .m ~ v ~ m. @ .Mm.w ~ mu | m, -.m = H «.mm. ^ Nm = uo .m fi. ~ m« ~ uw .vv 0m. @> ~ .m @ u ß @ .mw u .fl muæ .m ~ H .ev m. ~ 0 »æ.w Ammuo .mm .mv Ow.m ~ m. ~ Z Hm.N z ..zu | zu .md .w ~ v ~ m. @ .W ~. @ ~ Muo | m @«. m = -.mm. ^ ~ @ muo. = H. ~ m «> nn .uv ß« .mo ~. ~ @ U m ~. ~ mu ^ m ~ <.m ~ H .av vv »a» æ . @ ^ ~ = u H> mo »mow« .mw .vv ~ .H ou w. °. . ^ ~ ^ m = uvmu | mu .md .fl wo fi un .vv m ~. ~ ~ æ. ~ 2 mw. ~ z. ^ zu | mu .m fi .m ~ v mm. Vo ~. @ Fl ufm Nm .. m @m. «=. ^ ~ @ = Uo .mä. ~ =« Ssun. »Vm«. @ @M. «Wu> ~.« Wu ..m »æ .mw fl .ev.m.> ou ww: mccaw mæ fi mcm uøcxwnwß mšnmâ. Aøvwwmmaa mäz vm 79Û2467 ~ 5 55. ~. ~ = U. = U | mu. = H. ~ Mo ~ un. @. æ ~ .m _, mm. ~ H p N «H. ~ H m mm. ~ z Ä wm. ~ _ z. ^ ~ @ muø .md. ~ m. ~ nn .uy ~«. @ m | a > ~ .v = W ~ h. «_ m ..zu-mu | ..m fi .m ~. mmfw: oo -.w. om.ww U w ~ m.ww o. ^ mH @. = ~ H .ev m.> op mw _ mo. ~ HW _ «H.- m ^ ~ ^ mmuvmuLmu .m fl. ~ moHun .vv> ~. m «Qm z W æm. ~ z. ^ zu-mv | .mH..w ~. «M. @: Oo om.m mo _ 0w.« M M -. «M. ^ ~ Mmuø .mä .fl mwßum .vv mv.mm @ .mw U _ ~ m.ww u .ñmum. = ~ H. ev «.> 0» w. @ W. | . mm. ~ z _> w. ~ z ^ ~ ^ m = u.mu «mu .m fl. ~ moHnn .mv om.m Hm.« = N mm .. m ._zu | mu | .m fi .m ~. > m.w .-. @ w | m _ mm.mw.u W @ °. «m u ^ m» <.m ~ H .a. m. ~ oß m.w qw. ~ z W_ æm. ~ z ._zu | mu | . = H .m ~ v mm.m. ° mw mm .. m M ~ ß. @ M .à ~ @ = uo .md. ~ M.> Un .vv> «. @ M | m 2.3 u M 3.3 u .Små .m2 .E mš o »» á: occsw Vmä fl ncd _. vocxænwn mä fi mc fi nmulwmma .... mzz vm _ 7902467-5 56 .mmuo .mm _wv mm. ~ mw. ~ z Qw. ~ z ~ w. «=« m. «=. ^ zu | mu _m ~ .m ~, ° ~ .w: UG m ~. @ ~ muo | m «°.« wu ~ m. «wu. ^ =» <_m ~ H .av m.> op m. @ w ~. ~ z om. ~ .z fi mmu _m ~ .mv o «. ~ w ~ .m Wm ° Q.mv m ^ zu | = u | .æ fi _m ~ v H «. @: ua» m.w mmu »m @ ~ §mw u> °.> m u .fi mgæ .mw fl .sv 1.» ou æ. @ .mmu H> moHmom fl .mn .www ~. ~ 0 »wo ~ m. ~ zm>. ~ z. ^ ~ .mmuv = uLmu .wxo fi uw .vv m ~. ~ .m ~.« = O ~ .vm ..zu | mu | .m fi .w ~. Hq.w wcm ~ n. @ Fl uum m0. ~ W U ßm.Hw u ..mu <.m ~ H .ev m. ~ Ou m. @: Mc-Em maamcm "_ .ma fl mâ nmffmmnm: MEZ Fm e * 79o24e7-5 57 EXAMPLE 63 Preparation of α-ethynyl-m-phenoxybenzyl alcohol Acetylene is dried through three-pellets, dry-ice-acetone, X-concentrated sulfuric acid and calcium chloride and bubbled at a pressure of about 0,35 kp / cm 2 into fur THF The ethylene bromide (commercial, 0.14 mol) is added dropwise over 2 hours at such a rate that the ethane evolution line is slow and steady.After the addition, acetylene is bubbled through the mixture in 15151 mmsf. mlfefåsxibsnscafsfšhyd, 127.7 g. 1115125 mm was added to the reaction mixture at 15 DEG C. The temperature is allowed to rise to room temperature and the mixture is stirred overnight. The complex is decomposed with saturated ammonium chloride solution. The product is extracted with ether, washed with water and dried (Na2 SO4). evaporation of the solvents followed by vacuum distillation using carbon tubes gives the alcohol (21.5 g).

EXAMPLE 64 Preparation of α-ethynyl-m-phenoxybenzyl-α-isopropyl-4-trifluoromethoxyphenyl acetate Using the alcohol and α-isopropyl-4-trifluoromethoxyphenylacetic acid listed in Example 63 above and according to the procedures of Example 15 and 17 a yellow gum. NMR spectrum shows the characteristic alkynyl proton, as a multiplet at 2.52 d; and the benzyl protons at 6.35C1 Analysis calculated for C 27 H 23 F 3 O 4: C 69.22; H 4.95; Found: C 68.17; H 4.11. -, ... «v ~ .... 1 -_-.;. .. .W, .. ~ «......_..... 1..L, .. u ......, _1 ...... Following a similar procedure using the alcohol of Example 63 and α-isopropyl-4-difluoromethoxyphenylbutyric acid, α-ethynyl-m-phenoxybenzyl-α-isopropyl-4-difluoromethoxyphenyl acetate is prepared.

Analysis calculated for C 27 H 24 F 2 O 4: C 71.99; H 5.37; Funnef = c 71.59; H 5.53 EXAMPLE 65 The redissolution of α-isonropyl-4-difluoromethoxyphenylacetic acid A hot solution (60 ° C) of (-) - α-phenylethylamine (4.96 g) in aqueous ethanol (60% ethanol, 20 ml) was added to a warm solution (60 ° C) of the racemic acid (20 g) in aqueous ethanol (60% ethanol, 50 ml) with magnetic stirring. When the solution is allowed to cool slowly at room temperature, the salt precipitates as a white, crystalline solid. The mixture is allowed to stand overnight and the solids are collected by filtration, washed with aqueous ethanol (10 ml) and dried (9.5 g): melting point 184-1880. The redissolved acid obtained from the above salt was found to have the yield [α] D = + 37.1 ° (cHc13, c = 1.4e9 9/100 ml). Two additional crystallisations of the above salt from aqueous ethanol (60% ethanol) give white needles, m.p. 185-187 ° C, from which the redissolved acid is obtained with [a] É'T = + 40.4 ° (CHCl 3, C = 1.353 g / 100 ml).

EXAMPLE 66 Preparation of (+) - α-cyano-m-phenoxybenzyl (+) - α-isopropyl-4-difluoromethoxyphenyl acetate The redissolved (+) acid of the above example is converted to the ester using the procedures of Examples 7902467- 59 'and 16. Reach = 1.54s2; NMR (cDc13) δ 6.43 (f, J = 74Hz, 1H, ocHF2), δ, so and 6.23 <2s, 1H, cH_cN), 3.27 (d, J = 1 ° Jz, 1H, cH_cH (cH3) 2). EXAMPLE 6? Dissolution of α-isopropyl-4-trifluoromethoxyphenylacetic acid A mixture of the racemic acid (26.2 g) and (-) - α-phenylethylamine (12.1 g) in aqueous ethanol (60% ethanol, 2 l) is heated to cooling in a steam bath ooh is allowed to cool slowly at room temperature.

The salt is collected by filtration and dried (ïó, 9 g), m.p. 189-1930. The salt is crystallized twice from aqueous ethanol (60% ethanol, 1 l and 600 ml respectively): mp 194-196 ° (8.0 g). (+) - the acid is obtained by neutralizing the salt with dilute hydrochloric acid and extraction: with ether and evaporation of the solvent: [α] D = + 35.5 ° (CHCl 3, C = 6.0 g / 100 ml).

EXAMPLE 68 Preparation of (+) - m-cyano-m-phenoxybenzyl '(+) - α-isopropyl-4-trifluoromethoxyphenylacetate Using (+) - α-isopropyl-flu-trifluoromethoxyphenylacetic acid and the procedures of Examples 15 and 16, the product is obtained as a light: yellow ° 15 @ = [u] É'T = 6.1 ° EXAMPLE 69 Insecticidal activity The insecticidal activity of the compounds of the invention is demonstrated in the following test, in which "tobacco budworm", Heliothis virescens (Fabricius), 'Western potatisoíkada ", Empoasca abrupta 7 19o 214 p 71-p 50, DeLong and" bean aphids ", Aphis fabae (Scopoli) were used as test insect species; The methods used are as follows:" Tobacco bud worm "Heliothis virescens (Fabricius) First stage of development A cotton plant with two actual leaves developed are dipped for 3 seconds while stirring in a test solution (35% water / 65% acetone) containing 300, 100 or 10 ppm of the test compound.Each leaf 1 is placed in a cup with a tampon and a piece of cheesecloth infected M kmed 50 » 100 newly hatched larvae added s before the cup is covered with f to lid. After 3 days at 27 ° C, 50% relative humidity, under-A the cups are searched and the number of dead newly hatched larvae is noted. The information obtained is given as the percentage of deaths in Table IQ "aa fi zuqdlus" A hisnfqbqe (scenoii).

Five cm of fiber pots, each containing a cress plant, 5.1 cm high, and 2 days earlier infected with 100-150 lice, were placed on a table rotating at 4 rpm and sprayed with a% water / 65 l of acetone. solution, containing 100, 10, 1.0 and 0.1 ppm of the test compound for sprays using a DeVilbiss Atomizer and an air pressure of 1.4 kp / cm2. The spray top was kept approximately cm from the plants and the spray was directed to completely cover the aphids and plants. The sprayed plants were placed on the side in white enamel bowls. Mortality was assessed after one day at 210, 50% relative humidity.

Data are reported as% mortality assessed at the indicated amount (Table I).

'"Wešternï'otatiscikada" Em casca abru ta DeLan * A "Sieve" lima bean plant with the primary leaves expanded to 79o2467és _ 61 7.6 - 10.2 cm dipped in a 35% water / 65%: acetone solution containing 100, 10 or 1 ppm of the test compound The dipped plants are placed under a hood to dry and then a 2.5 cm long piece of the top of each leaf is cut off and placed in a 10.2 cm petri dish with a moistened filter paper in 3 to 10, nymphs of other stadlef are placed in the bowl and the bowl tüçks_däfter.Norphality is calculated after the so prepared bowls are kept for 2 days at 270 and 50% relative humidity.The data obtained are given in Table I. In these parties permethrin as standard or control.

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The procedures used to assess mosquito larvae, "Mexican bean beetles" and "Southern worms" are as follows.

The malaria mosquito - Anopheles quadrimaculatus (Say). One mm of a 357% water / 65% acetone solution containing 300 ppm of the test compound is pipetted into a 400 ml beaker containing 250 ml of deionized water and stirred with the pipette to give a concentration of 1.2 ppm. Samples of this solution were taken and further diluted to 0.4, 0.04 and 0.004 ppm. A wax paper ring,> 0.6 cm wide, to fit the inside of the beaker, is allowed to float on the surface of the test solution to prevent the eggs from floating up against the meniscus curve and drying out on the inside of the glass. A spoon made from a sieve was used to spoon up and transfer approximately 100 eggs (0-24 hours) to the test beaker. After 2 days at 270, 50% relative humidity, observation of the hatch was made. The percentage mortality is given in Table II.

"Mexican bean beetle" - Epilachna varivestis (Mulsant) Sieva lima bean plants (2 per pot) with primary leaves, 7.5-10 cm long, dipped in a test solution with 300, 100, 10 or 1 ppm active substance and placed under a hood for to dry. A leaf is removed from a plant and placed in a 10 cm petri dish containing a moistened filter paper on the bottom and 10 larvae in the last stage (13 days from hatching). One day after the treatment, a second leaf on the plant is removed and given to the larvae after the rest of the original leaf has been removed. Two days after the treatment, the third leaf is given to the larvae, and this is usually the last 7902467-5 72 needed. The fourth leaf was used on the third day after the treatment if the larvae-did not stop eating. The test now ends, and you wait until the beetles have reached the adult stage, usually about 9 days after the start of treatment. When development is full-I constantly, each dish is examined for dead larvae, pupae or developed beetles; malformed pupae or developed beetles; larval pup intermediate stages or pup-adult intermediate stages or possibly other disorders with normal development and transmission of pups or adults.

Data obtained in Table II.

"Southern Armyworm" - Spodoptera eridanía (Cramer) Methods: Sieva lima bean plants, with 2 developed primary leaves, 7.5-10 cm, dipped 3 seconds' While stirring in the treatment solutions and then sweetened under a hood To dry. When the leaves are dry, they are cut off, and each cut leaf is placed in a 10 cm petri dish, containing a piece of moistened filter paper and 10 Southern Armyworm larvae in the third stage, approximately 1 cm long. The petri dishes are covered and placed in a living room for two days at a temperature of 270 and 50% relative humidity.

Mortality calculations are made after 2 days. The results obtained are illustrated in Table II.

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"Tobacco bud worm" - Heliothís virescens (babricus) Third »stage of development Three cotton plants with newly developed cotyledons are dipped in solutions containing 1000 or 100 ppm of active substance and placed under a hood to dry. When dry, each cotyledon is cut in half and 10 leaf sections are placed in a 28 g plastic medicine cup, containing 1.25 ounces of dental tampon saturated with water and a budworm in the third nymph stage is added to the cup.

The cup is sealed and kept for 3 days at 27 °, 50% relative humidity, after which a mortality count is made. The test results are given in Table III. A Kållarv - Trichoplusia ni (Hübner) - Third stage of development 'A real leaf on each cotton plant is dipped in the test solution 7902467-5 83. containing 1000, 110 or 10 ppm test compound, stirred for 3 seconds and removed To dry under an airless hood. When the leaf is dry, place it in a 9.0 cm petri dish with a damp filter paper on the bite. fío larvae of the third stage are added, and a lid is placed on the dish. The mortality calculation is made after a days at 27 ° and so on 10% relative humidity.

The data obtained are given in Table III below.¶ 84 7902467-5 wm fl mmv wu flfl Nñomuozu po oo ooo o oo o oo oo - o oö | ofou-ou®ooou ~ ooö _ u zu __ _ // // ~ ^ o: uo = u - o oo fl H om o om oo fi 1 \\ o \\. N = u | o | ou-: u «Amímí @ Yo ~ ou ~ @ ou _ // ~ _omuv = u ooo ooo oo fi oo fi oo fi o oo oo fl oo fl \\. | O: u | o | ou | mu | Amííí @Yomou. .- zQ Emmämm Emm Emm Emm Emm Emm Emm Em fl .m fifi mvnwh oo oo fi ooo fi ooo oooo oo ooo ooo ooo ooo fi »w wu @ .an-.W Un fl xwm VÉWÜE .H ßm fi mwx / Å> m Hw> nmHHwm m ww hm> nmHHwm m nm» ßw »H> o» »m Hwo fi uH ~ & ww = H HHH qqmmæe 7902467-5 85 pwu fifi mpgoe w fl mbwwß NMGH HI ~ ^ mmu, mu - - Goa QQA oß QQH 0 O OCH | ~ = u | o «ou | = u o = u ~ w. ~ ^ m = uV = u. »Mod OOH ON om 0 OQH oc fi 1 o: w» o «ou | mu mmu ~ w ZU. _ .m = uvmu 1 QOH AND CCM AND QOH COA AND | o = w «@» ou-m mumm VA zu 2.5: lm .EE: RE Emm Ena Emm Emm Emm .mGwEwHO Tmñ co * V == c ~ cc ~ _ scc fl Q. AND ccm = cc ~ _ = m _. _ IE. mun .um mnm> m xwmE uwuw fi mïn> m nmëum fifi mx lmmoøxmxmßon. muawum fi wmuummmom u ..w »Howw.HHHÅqqmm 86 7902467-5 Umßmmu wv fifi H I Å mmu ~ nu. _ É | oo fl .oo fi oo fi oo fl o ooa oo fl | O mwaolouamu ou m zu,. m: u ~ = u | oo fi oo fi oo fl oo fi | o oo fl | > O Nmunonøuomu Oumm m fi mmuvmu _ | oo fl oo fi oo fi> oo fi o oo fl oo fl | O munolouumu Omumm zu _.

Emm EQ; Eau Emm Emm Emm Eam amg Emm wc fl cwnøm CM oc fi coca cc fi coca ca oo fi: cm occ fi .um wum. uw fi vmum mum bß. La + f> m Hm> umHHmM «Mmm fi mmocxwxmnoß mucæum fi wmuummmom uwu fl Hm # uOE w. ^ .M» ~ owv HHH qqumaß 8, 7902467-5 fl mumwu wur fl. I I _1 _ Nßmmuvmu _ O Om AND om, AND 0. AND oo fi | _mw | o | ou-mu¿ @ íííLv _ zu ommu M N N N W ~ = u mu zu _ _ p u - co fi .oø fi ca ca | AND 1.. = W »o | ou | = u1A% LiL @ Toum @ _ zu _ m = u ~ = u ~ = u 1 cv Qø fi om cm | 0 .om 1 ~ = u | o | ou | = u | A & 1L> v »ou ~ @ _ Emm sam Emm Emm Emm Emm Emm aan sam ms fl zwuwm Q fi COA coca QQHV oøo fl cd OCH Qom ooo fi MOHUQMW UUM. UÜHUNUW UUM> G .HOMMHN> ¥> m nm> nma. Fi wm xmmëmmocxwxmnoa wunmum fi mmuumwwom u.® \. ~.% HM ¥ .HOE M.

|| Tm fi owv HHH anamma ZU _ _ _ _ NNN OOH OOH OOH OOH OOH OOH 1 O OOH OOH H muO = w N _ O mw1O1Ou1 = u Omu N _ _ ._ _ Nmu NN, _ _, _ _ _ u Om _OOH OOH ON, _OOH _ _ 1 1 _ O OOH _ H muOm_ N _ _ O mw1O1Ou1mu Omu N ZU 88 790246795 zu _ _ _ Hv _ NO OO OOH OOH OO OOH. 1 1 O _ OOH _ H = u. = W N. _ O _ = w1O1Ou1mu Omu N Emm Emm Emm: Nu Emm amm emmmemm Emm _ OOHOOHO 1 @ H1-_OOH_ OOOH 1pOH »OOOH111111OH1OOHfOOH _ _ _. = O _> w @ Ww »wwHWw _ HOHOOHO ~ HO_> O _ _ _ _. ._ xwoëmmocxwxumoh c fl cu fl mwwwm + owmom .I íll fl leltínlá fifi wv fl uoë- w H «« H> H «$ N.HOOHOHH ¥ ww = H OOHOHHOWHHQO 1 HHH HHmO <» _ _ OUO NHO OOH OOH m ~ OOH 1 11 N 1O mw1O1Ou1mu / \ Omu h CJ _ 7 / _ _ M 6 _ _. : u _, N m: u 4 _ Q QS E: 2 03 1 o 2: E: _ / _ Bm. m 2 __ _ _ _ __ \ Q muåuouåu | ou .w nu _ _ _, A _ _ _01 _ _ _ _ _ zu _ _ _ _ _ Ü _ _ N m 03 03 03 8 03. o 3 03 Sf _ / _ mušw _ m _ _ \ o mwånoußmu ou m _ _ zu <1 x / _ fmmušu __ o Så 03 8 03 _. 1 .. o _ _ _ ~ _ _ _ _ _ _ \ Q mu | o | ou..mu 26 .m _ J. _ _ m _ _ 9 zu 8. _ __ _ _ _ _ _ _ _ _ / fm 85 ooa oo fl ooA _ ooa óo fl | o. om oo fi _ _ m _ _ _ _ m \ _ o = w | ø | ou | mu | ® | o = u ~ m Emm Emm Emm Emm Emm Emm Emm Emm Emm _ - SI: QS E Ehlßoø fi 2 cø fi oom S3 m fi äüwm wmw fl owm mun. l fi dwvuwm mnm> u _ .hmwm c> __ _ _ \.> u nm> no ~ Hwx _ xmoEmmocxmxunoh_ _ Ovcuæmwwmnvc wO f_L_ _ - _ __ + N + wHß # HOE- w mššlw fl ä * 1 HE .fi wmï 9090 m nu: u Q 23 23 om 2ä_ | o E: 23 mu fi wouvmwü oumw v _ 2 Ü, 20 ~. 2: 2: 2: 3 03 o 3 23 25 get 353m. m k? 0 h monoéunmu ou m _ _ zu. , .. ,,. ,, .w, ~ ñmmušu o 23 23 3 23 1 .. u Q g | x / Ü _ ~. _ _ _ \ _ o x., mwåïoušu Sö m m, zu. . 1 / f. ~ M. 23 03 23 23 23 | o 3.23 .mušw. . m h _. N mw | ø | cu | muüwgmu ~ m »zu _ så. så så så så .än så Emm emo .. 3 G3 33 03 2.3 3 Q fifl oom 2: 3 _ fifl wvovw ann _ + m «¶u« Wm “w> u» _ no + wAo> x mcwcmhmu> u uw> «oHHwx xwoeaaocxmxonoh u +: owwwwwu # uwmam \ ßaë fi n fi oa w 2 mcwcwwwwvnow | HHH 44mm 79o24s7-5 _ _ _ _ _ / fmmuzö _ o .om ooo om ooo .. o .ooo oo fi o _ \ _ mu | olouåmf®l ooö fl _: Umu_ __ _ _ _ o oa oH _ / __ Émmuomw _ m ooo .. oo _ o oo oo fi o _ _ o .. \ mwooHTmUÜoUÜ mf _ _ mumu _ __ _ .Émmuomu ooH ooo oo fi oo fi ooH »oo _ ooo .. ooo ou | o | ou | own®l ouom _ _ .zu _ .m _ _ _ muo _ /. _ fmzuomw oo ooH ooH oo .oo fi .n _ o ooH ooH _ \ o mw | o | ou | mu | ®vouom o _ ._ _ _ zu. eamm som emo emo som _ som aoo_e @ o emo. 3 m ooo oooo oo fi ooo fi 3 .oowzoom ooo fl. om fi wcww mn.> m M> no ~ fl m B40 wo fi¶ n + w mum> o xmo & mao: xwxßmoH_ _ ___ Hw «wHo> ¿u«: u «m« mmH «o + wom _ + w« wHU «noE.æ mc fi cmnmm «U: fi: ++ æm ~ How 1 HHH 44mm 92 7 # 9Ü2.4> 6.7'-5 _ N m Ü. fl _ .. ... i _ J _ /. _: öšw _. o ø so. 03 .å _. . \ .F o \ | muèøounmu EÜN ». . : \ J _ /._ fmmuïnw | S 2: S 03 .. 0 .G3 23 \ f o \ ï muèè fl ïmu. SÜÛ ~ n. »M. . /. Å mušu «3 2., om .ä | | o 23 _ N. _ Eö fl w o l: uiïonïmu h 3 E: .QS .S 2:. . o .Q 23 _ fi mmämw _ c \\ mwåèïmu Sö fl »_. zu mä Emm Emm Emm Emm Emm Emm aan Emw S. 03 S3 03 .S3 .3 ... ß fl wmmww fi. w, n. _. m .mn. _. . v. ._ LW .M fi wmwm fi mm fl vmmä fi mwnxnvwmnw fi. _ .Uuccww fl wuwwuwma mn fl cwhmm * v flflflfl ßwgß w .. fnšæmwuuo »1 ä: wmï Ud fl cwwmmwaøv. | .HHH | _.._ mm <._. _,, .mw C ~ .CmuCmw Mm AND AND AND .COH COH 1 C COH AND C: // w \ mu | O | Ou | mu. ^% lLv + OCu ~ m Mm HC; CHC «HCzw Å. COHC A +. _. / C. _ i C C OH C CO COH Nmmmuvmw Hu O O C | O OCH O H Cl mw | O | Cu | mu Omu ~ m _ zu .Ü C CO COH OH CC | «Om AND Nmmnuvmw Hu 3 C- ~ mu | O | Cu: mu Cmu ~ m 9 Hu. . . N m. .NU AND AND AND CO AND 1 C COH AND. muC = w V O- Cw-O-Cu | mC Cwu ~ m ZU Emm Emm: mm Emm Emm _ Emm Emm Emm amm CH COH CCCH AND CCCH OH AND CCO COCH. .we uwm "._.,.»> Cm .wmfwu flfi wm xwmæmmmmxmwmßw fl. uæcvwm fl wmw fi wwæmww. mcÉmnmm »mmä fi cvnoë w 7902467-5 _94 EXAMPLE 72 Insecticidal activity on soil to the southern part of the barley. two ml of this solution is then diluted to .ml with acetone to solution B. Approximately 0.7 g of Pyrax ABB talc is then placed in a 28 g wide-necked container and 1.25 ml of the selected solution is sweetened. to the talc to give the following concentrationsà '1.25 m1 solution A gives 56 kg / hq 1.25 ml solution B gives 11,2 kg / ha The selected test solutions are mixed with the talc until evenly wet before it is dried under an air dryer in 10-15 minutes 25 ml of moist sterilized potting soil and approximately 0.6 g of millet seeds (food for larvae) were then placed in the container containing the test compound.

The containers are closed and the contents are mixed on a vibration mixer. Each container is then fed with 10 southern corn rootworm larvae, which are 6-B days old. The containers are loosely closed and placed in a living room at 27 ° and 50% relative humidity with constant light. Mortality calculations are made after 6 days.

In this test, α-cyano-m-phenoxybenzyl, α-i = opropyl-4-trifluoromethoxyphenyl acetate gave 100% control of southern corn rootworm at an amount of 56 kg / ha. fxeMPsL 7th Remaining insecticidal activity obtained by foliar treatment cotton buds Young cotton plants with at least 2 developed true leaves, growing in 10 cm plastic pots, dipped, Usually one leaf Once 95 times, in a 65% acetone-35% mitten solution of the test compound while stirring for 3 seconds. The concentration of each compound in the solution was 30 ppm, 100 ppm, 300 ppm or 900 ppm of the active ingredient.

When the leaves had dried, two leaves from each of two plants were disassembled and placed in petri dishes (90 mm x 10 mm) on damp filter paper (9 cm Whatman No. 1). Five third-stage tobacco bud worms were placed on each leaf and the petri dishes were sealed.

The infected dishes were then placed in a continuous room with continuous light, a temperature of 270 and 50% relative humidity. The laurel calculation was done after 72 hours.

The remaining plants were placed under kitchen-intensive light in a greenhouse that received 14 hours of light per day. Leaf samples were assessed with third-stage tobacco bud worms after 3,7,10 and 14 days of exposure in the greenhouse. 79D246¿7 ~ 5 96 7902467-5 omumø .umoo> ooxo wucmwom ~ wu <uo fl mxmuwwow womwmñ n TN ooëoošooooe oo omooooooos oowows .. L oo oo .ooo o oo. o ooo o ooo. o - ooo fi oxš i. oooíoo oxoooalooow o ooo .. o ooo o .ooo o ooo o. ooo ooo / o o o oo o oo o oo o ooo o ooo o oo ooo i. o ooooo .l o ooo oo.o oo o ooo o oo o ooo ooo _ | -. oo.o oo oo oo oo ooo oo oo oo oo.o oo oo \ o oo .. o | oo oo @ oo. oo _ GoHumEum @ o ooo o oo o ooo o ooo o ooo ooo / ooo o o oo _ o m oo o ooo o ooo o .ooo ooo o oo o; oo o o.o .o .oo oo.o oo oo.o oo o oo ooo \ o oooooli! o oo ooo oo o S oo .o 2 oo oo oo oo oo oonoooo o ooo o ooo o ooo o | mo «:« o ooo ooo _ \ »N oo ooo o ooo o ooo o ooo o ooo ooo 7> z @ w ; | .%> @@ ¶1f A ooooo oo.o oo o oo o ooo o ooo o ooo ooo - - _ o oo oo oo.o oo o oo o oo o oo oo oo \. \ O ow o oo oo®o oo _. .oo få Å.: N Å få »å» Så .Ä: N »å som _ uo fl ocwHßm I 3 .oo o o o oooo fl o. mcocëmøwnoon www umoøuum mom> m uw> umoxmm & @ mocxmxmnou> m m: ocwcm> cm ømë »coon om; osams .om .oaumnc fl oomuæ; > H Adam-Mon.

Mumma> m uæuo> ouxm ocwouovxwwso w © cmum> um> M 7902467-5 97 EXAMPLE 74 Ixodicidal activity Effective control of acarid larvae is demonstrated in the following test with larvae of Baophílus mícraplus, a solitary füsting, which can remain on a single host through its three life stages , i.e. caterpillar, nymph and I adult. In these tests a 10% acetone - 90% water mixture containing 0.025, 0.1, 0.5, 2.5 or 12.5 ppm of the test preparation was used.

Twenty larvae are enclosed in a pipette, sealed in one side with a nut material and a solution containing the test compound is then drawn up through the pipette with a vacuum bladder which thereby simulates a spray system. The fissures are kept for 48 hours at room temperature and the mortality is determined. The results obtained are given below.

Table V Percent tick larval mortality of Boophilus microplus larvae pan Compound 12.5 2.5 0.501 0.025 cn I cr3o / ^ \ çxx-co-o-åu o 100 100 100 100 100 I * "" cmcx-ayz The above procedure was repeated except that the test compound concentration was 0.1, 0.025, 0.005 or 0.001., TABLE VI Egpçent mortality of Boonhilus micro-plus larvae In Cn (Cn3) 2 DTI? Compound 0.1 0.025 0.005 0.001 * CN. '. The above procedure was repeated except that the concentration of the test compound was 0.1, 0.01, 0.001, 0.000] or 0.00001. ../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../../ ..

TABLE VIa Percent mortality of Bpophilus myofoplus larvae Compound CN CH-co-o-A F2CHO ~ CH (CH3) 2 0.1 5 0.01 0.001 0.0001 o.0o001 pen I Ppm ppm pøm gym 100 § 100 100 50 0 The above procedure repeats except the off concentration ov test compound ör 100.

TABLE VIb 7902467-5? Rocent mortality of Boonhilus microplus larvae Compound 100 pmm, CN '- I F2cns ~ <::::> - ca-co-0-cu 0 100 I ~ c fl (cH3) 2 P2cHo4 <:: :> »CH-co-o-C02 o 100 I CH (CH3) 2 - F3c0« <:::> »cH-Co-o-cuz 0 V 100 V .A CHZCH3 A 'CN I F3co ~ <:: ::> - cn-co-o-cn o 100 _ cn2cn3 CN I F3co - <::::> ~ cu-co-o-cn o 100 I cn2cu2cH¿_ V 7902467-5 100 -TABELL v10 _f ° rfsaffning X,. * - o - Hcrzo- O ~ cH --_ co- o -cH-m- f I \ cH (cH3) -2 R; RB z _ I 1 morph clifet R Y Z R2 R3 vid - ppm H H H cm p-c1 100 @ 100 ppm H H H cm wp-ocH3 vs @ 100 H H H cm p-cH3 100 @ 100 H H I H cm p-F 100 @ .1; 30 @ .o1 H H H cm m-F 100 0 100 H H H cm 0-F 100 0 100 H H V H 'cm p-c1 so @ 100 H H H cm p-cH3 100 @ 0.1; 10 @ 0.01 F H. H cm p-ocH3 90 @ 100 H H H cm p-H 15 @ .o1; 20 @ .001 r HH '-c§cH H 100 0 100 HHH -c§cH f H 100 @ 100 H. cH3 H cm H 0 H 100 H Hr HHH 0 @ 100 H Hr H cm _ H 100 @ 700 H c1 HHH 100 @ 100 H cl H cm H 15 @ 100 H c1 c1 HH 40 @ 100 H c1 c1 H cm 90 @ 100 HHH -HH 100 0 100 PHHHH 100 @ .004 HHHHHI 100 @ 100 0 'ethyl 1 »HHHH 100 0 100 U * ethyl- _ Ä FH cm H 100 @ 100 TABLE vn »-L farfsàff fi ing * z% 1ó1j v: v% [19o2¿s7êsf1 fl wnqi-'taliteâf- 'vid _P?“,' A "MGN 7 crf 'as é'.qf <> _' o6% 1_ = V __ f as! 11.

. The effect efficacy of the compounds of the invention for controlling adult Baophilus microplus ticks is determined in the following test, in which the party compounds are prepared in solutions as described in Example 74, except that sufficient of the compound was used to give solutions containing 125, 52.6, 31.2, 15.6 or 7.3 ppm of the test compound.

Adult blood-filled female feces are dipped in the test solutions for 3 V seconds and placed in individual containers and kept for 48 hours in a room at 270 and 50% relative humidity. At the end of the storage period, the fasteners are examined and the laid eggs are smoked. Blood-filled females, which have not laid eggs, are judged dead. The data obtained are given in Table vxl. 1 'TßBELL VII Ixodicidal activity against adults Boophilus microplus% adult fortress mortality at concussion at xæ fl ng 1 LIS 6 Compound I 2.5; 3'i.Z.l§.: É: 7.5 pgp Dam ibøm cam iosm I CN 1 | e CFBoQCH-cooån / I o / l 1oo 1oo 99.4 9s.s: s7.2a ..._ 'V, ca fi czg) -> 2 \. \\' »\ cnÅ ~ + -bd-o + CR (CH3'V ) 2> R: ~ '1 _m Hi Ju í:' :: - ¿: I: š ”: ¶ í a; T mz 'apr i:: z 1: Ü': na:: ni n: .V n: V: A = _A ": ': Än: 1 ::, F y» a, .CN-% fl f ïcuÅï% - cN. ¶ i ~ ¿N H .; _ en ¿eu "¿'Proca ._ _¿, N: 94Äé' lä5Å @ f1zs; sz * e 31 "V ¶A? j9¿.9" 914 A issf 77 79o2467è5gf B * írgduEfš§n> fl§ ßivs- "H Afsoo:> 6s: @b; zs -v 736." 8 * I .'v8: 4§§6 “@ f2; .1s%, _. "soo fi @ ° j1 _soo _, _ Gzi 47“ e s- "c. «@3 .._. \ ..__, _ \ _ ¿fl¿ 4 .___ _ I25; 7§QG Qi ppm f: - e igsí 37.9 e az. 135: sz e¿31; V, "7902467-5 z 1n4 EXAMPLE 76 The efficacy of the compounds of the invention for controlling" screw worms "Cochliomyía homínívorax, a very degrading bøskëpßñjukäß fl h 'is demonstrated in the following test, in which 4 larvae of the first stage homin of Cochliomaid receive eat a mixture of minced meat (8.0 g), blood (7.0 ml), H 2 O (2.1 ml) and preparation (0.9 ml), containing 1.5 or 25 ppm of the test compound.

Two replicates of 20 larvae per dose level were used in the assessment no. The larvae are allowed to eat ad libitum for 24 hours on the composition medium. After this period, the number of dead larvae is calculated. For each treatment and each replicate,% mortality is calculated. The information obtained is given in Table VIII below.

TABLE VIII Evaluation of the compounds for control of screw worm larvae, Cochliomyia Qgminivørax% mortality at concentration Compound 1 5 ppm took ppm a 'cF3o-®-cx ~ co-o-ån o 2. 4 69. 2 1oo | cn (cu3> 2 1% 7902467-5 EXAMPLE 77 Determination of LC50 for the test compounds against "tobacco bud worm" on cotton plants Young cotton plants with at least 2 expanded true leaves growing in 10 cm plastic pots were dipped, usually one leaf at a time, in a 65 % acetone-35% aqueous solution of the test compound is stirred for 3 seconds, the concentration of each compound in the solution being 1.1 ppm, 2.8 ppm, 7.5 ppm, 20 ppm, 60 ppm or 150 ppm of the active compound. the component.

When the leaves have dried, two leaves are cut from each of the two plants and placed in petri dishes (90 mm x 10 mm) on moistened filter paper (9 cm Whatman No. 1). Five third-stage tobacco bud worms were placed on each leaf and the petri dishes were sealed. The infected dishes were then placed in a living room with continuous light, at an ambient temperature of 270 and 50% relative humidity. Calculation of the larvae was done after 72 hours. Each treatment was repeated 4 times. The data obtained are given in Table IX below, where it can be seen that the compound of the present invention is stated to be 2-5 times more effective for controlling tobacco bud worm than compounds known in the art, assessed in the same test, 7902467-s 106 ~ _ NOOO \ ON OxHHw <-ONw _ ON ONOO.OON. _ _ _ ON ON OO.OO NN NO ON __, OO.ON _ _ A = uOm «_ NO ON OO.N o = U | o-øu-mu Nu OO N ON ON.N 2» O C fl uumåuwm _ _ ON ON OO.OON // _ Nwu NO ON ON _ OO.OO f ~ _ N mv ON ON OO.ON _ ”0 \\\ mU-o-oU _ m v fi N om om ß% mUnUrHU_ O ON ON OO .OO% NN ON OO.ON ONN _ O ON ON OO.NM Å muO = w_ M. O ON OO.NMQ = u «o» ou-mu o Ou_ nn O m _ OO NN ON _ ON HW _ zu E MM Omun .Nmukwmc fl fl umw fi w fi mw tån: ... moa _M mc fl nwwmm _ * _ _ WUDÛ HGQCG IC fi Hmu fifl- __. _ å _. äs Éëå fi =! @ NOOOm fl._. N || d1i | i \ | 1ai || OO UB ä O fi a fl šwwm NH .H fl mmwwñ 7902467-5 _10? . EXAMPLE 78 Determination of LC50 for test compounds against adult mosquitoes Anopheles guadrimaculatus (Sax) The compounds to be evaluated were prepared in acetone at the desired concentrations in ppm. To prepare an aerosol mixture, the insecticide solutions (0.15 ml) were pipetted to the top of a nozzle and siphoned through the atomizing nozzle. The sputtered droplets were carried by a stream of air (6.4 km / h) to the captured mosquitoes (25 adult female mosquitoes / cage) for exposure for 4-5 seconds.

The mosquitoes were then anesthetized (3-4 seconds) with CO 2 and transferred to living cages. The living cages with treated mosquitoes were placed in a living room at 29 ° C and 46 ° F 2% relative humidity. The mortality calculation was done after 24 hours.

The dates obtained are given in Table X below, and it will be seen that the compounds of the invention are about 4 times more effective than compounds known in the art for the control of Anopheles quadrimaculotus. 7902467 - 5 108 ~ ww «\ mß Cmxwm fl mßcm m> u» mms ^ ~ v ppm umwß ^ Hv »mm mxwcmx fl nwm fl ww cww fi m> fi nxmwm +« xmwumw mx flfi o w> u fl mc flfi wshm mßmo «. o «NM. _ w.wH ANV om ww Q. @ ~ a muvlw H wm flfi Q. @ H o. mu | o «ou-mu dum - ^ ~ ._ w ^ ~ v O fl ^ HV @ .m zw.« ”u mm ° .mH Nm ° .m .M% .w J // ~. ~ muV = u _ _ O fi OH o |% w \\\ = u | o | oU | mU ømmu unm ø fi m Q zu Om * uwp fifi m fl uoa Aeamv 4 _ Äämmæ w co fi umuucwucom mcwcwnmm «>« + oE @ xoHaa <uommwëcoc m = N5> X QAHNQB m: um fl øumE fl u © mDv mm fl wsmoc fl uoE mcnmmc fl cuumwumwu eww 0ww mmm of small volumes of the test compounds The test compounds were dispersed in 65% 1acetone ~ 3E% water mixtures in sufficient amounts to give 0.08 kg / ha of the mixture in 19.3 l of water. Cotton seedlings were then placed in a spray cabinet and sprayed with a stationary spray, located over the plants as they were carried under it.

When the leaves were dried, two leaves were cut from two plants each and placed in petri dishes (90 mm x 10 mm) on moistened filter paper (9 cm Whatman No. 1). Five third-stage tobacco bud worms were placed on each leaf and the petri dishes were sealed. The infected dishes were then placed in continuous light living rooms, an ambient temperature of 27 ° and 50% relative humidity.

Larval fumigation was done after 72 hours.

A The remaining plants were placed under high-intensity light in an inn. Blood samples were assessed with third-stage tobacco bud worms after 3,7,1O and T4 days.

The data obtained are given in Table XI below. 110 79Û2467 ~ 5 ll pmxw fi mwu @ \ ~ owmMmm @ cHH @ ~ 0 «»: wl fi wwwz .. ~ Amc fl cxmnunmumu fifi muuoí mnmëš fl u Nßv ux: øm \ 2mH ow uwu fi Hmuu0E w | _mw ~ _m. ~ .H «om m. ~ M * ° _m.mm Q. m. ~ M c M HHo ~» = @ «_ _ _ * ¶ m. I. _ _ ._ _ ~ .fi = u. = u W u _ _ __ u @ .H “om _wß. @ .am m» ~ Qæ o.m Gm H.Q mm = u | orou | mu Mun _ _ _,. _ _ _ _ ZU _ _ _ à _ Ü _ _. . _ »N. _. _ _ »_M _ ~. ~ = Uv = m _ _ ~ @. ° om Q om ~ o. ° Om 0 oo fi W ~ ø. ° man @ ° .Q, o mu» o | ou | mu_ o ~ mu_ _ _ _. . . ». . _ W f «~« «*« ~ * A __ «« ~ «~» + «~ * H _« «N_ * A_ mz \ mx mc fi zmußm _ vä @H _” _ ___ ~ _ QM wwøm _ ~ nmmmu. uwvw> «uxm mncmum> um> M _ _ _ _ uounm fl mw flfl nëca wm co fi umx fl Hmmm> mumwE» Hø> mwH nam mvmcxwwun Hmxwmëcnocxmxmnou u0E umuw> fl uMm Hwmmu_Mm oq fl m>> to illustrate the oxidative activity of the compounds of the invention at concentrations of 12.5, 2.5, 0.5, 0.1, 0.02 or 0.004 ppm. The results obtained are given in Table XII below. 112 79Po: 2: 4ß: s'7 @ * - 5 w. I Ä _ N. m u 3 2 S: E: E: 3: m _ N a mušw N N o Q o 2: E: 2: N o muloøuèu o | .waö m M,, m. N m _ ä 3 E: QQH E: E: m _. Ä: ušw N N o Q E: 2: 2: 2: ~ o muåoušu o- .fi šu .I. . .. _. _ V V zu _ .Emïc S6: Af m ... m: mä: fl mvmw fl m5: _ Éâa. .ocox vf »umw fifi muuoä uhwuoum Iunmsunumuwm mc fl cmuæm“ _ Hšwm fl nww fifl omomw fi En .. uwuw fl muhošum fl cc fl ummm unmoøum 7902467-5 113 'EXAMPLE 81 Etfektivíteten hos beredninga såvna r the test compounds were prepared in the sweet manner described in Example 74. Sufficient compound was used to give solutions containing 100, 10 or 1 ppm of the test compound.

Adult blood-filled females were dipped in the test solution for 3 seconds and placed in individual containers and kept for 48 hours in a room at 270 and 50% relative humidity. At the end of the residence period, the fastings were examined and egg laying was counted.

Blood-filled females, who did not lay eggs, were judged dead.

The data obtained are given in Table XIII below.

OV H4 7 90 2 4-67 - 5.

S 2 :. H Nav V m ä E: OH. A: Bmw _ _ E: _ 03 G3 o = uøou | mu o .Ü _ _ m _ zu h..>. @> .M.m__ Emm HM V .., Å N - Mmvø fi uwww mcx:>, = oA »« »» Q @ u @ n »mn fl cwumw _. .umu flfl munoë unwuøum. > W ^.>. Ow w «~ fi nm« Hm> uoucmumåuvn nov ^ .w.m. msmc fi zvcmm ms fi mznwu fl a fl zm mcx fl> # 05 uuuw> wuMw Høw fl o «vozH www Aqmmmæ H5 EXAMPLE 82 Test In vífro on adult Cfenocepholides felis., ..

In this test, 10 adult fleas of the locus Ctenocephalides are sprayed for 30 seconds with a ucetone / weapon solution containing 100, 50 or 50 ppm of the test compound. After this treatment, the flea is kept for 48 hours at room temperature and 80% relative humidity.

The flea is examined at 24 and 48 hours and a mortality calculation is made. The dates obtained are given in Table XIV below.

N n h. . ... _ _. , Å IUv ZU Q. @ _. Om_2m .ä .. _ N. ~ _ O Q _ Om _ Om W wN _ ZUOOUIEU O .wUEU m _ H. _ _. .

Q h ... å ä _ .OS .ä fršmw. p ~ N O. O _ ".bß OCH. WN IUOOUIÄU OI .WUIU h,, ß _ m _ .. W zu uuu fi mßwwoš ucwoOum nucmnwnuwuum. .Mcummc fl øwumwuwwuu än. ... fl wuwäwwxw .fl øuwowumudmnæfar24 fi m. except that the concentrations of the fixation are 80, 40, 20, 10, 5 or 2.5 Data are averages of two replicates at each level, depending on what is stated. * LABEL xïva Siphanaptericidal activity of test compound Compound F2cæxo cxa> co ~ oo I cn (ena) 2 Post-treatment_ Percent mortality at ling 'hours concentration - (m) 80 40' 20 10 5 2.5 0 24 100 * 70 4530 40 20 o * I Single test EXAMPLE 83 The experiment in Example 81 was repeated except Adult male and female adjuvants, Rhipícephalus sanguineus (R. $.) and Dermacentar variabílís (DV) were used, sufficient of the compound was used to give solutions containing 1.0%, 0.1%, 0.01 % or 0.001% of the party association Mortality calculations are made 24 and 48 hours after the treatment.

The data obtained are given in label XV below. 118V 7 9012 461.7 - 5 uwwu fi mmn fl w * u ä _ _ A. 3 _ 3, E: E: 30.0 _ v03 23 1: 3 E: Sá _ | åS | 1: 3 To, ß ßöšu * A - 1.3 | _ 1 :: _ 04 o, EUATOUåQÜOmUNW _ M ä w: w fi fwwäwwæ fi ... nw- | m .... v.w, i.mnš%; m: ššæuwm M? w ~ wwmww »m> _. c _. m: æ: m: vcmw <.m, co fl vmmmMMm: o% _ ä umu fifi mnuoñemc fi ummm: mxwš ucwuuum. _ _, F mmmw al umxwmä Eousumw Jèmv flfi MWU m> u ämæwu al wvuä um mumn: .SAS w. F .._ ,. ~. Mu. «. Um | m Nd al wwd al muud cam Ümßï in. Mwmc al nmcmm mwšmnmwu f m f cm MNX fi š UOE uwu fl> al UXM. Fi MW fl u al voxH ww qqmmæa 7902437- EXAMPLE 84 The efficacy of the compounds of the invention for controlling Museo autumnalis is demonstrated in the following test in which one day played fly larvae for eating on kodyngo containing 0.13, 0.25 or 0.50 ppm of the test compound.

Two replicates of 10 larvae per dose level and untreated controls were used in the assessment.

At each test level, an acetone solution of the amount of the test compound in question was sweetened to 1 kg of fresh cow dung and mixed for one minute with an electric mixer. The manure used for untreated control is processed in the same sweet except that only aoetone is added. The manure samples are divided between four paper souffle cups. At each concentration level (and controls), two cups of A 24-hour-old fly larvae are sown. The cups are kept for seven days at about 27 ° C and 50% relative humidity. Any pupae are then examined, which are counted, weighed and placed in plastic bottles to develop and die. When the flies are dead, they are counted and the percentage is calculated.

The data obtained are given in Table XVI below.in 120 7902467 ~ 5 q. Fl @ ~.> @ Om.o «.« M m.w> m ~. =. , ~ ^ ~ = u. = u, _ _. @ .o @ m.wæ. mH.c o = u | o | ou | = u .o = U ~ m .zuí @ .c ° .o H fi okucqm W \ Um. .._ | .n | \ ,. ,, .n, llCQWÖ bm C fl m flflfl í _ Cmmüä fl w UG fi CwH®h hë fl cäum fi xømn: www vw co fl umwucmomnm | w = fl: »wm, | @a fi nHmm V uomn fi m> _% Wñwmm m _ m> _% Wñww mx m. E fl CEDUwQQHuw> GH> «uwwwmum¶owHm fi u: wu0a.Eow cwucwcc fl w 1 u flfi mw mnnm c fl cmumw> m H> x AAWNGB 121 Particularly preferred embodiments of the invention relate to compounds of the formula ncr2x«. ® cu-co-ø-cr fl _ÛO V | In R4 R [: 5 R2 3 V V wherein R represents H or F; R 2 represents isopropyl, R 3 represents CN, X represents 0 and R 4 represents H or F. Particularly preferred compounds are Q va-cyano-m-phenoxybenzylphisopropyl-4-difluoromethoxyphenyl acetate; (i) -α-cyano-m-phenoxybenzyl (+) - α-isopropyl-4-difluoromethyloxyphenyl acetate; 1α-cyano-m-phenoxybenzyl-α-isepropyl-4-trifluoromethyloxyphenylacetate; (i) -u-cyano-m-phenoxybenzyl (+) - α-isopropyl-4-trifluoromethaxiphenyl acetate; Vα-cyano-m-Phenoxybenzyl-α-ethyl-4-trifluoromethoxyphenyl acetate; m-phenoxybenzyl-α-ethyl-4-trifluoromethoxyphenyl acetate; Α-cyano-m-phenoxybenzyl-α-ethyl-4-difluoromethoxyphenyl acetate; m-phenoxybenzyl α-isopropyl-4-trifluoromethoxyphenylacetate; m-Phenoxybenzyl α-isoprobyl-4-difluoromethoxyphenyl acetate; α-cyano-m-phenoxybenzyl-α-isopropyl-4-trifluoromethylthiaphenyl acetate; α-cyano-m- (p-fluorophenoxy) benzyl α-isapropyl-4-difluoromethoxyphenyl acetate; Α-Cyuno-m- (p-Fluorophenoxy) benzyl α-isopropyl-4-trifluoromethoxy-Aphenyl acetate.

The invention also relates to methods of preparing compounds of formula 790246-7-5 79o24e7fs 122 Rc? x »IU cH-» co-o-ca 'Ûo vorirRCF2X-, Y and Z, are in the meta- or para-position to the carbon atom to which the olconic acid spheres group is attached ooh wherein X represents O, -S, 50 or SO 2, Y and Z each represent H, Cl, F, Br, NO 2, CH 3 or OCHS, R represents H, F, Cl, CHF 2 or CF 3, R 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl, R 3 represents H, CN or -CÉCH, and R4 represents H, F, Cl, CH3 or OCH3 - in that a compound of the formula .RCF X 2 cucocl I m. R r.z_2 may react with a compound of the formula nocal, gl e , \ I 1 CF il 3 V 34 in the presence of pyridine.

The invention also relates to a process for preparing a compound of the formula W r Û '17 now a '¿' e. 0: 1 9 -n h-lwmv O 1% 7902467-5 wherein RCF2X is in the meta or para position to the carbon atom to which the alkanoic acid ester group is attached and wherein X represents S, O, SO or SO 2 and wherein R represents F; Cl, CHF 2 or Cfa, R 2 represents ethyl, n-propyl, isopropyl, t-butyl or isopropenyl, R 3 represents H or CN by a compound of the structural formula: CH-'COA I e R ncrzx 2 wherein Å represents halogen and R and R 2 are as defined above may be reacted with an m-phenoxybenzyl alcohol of the formula: wherein R is as defined above in the presence of a tertiary organic s YV amino acid acceptor or an inert organic solvent at a temperature of 10 ° C to 10 ° C.

The scope of the invention also includes a sweetener for controlling insects and acarids, by contacting the insects and acarids, their site, place of production or feedstuff with an insecticidal or acaricidal effective amount of a compound of the formula: in RCH2x ca-co-o- ca n _ 'R4 A 32 R3.

ZY 7902467-5 124 wherein RCFZX, Y and Z, all of which are in the meta or para position of the carbon atom to which the alkanoic acid ester group is attached and X represents O, S, SO or SO 2, Y and Z each represent H, Cl, F, Br, NO, CH 3 or OCH 3, R represents H, F, Cl, CHF 2 or CF 3, R 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl, R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 or OCH 3 or the optical isomers thereof.

Preferably, compounds of the formula are used: 1 RCPX 2 few from * from * az 113 \ wherein RCFZX is in the meta or para position to the carbon atom to which the alkanoic acid ester group is attached, R represents H or F, X represents 0 or S, R2 represents ethyl, n-propyl or isopropyl, R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 or OCH 3 and especially the compounds α-cyano-m-phenoxybenzyl-α-isopropyl-4-difluoromethoxyphenylacetate; (Α) -α-cyano-m-phenoxybenzyl (+) - isopropyl-4-difluoromethoxyphenyl acetate; (i) -α-cyano-m-phenoxybenzyl (+) - α-isopropyl-4-trifluoromethoxyphenyl acetate; F m-phenoxybenzyl-α-ethyl-4-trifluoromethoxyphenoxyacetate; m-phenoxybenzyl α-isopropyl-4-trifluoromethoxyphenyl acetate. 1-25 .I fi om.; ¿M§nëförVüppfinní fi àèn, íhnéfuftás ^ É @ §n \ ep; insekt§çi fl Él; kbmå.M ÅÄ '_ vp§sífioñ.u9_én'föreníng mad¿forme1n ::; ncf-ígác: Ä A V çf * v, h 'C fl "CÖ" 0 "fc fl v v r.

'.Y \ Vu & íHsubstÄtuenterñq hur oQqh ~ ahgiván bétydél fi é o¿H "eft emuigßif I Ûumedél, iett \ ytak {ivtÅm§dé1» eLl§k qtt löáningsmedql, Sp§šie11tldv $ e§¿1 Åins§rkticiħ "betedknøÉ S ç1lér 0.v

Claims (8)

7902467-5 126 PATENT CLAIMS 1. Compounds of the formula: - RCFZX * CH-Co-o-CH 'Z Å W zf "-' '\\ I R4 RV wherein RCFZXQ, Y and Z, which are true in the meta or para position to the carbon atom to which the alkanoic acid ester group is attached and wherein X represents O, S, SO or SO 2, Y and Z each represent H, Cl, F, Br, NO 2, CH 3 or OCH 3, R represents H, F, Cl, CHF 2 or CF 3, H 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl, R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 or OCH 3 or the optical isomers thereof. A compound according to claim 1 having the formula: 1 Rc? x '_ I 2. ® cH-co-o-CH _ © -o Û R i I '. Wherein R 2 F 3 is in the meta or para position of the carbon atom to which the alkanoic acid ester group is attached, R represents H or F, X represents O or S, R 2 represents ethyl, n-propyl or isopropyl, R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 or ocH 3. The compound (1) -α-cyanoem-Phenoxybenzyl - (+) - α-isopropyl-4-difluoromethyloxyphenylacetate according to claim 2. m7 79Û2Ä67 * 5 The compound (i) -α-cyano-m-phenoxybenzyl - (+) - u-isopropyl-4-trifluoromethoxyphenyl acetate according to potent claim 2. 5. A process for the preparation of a compound of the formula: wherein RCF2X ~ ¿Y and Z, all of which are in the method ~ or poro-stüll- X Rcvz, to the colotome to which the olcanic acid ester group is attached and wherein X represents O, S , SO or SO 2, Y and Z each represent H, Cl, F, Br, NO 2, CH 3 or OCH 3, R 1 represents H, F, Cl, CHF 2 or CF 3, R 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl, R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 or OCH 3 by reacting a compound of the formula: RCFZX - CHCOCl IRYZ 2 with R 3 in the presence of pyridine. 6. Use of compounds of the formula RCF x 2 en-co-o-ca Z '-' 4 nz ns _ YW 7902467-5 128 wherein RCFZX-, Y and Z, all of which are in meta or para positions. to the carbon atom to which the alkanoic acid ester group is attached and wherein X represents O, S, SO or SO, Y and Z each represent H, F Cl, br, NO 2, CH 3 or OCH 3, R represents H, F, Cl, CHF 2 or CF 3 ethyl, n-propyl, isopropyl, isopropenyl or t-butyl, R 3 represents H, CN or -CECH and R 4 represents H, F, Cl, CH 3 or OCH 3 or the optical isomers thereof, for the control of insects and acarids by the insects and the acarids, their site, place of production or feedstuff are brought into contact with an insecticidal or acaricidally effective amount of the above-mentioned compound. Use according to claim 6 of the compound (i) -α-cyano-m-phenoxybenzyl - (+) - α-isopropyl-4-difluoromethoxyphenyl acetate. Use according to claim 6 of the compound (+) - α-cyano-m-phenoxybenzyl - (+) - α-isopropyl-4-trifluoromethoxyphenyl acetate. 9-I Insecticidal composition comprising a compound of the formula:. É RCF X § 2 cu-co-o-cz: / 'z | '. Rá x R2 Ra Y | wherein RCFZX, Y and Z are all in the meta or para position of the carbon atom to which the alkanoic acid ester group is attached and wherein X represents O, S, 50 or SO 2, Y and Z each represent H, Cl, F, Br, NO 2, CH 3 or OCH 3, R represents H, F, Cl, CHF 2 or CF 3, R 2 represents ethyl, n-propyl, isopropyl, isopropenyl or t-butyl, R 3 represents H, CN or -CECH and R 4 represents H, F , Cl, CH 3 or OCHS or the optical isomers thereof, an emulsifier, a surfactant and a solvent.