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    • 专利摘要:
    Insects and mites, their habitat, their breeding sites or their food are brought into contact with compounds of the formula: <IMAGE> in order to control the insects and mites. In formula I, R, R2, R3 and X have the definitions given in Patent Claim 1. The substituent of the formula RCF2X- is in the m or p position to the alkanoate group. An insecticide contains a compound of the formula I, an emulsifier, a surface-active agent and solvents. The compounds of the formula I are prepared by reacting an acid halide with an m-phenoxybenzyl alcohol in the presence of a tertiary organic amine and an inert organic solvent at from 10 to 30 DEG C. The compounds of the formula I in which X denotes sulphinyl or sulphonyl are also prepared by oxidation of the corresponding compounds in which X denotes sulphur.
    公开号:SU1082782A1
    申请号:SU782672702
    申请日:1978-10-12
    公开日:1984-03-30
    发明作者:Беркельхаммер Джеральд；Кеймсваран Венкатараман
    申请人:Американ Цианами Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the synthesis of biologics of active chemical compounds, in particular, metaphenoxybenzyl or p6-cyano-metaphenoxybenzyl esters 2 haloalkyl (oxy; thio-, sulfinyl- or sulfonyl) phenyl-alkanoic acids exhibiting insecticidal or xxodicidal activity.
    Known esters of phenylacetic acid, such as about 3 -fenoksibenzil- -isopropyl-Fmetoksifenilatsetat ,, 3 -fenoksibenzil- oC -izopropil- 3- meyuksifenilatsetat, ot phenoxybenzyl 3 -isopropyl-4-chlorophenylacetate, 3 -fenoksibenzil ob isopropyl-Fmetilfennlatsetat , 3-phenok 3 benzyl-oh-isopropyl-3-chlorophenylacetate to 3-phenoxybenzyl-ci-isopropyl-4-fluorophenylacetate 1. Many of them are effective agents for the control of insects and mites.
    The purpose of the invention is the metaphenoxybenzyl esters of 2-haloalkyl (hydroxy, thio, sulfinyl or sulfonyl) phenylalkanoic acids of the formula
    RC1.
    JgV-CH-CO-O-CH / VOl XsJ
    G NgBS
    where in SRZH, Y and Z are in revenge-or shra-position in relation to carbon
    Ricfgx
    the atom to which the alkanoic ester group is attached;
    X - O, S, SO or SOj; Y and Z - H, C1, F, Br. NO, CH or OCHj;
    R - N. F, C1, CHF2 or
    R is ethyl, N-propyl, isopropyl, isopropyl NIL or greg-butyl;
     H, CM or
    R4 is H, F, C1, CH3 or OCHD, or their optical isomers, provided that Y and Z are hydrogen; R is H or F; X is O or S, R 2 is methyl, α-propyl or isopropyl, exhibiting insecticidal and ixodicidal activity.
    Metaphenoxybenzyl esters of {1 2-haloalkyl {hydroxy, ther-, sulphish- or sulfonyl) phenyl-alkanoic acids of formula (1) are obtained by the reaction of-substituted 2-haloalkyl (oxy-, thio, thiol, sulphinyl- or sulfonyl) phenylacetylhalide of formula (II) chloride, with metaphenoxybenzyl alcohol of the formula (111). The reaction is carried out in the presence of a solvent, such as diethyl ether, benzene or toluene, at 10-30 ° C in the presence of an acid acceptor, in particular tertiary organic amines, trimethyl, triethylamine and pyridine;
    sn- he
    Accegroid or acid where R, Cf is in the meta or in the position of the carbon to which the alkanoic acid group is attached, X is O, S, S O or Rj is H, F, C1, CHFg or Rj is ethyl, Ni propyl, isopropyl, isoprop "| penyl or fjjer-butyl; RI is H or CN; A - halogen, preferably chlorine. Compounds of formula (1) can &amp; g obtained as optical isomers. For example, the iqw synthesis of esters of the formula (1), where R is hydrogen, and in Rjj there is a chiral center, is obtained with a right rotation, a juicy and a luster isomeric pair. In addition, “6-cyanosubstitution in Ri introduces an additional chiral center, giving additional u-rotation and left-rotation pairs. If is isopropyl-4-trifluoromethoxyphenylacetic acid. mixed with 0.5-1.0 mole. (-) - "C, .- phenzthylamine in dissolving e, such as ethanol or aqueous ethanol, then the salt of (+) - acid precipitates. Upon acidification, this salt releases an acid that contains more than 85% of (+) - isomer. Higher separation of the optical isomer can be achieved by recrystallization of the (-) -, 6-phenethylamine salt or by repeating the separation of the optical isomers with fresh (-) -phenethylamine. Metaphenoxybetszilovye or about - iano-metaphenoxybenzyl esters completely separated (4 -) - in &amp; -isopropyl-Trifluoromethoxyphenylacetic acid twice insecticide than the corresponding esters obtained from racemic acid. In the case of use of the ob-cyano-metaphenoxybenzyl ester, the activity is further increased if the corresponding optically active o-cyano-metaphenoxy benzyl alcohol is used in the ester formation stage. About -substituted 2-haloalkyl (hydroxy-, thio sulfinyl- or sulfonyl) phenylacetyl halide of the formula (11), where Rj is ethyl, i-propyl or | Isopropyl, you can use the corresponding toluene of the formula (IV) as a starting material. The preparation method includes five stages, the first of which is the halogenation of toluene of formula (IV) with bromine, chlorine, N-bromo-cation with imide (NBS), etc. in the presence of an inert organic solvent, for example, tetrachloride carbon, and a radical initiator, in particular light, benzoyl peroxide or zo-bms-isobutyl nitrile to obtain benzyl halide (V). The benzyl halide of formula (V) is then converted to the corresponding ferrous acetoshgril of formula (VI) by reaction with sodium or potassium cyanide in the presence of dimethyl sulfoxide (DMSO), ethanol, or the like, at an elevated temperature, which is slightly alkylated when treated with alkyl halide in the presence of base and inert organic solvent; and crown ethers as catalysts. Hydrolysis of oL-alkyl (substituted phenyl) acetonitrile of formula (VII) with an alkali metal hydroxide in the presence of alkylene glycol and water gives about -alkyl (substituted phenyl) acetic acid of formula (VIII). Treatment of an acid of formula (VIII) with thionyl chloride, thiol bromide, or others, preferably in the presence of an aromatic solvent, such as benzoyl or toluene, gives an oC-alkyl- (substituted phenyl) acetyl halide of formula (I), which is reacted with fortluoroxyfenzoyl alcohol ( 111) or t-cyano-methvphenoxybenzyl alcohol to form the metaphenoxybenzyl ester or the oC-gushano-metaphenoxybenzyl ester of 2-haloalkyl (hydroxy, thio-, sulphinyl- or sulfonyl) feshalkane acids of formula (1). These reactions are graphically depicted in process diagram 1.
     ig l ys tv
    (v-CHCN + con- V y-CY
    / / L-AH I). Thu L ttJy 1 f f
    xAzz / IHOCfJnCHo OH „„, 5 ... hGGU t
    2, W%
    7 cttcoon + socey- "V-CHCOCP
    -A- / Ioenzene- uL- / I
      (I) l,
    Pyridine
    benzene
    As an alternative to benzyl Zyrobium of formula (V), indicated in process diagram 1, where the products are limited to substitution in the schrv position, the corresponding haloalkyl (oxy or thio) benzene of formula (IX) can be chloromethylated. use the mixture // l .., RCF2Y-f3 (H20) j HC where Y is O or S Metaphenoxylbenzyl and 06-cyan9-meta (its phenoxybenzyl esters. alkyl-3 (4) tfluoromethoxyphenylacetic acid can also be obtained by alkylation of the metayl methoxyphenylacetonitrile when using alkyl halide in the presence of crown ether and base. By using metamethoxyphenylacetonitrile in this reaction, t6 -alkyl-3-methoxyphenylacetonitrile is obtained, and using the para-isomer on alkyl-4-methoxyfluoroacetonitrile. The position of the trifluoromethoxy substituent in the final product is determined by the alkyl starting material. the phenol thus obtained with triphosgene and a base in the presence of a solvent, for example chloroform, results in chlorothiol sucrose 0-, metha-formaldehyde or trioxane with zinc chloride and anhydrous hydrogen chloride to form benzyl of formula (X), which is then used in place of benzyl bromide of formula (V) to complete the synthesis of the compound of formula (1) Clg .RCFgY CHgCl OR para- (1-ionia-2-methylpropyl) femiyl formic acid. This ester is converted to OC-n-3-d (3) -trifluoromethoxyphenylaceto nitrile using trichloride molybdenum. The compound is then hydrolyzed to the corresponding alkyl-3 (4) -trifluoromethoxyphenyl acetic acid by reacting with thioyl glycol in the presence of an alkali metal oxide hydrate and water. (benzene or toluene) gives the acid chloride of the corresponding acid, which is reacted with metaphenoxybenzene or o-cyano-metaphenoxybenzyl alcohol to obtain methanobesilic or oC-cyano-metaphenoxybenzyl false zfir about -alkyl-3 (4) -triftorometoksifeniluksusnoy acid. These reactions are graphically shown in process diagram 11.
    CH-C11 VVgz CHjOKGNO
    ft r-CH-CO-O-CK CFjO R2
    In the reactions indicated in the process diagram 1L feces. However, it can be re-injected with the adyl - ethyl, M-propyl or isopropyl; R ,, - in the reaction of the corresponding phenol
    Dorod or cyaio group. 2p ™ of trifepol with chlorodifluoromethane in a mixture
    With alkaline hydrolysis of nitriles in an aqueous alkali and dioxane. pax, compounds where RCF2X is a - or Synthesis of compounds involving HCF ,, jOHCF-S, can occur wiping HCF2 rad-, the group is shown in the process diagram 111.
    Process Diagram III
    . (- “48% HBi .iJT YusN-SOGN
    CH O-Agg / .. I
    r viochsan
     usn-sogn-nss№2 vodshsh tmoon
    BUT Lzg /
    K2
    Pyridine ij
    CH-OH S (CH5),
    Scheme IV of the process shows, as an example, the synthesis of g, tp-e au by 3 (4) rpvfropo of methoxyfegacetic acid. 1slogs can be converted into the corresponding esters according to the process scheme 1.
     compounds of formula (1), in which I am an isoprestesh, the introduction of an o-nzoprrphenil group can be carried out using the scheme
    Y13
    "I-OH M
    X
    SNS SNZ
    ns-so-o-cng-f o Ii J and
    CFgO
    sleep
    SNS SND
     co - o - CM -YCNS-O -.x: 5.
    V. / II / 111
    / V
    KdOCHN SNS
    vS-sn-so - o-cHa-fi Iand
    Rdo
    / h
    SNS%
    Synthesis according to the scheme of the process V is illustrated on the scale of the penumbra of metaphthaloxybion-50 -th ovine ester about isopropyl-4 (3) t {“fluorohexynphenoneacetic acid.
    P1Zh obtained about-ciaio-metaphenoxy-6 and 11 new complex effects using methods 55 according to the process scheme 1 or according to process 11, there is no need to separate the predecessor &amp; cnano-metafenoxibeyl alcohol. Tolerate the appropriate meta or para -substituted “FENI LUXUSIN acid” using software
    the sequence of reactions represented on the i axis of the process Vn involving the reaction with two equivalents of isoprosh chloride I magnesium and acetone; conversion of the acid to ester and dehydration of the ester, hydroxy acids with phosphorus pentoxide.
    U-CH-soon / e-one
    SRDC / L
    SNS SNZ
    It is also possible, and sometimes it is preferable, to conduct mixtures of metaphenoxybenealdehyde, alkali metal cyanide, for example sodium cyanide, and the corresponding about -membrane (2-haloalkyl (hydroxy; thio-, sulphinyl or sulphinyl) sulfide) phenylacetal-1 halide in one stage to obtain the-cyano-acid .
    Process Scheme VI is a general process flow diagram for the test substance. BUT where r and Y - N, vr il U CH-COOH V21 | PAS12 BUT -. VcHCOOH R2X Process Diagram VI Y 2
    but -g CHCOOH NaOH CHF2ei - FgCHO
    "
    HjO CH2B1 "NaCN CH 50 CH2 CN
    CH2CN R2Bi llaOH
    fA
    CHjO- CHC N + NVG HO
    FR2 HO- CHCOOH NaOH CHF2C1CHCOOH "2 F5.CHO - VCHCOOH
    V rWCOOH

    / B2
    N02
    // v
    L CHCOOH NaOH + C HF2Cl-- -F2CHO - VCMCOOH
    HONO.
     l
    N02 -CHgO-Olen. VcHeO- CHgBj + NaOH OCHj-CHeC OC "5
     VcH20- V- JHC N HCl --- HO- / fHCOOM
    osnz S I-SOOYa CTOfgCl KONR OCHj
    o4 V CHgOlT РВГз -CH, 0-Q-CH2Br Л-СНгО-СЖ2С Г ОШ5 «З ОСИ, -Т2. f 2 b
    CIO 4HCN ("0-t -GHCN
    -o
     five
    k U AH
    H4
    :
     SNOM
    with SI
    CHClj
    ft V-CHOTi + with SCI
    Z y
    "CX T R2
    CHCN nosngs he "
    m: L2
     JV CFjX
    RCFgX
    gOClg .1. I j.
    HCFjX
    CHCOCH-H6
    R2
    R4 Pyridine
    CH CO-O-CH R2RS
    benzene
    The studied compounds are highly effective contact and gastric dyes for ixodid ticks and other insects, in particular, dipteridae, lepidoptera, coleoptera and even-winged insects. They exhibit a very long-lasting residual insecticidal activity on tissue crucians, are effective in the soil for controlling ticks and other insects when injected with animals in animals orally or parenterally or when applied as a local insecticidal or ixodicidal composition. 0 To obtain stable insecticidal and acaricidal compositions, the compound does not require stabilizers. They can be used in combination with biological chemicals, e.g. pyrethroid sinergetikami, 5S In particular carry piperonyl butoxide, sesamex or m-oktilsulfoksidom isosafrole, and insecticides such as phosphates, carbamates, formamidines, hlorzamescheknye hydrocarbons or halobenzoylureas. To combat the colony, including soil insects that attack plants and / or harvested crops, including stored grain, the proposed insecticidal compounds can be applied to plant foliage, insect habitats and / or naseko food resources: we are X . The active compound is applied by spraying a liquid, but it can also be in the form of an aerosol, I dust, granules or wettable powder formulations. Liquid oily spray solutions and emulsifiable concentrates are most suitable.
    For convenience, during handling and loading, they are dispersed in water at the place of use, and then applied as a sprayed solution to the foliage of the plants, the soil, or the surface of the area to be treated.  Emulsified, syifiruemy concentrate, suitable for the protection of diverse crops, such as hghebnyh cereals, cabbage, pumpkin, corn, cotton, tobacco, soybeans, ornamental plants and shrubs, etc.  P. may contain weight. %: active substance 20; emulsifier used in the preparation of pyrethroid compounds 4; surfactant 4; organic solvent (cyclohexane) 25 and petroleum solvent (minimum aromatic content 83 vol. %) 47.  The proposed compounds, when used as systematic insect and ixodicidal agents for animals, can be administered to the host animal either orally or parenterally.  When administered orally, it is used in any conventional form intended for oral administration (pill, capsule, tablet or oral, infusion).  The active agent can also be included in the food of the animal, such as a balanced diet, containing 0.0001-0.1 weight. % (preferably 0.001-0.05 weight. %) active compound.  If necessary, systematic insecticidal and ixodicidal agents can be introduced into the body of an animal by subcutaneous, intraperitoneal or intraperitoneal injection so that it is distributed throughout the body of the animal with a blood flow.  The systematic agent can be dissolved or dispersed in a pharmaceutically acceptable carrier for administration (water, propylene glycol, vegetable oil, glycerol formal, etc.).  P. ).  Systematic agents have a large safety and efficacy reserve for the protection of a variety of animals, in particular, livestock and domestic animals (cattle, sheep, horses, dogs, cats, etc.) P. ) from the attack of fleas, mosquitoes, flies, ticks, etc.  P.  As an insecticide -T-Cyano-Metaphenoxybenzyl ester Qt-Isopropyl-Phlorodifluorometroxyphenyl acetic acid ", -Metaphenoxybenzyl ester, (X-Isopropyl- 4 (1,1,2,2-tetrafluoroethoxy) fenite of acetic acid OS -Cyano-metaphenoxybenzyl ester about -isopropyl-4-pentafluoroethoxyphenylacetic acid Metaphenoxybenzide; new ester-ethyl-3-trifluoromethoxyphenylacetic acid.  W.  - webshop m-cyphenoxybenzyl ester 06 -n-propyl-4-chlorodifluoromethoxyfestoxyc; - cy-methaphenoxybenzyl ester ob-reg-butsh-1-4-trifluoromethoxyphenes-acetic acid eC Cyano-metaphenoxybenzyl ester () C, -isopropyl-4-trifluoromethylthiophenylacetic acid Metaphenoxybenzyl ester, OC-ethyl-4-. triftormetilsilfinsh1foniluksus- acid of cyano-ester 06 metafenoksibenzilovy -isopropyl-W-diftorometilsulfonilfe niluksusnoy acid metafenoksibeneilovy ot-cyano-ester of ethyl-4-triftorometoksifeniluksusnoy acid oi cyano-metafenoksibenzilovy stacked efiroO -izopropenil- 4- triftorometoksifeniluksusnoy acid Metafenoksibenzilovy ssfr b6 isopropyl-3-bromo-4-difluoromethoxyphenylacetic acid Qi -Cyano-metaphenoxybenzyl complex sfir about -isopropyl-3-chloro-4-difluoromethoxyphenyl acetic acid lots Metaphenoxybenzyl ester (x ;; isopropyl-4-chloro-4-difluoromethoxyfesh luscus acid -Cyano-metaphenoxybenzyl ester OU-isopropyl-3-bromo-4-difluoro-methoxy-xphenyl acetic acid; Metaphenoxy-benzyl ester; dichloro-4-difluoromethoxyphenylacetic acid c6 -Cyano-metaphenoxy-cisyl ester of OC-isopropyl-3-me1-IL-4-difluoromethoxyphenylacetic acid for an ф ф-с аф аф аф аф аф аф мет мет мет мет мет мет мет мет мет мет мет мет мет мет мет мет мет мет мет мет oC-isoprosh1l-3-nitro-4-difluoromethoxyphenylacetic acid ester of ot-cyano-methaphenoxybenzyl ester of isopropyl-3-methoxy-4-difluoromethoxyphenylacetic acid -Ethinyl-metaphenoxybenzyl ester; ) -Oi-Cyano-metaphenoxybenzyl ester (4 -) - () i-isopropyl-4-difluoromethoxyphenylacetic acid (t) -ot-isopropyl-4-t {| fluoromethoxyphenyl acetic acid.  Example 1   Metaphenoxybenzyl ester of sb-isopropyl-4- (1,1,2,2-tetrafluoroethocot) phenylacetic acid.  To a stirred mixture of 6.81 g (0.0340 mol) of metaphenoxybenzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) of anhydrous pyridine and 20 ml of methylene chloride are added over 20 microns of a 20 ml solution in chlorine methylene and 10.6 g (0.034 mol) of 2-metsh1-2-para- (1,1,2,2-tetrafluoroethoxy) phylnyl butylchlo {SD8.  The mixture was 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 with sodium sulfate, filtered, and then heated.  .   16.24 g (100%).  This product is purified on a dry silica gel column (116x5 cm, eluent 1: 1 hexane-methylene chloride), collecting samples between 85 and 63 cm (4FONT solvent 113 cm).  12.60 g (78%) of a clear, yellowish colored oil are obtained.  Calculated,%: C 65.54; H 5.08; F 15.95 C26H 4F404; Found: C, 64.99; H 4.96; F 19.10 Example 2.  Paul) oxy-isopropyl-4- (1,1,2-tetrafluoroethoxy) phenylacetic acid.  To a stirred mixture of 8.81 g (0.0333 mol) of y, α-cyan-metaphenoxybenzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) of anhydrous pyridine and 20 ml of methylene chloride are added over 20 minutes 20 ml of a solution of 10.6 g (0.034 mol) of 3-methyl-2 pb- (1,1,2,2-tetrafluoroethoxy) phenyl butyrshchloride in methylene chloride.  The reaction mixture is stirred at room temperature for 66 hours and then diluted with 0 ml of ether, washed with 200 Ml of 20% strength (lactic acid and 200 ml of water, dried with sodium sulfate, filtered, and then evaporated to obtain a dark red oil.  In order to remove the impurity of metaphenoxybenzaldehyde, the oil is subjected to recovery with 0.5 g of sodium borohydride at an ice bath temperature.  The resulting oil is purified on an anhydrous silica gel column (121 x 5 cm, eluent 1: 1 hexane-methylene chloride), collecting samples between 77 and 57 cm (solvent front 113 cm).  Obtain 11.17 g (66%) of clear oran.  chewing butter.  Calculated,%: C 64.67; H 4.62; N 2.70; F 15.16 CnH. 2, F4N04 220 Found: C, 65.26; And 4.81; N 2.82; F 17.94 Example 3.  Obtaining os-cyano-metaphenoxybenzyl puffed ether ci.  -isopropyl-4-trifluoromethoxyphenylacetic acid.  The mixture (X-isopropyl-4-trifluoromethoxyphenylacetonitrile (2.0 g) and potassium hydroxide hydrate (3.0 g in ethylene glycol (35 ml) and water (3 ml) is heated at} 40 ° C for 8 hours.  The solution was poured into 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 and evaporated to an oil.  OC-isopropyl-4-trifluoromethoxyphenyl acetic acid (1.23 g) is obtained.  Infrared spectrum (pure) 1700 cm. A solution of ω-isopropyl-4-trifluoromethoxyphenylacetic acid (1.2 g) and thionyl chloride (0.6 ml) in benzene (5 ml) is heated under reflux for 4 hours.  Evaporation of the solvent and an excess of thionyl chloride gives about -isopropyl chloride: L-4-trifluoromethoxyphenyl acegyl.  A solution of obi-isopropyl-4-trifluoromethoxyphenylCethyl chloride (4.58 mmol) in ether "(5 ml) is added to an ether (20 ml) solution of about-cyano-metaphenoxybenzyl alcohol (4.58 mmol) and pyridine (0.5 ml ).  The mixture is stirred overnight and filtered.  After washing, the filtrate is evaporated and the residual oil is purified on silica gel plates 5x2 mm, using a 1: 1 mixture of methylene chloride and hexane as eluent.  The R-0.55 zone is extracted with ether and evaporated to give the desired ester (0.85 g).  IR spectrum (pure) 1755 cm.  NMR (CDCC1); 5 6.8-7.6 (t, 13 H, aromatic H); 6.31 and 6.28 (s, 1H, -CH-Ar); 3.27 (|, J = 7 Hz, 1H, -CH-CH (CH3) g); CN 2.0-2.6 (t lH, -CHCHj); 0.6-1.2 (four doublets, V 7 Hz, 6H, isopropyl CH); 19f chemical shift 58.8 s with respect to example 4.  Preparation of metaphenoxybenzyl complex fir oL -isopropyl-4-triFluoromethoxyphenyl acetic acid.  1 To a solution of metaphenoxybenzyl alcohol (1.89 g) and pyridine (1 ml) in methylene chloride (6 ml) was added a solution in methylene chloride (7 ml) of oC-isopropyl-4-trifluoromethoxyphenylacetyl chloride obtained from the corresponding acid (2, 46 g) similarly to measure 3.  After stirring the reaction mixture overnight, it is washed with water, a dilute hydrochloric acid solution and a dilute solution of potassium hydroxide and evaporated to an orange oil.  Purify using a silica gel chromate decanter to get the desired ester (2.76 g).  IR spectrum (pure) 1738.  NMR (CDCl1) 6.73-7.45 (m, 13H); 5.03 (s, 2H); 3.20 (OC, J 10.5 Hz, 1H); 2.26 (m, IH); 0.66 and 0.94 (two vol, J 6.6 Hz, 6H).  Example 5  Production of esters of oC-ethyl-io-n-propyl-4-trifluoromethoxyphenylacetic acid.  (1-Ethyl-4-trifluoromethoxyphenyl) tssusnuyu and ot -n-propyl-4-trifluoromethoxyphenylacetic acid are converted into esters {1 similar to examples 3 and 4, respectively (Table.  one).  Example 6  Preparation of α-cyano-metafen oxybenzene ester of 2-isoprosh-4-trifluoromethylthiophenidacetic acid.  o (i-Isopropyl-4-trifluoromethylthiophene acetyl nitrile (6.9 g, 0.0265 mol) and 50% sodium hydroxide (25 g, 0.312 mol) are mixed ± in 53 ml of 31131 lhlenpolicol and heated to a moderate reflux for 18 h.  The reaction mixture was poured into ice water and extracted with ether.  The aqueous phase is acidified with concentrated HC1, then re-extracted with ether, the extract is washed with water and dried over sodium sulfate.  Evaporation in vacuo gives 2.05 g of an oily product about α-isopropid-4-trifluoromethylthiophenylacetic acid.  To synthesize, respectively, about -ethyl-4-trifluoromethylthiophenylacetic C-and-C-4-trifluoro-methyl-thioacetic acid as the starting material is used ot - methyl-4-trifluoromethylthiophenylacetonite | W or her n-propyl-4-trifluoromethylthiophenylacetate.  Using isopropyl L-4-trifluoromethylthiopherylacetic acid, as in Examples 3 and 4, the product is obtained in the form of an oil.  Vyisleno,%: C, 64.32; H 4.57; F 11.74; N 2.79; S 6.60 Found: C 64.27; H 4.62; F 11.68; N 2.68.  S 6.43.  Comparable results are obtained using L--etnl Ftriftorometiltiofeniiztssusnuyu or both - "- prosh1l-4-triftorometiltiofeniluksusnuyu acid, respectively, to synthesize a (- cyano - metafeioksibenzilovy ester -ztil-4-oL triftorometiltiofensh1uksusnoy acid and cyano-complex metafenoksibenzilovy ester on —H-propyl-4-trifluoromethylthiophenylacetic acid.   Example 7  Preparation of metaphenoxybenzyl ester with isoprosh1L-4-trifluoromethylthiophenylacetic acid.  Using a C-isoprosh-4-trifluoromethylthiophenylacetic acid, similarly to examples 3 and 4, the product is obtained in the form of an oil.  Example 8  Preparation of ot -diano-metaphenoxybenzyl ester of α-isopropyl-4-difluoromethylthiophenylacetic acid.  Sodium hydroxide (18.4 g, 0.46 mol) in 50 ml of water and c-isopropyl-4-mercaptophenylacetic acid (11 g, 0.05 mol) in 40 ml of dioxane is mixed and heated to 50 ° C.  Chlorodifluoromethane (freon-22) bubbling slowly under the surface of the liquid, causing a direct exothermic temperature rise to 75 C.  The addition is continued until the exothermic evolution of heat begins to subside (about 0.5 h).  The reaction mixture is cooled to room temperature and treated with 100 ml of ice water.  The aqueous layer was extracted with 3X 200 ml of ether, then acidified at 15-20 ° C with concentrated HCl.  The resulting oil is removed with ipf (I) oh extraction.  The ether solution is washed with water and saturated sodium chloride before drying over sodium sulfate and evaporation in vacuo.  10.2 g of a dark brown resin of ot-isopropl-4-difluoromethyl-1-phenylacetic acid are obtained, which is used without subsequent purification.  Similarly, they obtain about -isoprosh-3-chloro-f-difluoro-umethyl thiophylamine acid using oC-iso-1-3-chloro-4-me1 Isaptophenylacetic acid.  When using o-isoprosh1-4-difluoro-neophenyloxy-acid, acid, similarly to examples 3 and 4, the product is obtained as an oil.  Outlined,%: C 66.79; H 4.96; F 8.13; N 3.00; S 6.86.  CzfeH FiNO S Found,%: C 66.59; H 5.13; F 8.02; N 2.8; S 6.95.  Example 9  Preparation of oi, α-isopropyl-4-di-: fluoromethoxyphenylacetic acid metaphenoxybenzyl ester.  Mixed with a magnetic stirrer at 8 (w / w mixture of 10.00 g (0.0515 mol) of isopropyl-4-hydroxyphenylacetic acid, 65 ml of dioxane, 19.08-g (0.464 mol) of sodium hydroxide and 30 ml of water are bubbled 47 g (0.532 mol) of chlorodifluoromethane for 4 h.  The reaction mixture was poured into 250 ml of ice-cold water, 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 with sodium sulfate, filtered, b then evaporated to obtain a white paste.  A mixture of hexane and methylene chloride is added and the mixture is filtered to remove the solid — starting material: Fnlyrate is evaporated.  Get 5,41 g of a clear brown oil ot-isopropyl-4-difluoromethoxyphenylacetic acid with a purity of at least 85%.  NMR (SSCN-o 5-pyridine) S 7.43, (° C, J 8.2 Hz, 2H); 7.08 (vol, J 8.2 Hz, 2H); 6.57 (t, J 74.3 Hz, W); 3.63 (s, admixture); 3.25 (d, J 10 Hz, 1H); 2.37 (t, W); 1.19 (d, j 6.5 Hz, 3N); 0.78 (d.  J 6.5 Hz, ZN); 13.82 (s, Ш).  Similarly, ob-ethyl-4-difluorometok (zhfennluxusn) pu and v6 -propyl-fafluoromethot-phenenl acetic acid are obtained using e6-e-w-4-oxnfennluxus or oL -n-4-oxyphenylacetic acid, respectively.  Using C-isopropyl-4-difluoro-metoxy-phenylacetic acid, analogously to examples 3 and 4, the nкduk ± are obtained in the form of a pale yellow.  oils.  Calculated. %: C, 70.41; H 5.67; F 8.91 Cj H24FjO4 Found: C 73.36; H 5.96; F 10,56 Comparable results are obtained using Bi-ethyl-4-diftorometoksifeniluksusnuyu ishs O repelled-4-diftorometoksifeniluksusnuyu acid to synthesize metafenokeibeneilovy oi ester Ethyl 4-diftorometoksifeniluksusnoy-propyl or s-methoxyphenylacetic acid, respectively Fdiftora EXAMPLE 10 .  Preparation of cyanometafenoxybenzyl ester 6i-isopropylfluoromethoxyphenylacetic acid.  Using α-isopropyl-4-difluoromethoxyphenylacetic acid, as in Examples 3 and 4, the product is obtained as an oil.  NMR (CDCC1,) S 0.88 (four doublets, J 6 Hz, 6H, CH,); 2.30 (t, 1H, -CH-CH (CH,)); 3.24 (et, j 10.1 Hz, W, -CH-CH (CH. ),); 6.33 (two singlet, W, -CHCN); 6.45 (t, J 74 Hz, W, CH, 0-); 7.16 (t, BH aromatic H).  Vychnseno,%: C 69,17; H 5.13; F 8.42; N 3.10 CigH2, Found: C, 69.41; H 5.20; F 10.25; N, 3.70 Comparative results are obtained using ti-methyl-4-dfluoromethoxyphenyl acetic acid or ot -c-propyl-4-difluoromethoxyphenyl acetic acid to synthesize with α-cyanometaphane co-benzyl ester on ethyl ethyl-4-difluoromethoxyphenyl methyl acetylmethyl phenylmethyl benzyl benzoyl methyl 4-difluoromethoxyphenyl acetic acid; -etaphenoxybenzyl ester of ei - "- 11p011Il-4-difluoro1-oxyphenylacetic acid, respectively.  Example 11  Preparation of meta-phenoxybenzyl ester on isopropyl-4trifluoromethylsulfinylphenyl acetic acid A mixture of 10.0 g of metaphenoxybenzyl ester oi-isopropyl-4-trifluoromethylthiophenylacetic acid and 4.1 g of metachlorophenol-benzoic acid (85%) are heated for a given time to be given in a given case to be given in a given case to be given by the amount of the product for which I am given to one of an account for an account for an amount per set of c, I will be given to the same for a given case, but I will give you to the amount of foodstuff for you. filtered off.  The concentrated residue is purified from a silica gel dry column (2: 1 methyl chloride | - hexane).  Get the product in the form of a pale yellow oil.  Similarly, they receive a metaphor for them. trifluoromethylthiophenylacetic acid, respectively.  Example 12  Getting o4-cyano-meta.  Phenoxybenzyl ester on -ethyl-3-difluoromethylsuponylphenylacetic acid.  A mixture of 10.0 g of the about-cyano-metaphenoxybenzyl ester of α-ethnyl-3-difluoromethylthiophenylacetic acid and 9.0 g of metachloroperbenzoic acid (85%) is boiled under reflux in 100 ml of dichloroethane overnight.  The mixture after filtration and concentration is purified by chromatography on a dry silica gel column (2: 1 (methylene chloride / hexane)).  The product is obtained as a yellow oil.  Similarly prepared metafenoksibenzilovy of cyano-ester y-isopropyl-4-triftorometilsulfonilfeiiluksusnoy acid oi cyano-metafenoksibenzilovy ester oi -n-propyl-4-triftorometilsulfonsh1feniluksusnoy acid using ot metafenoksibenzilovy -cyano ester of -isopropyl-4- trifluoromethylthiophenylacetic acid or d-cyano-metaphenoxybenzyl ester of n-propyl-4-trifluoromethylthiophenylacetic acid, respectively.  Example 12  Preparation of 4-trifluoromethoxy-3-isoprophenyl acetic acid metaphenoxybenzyl ester.  To a solution of laria-trifluoromethoxyphenylacetic acid (22 g, 0.1 mol) obtained by alkaline hydrolysis in ether (50 ml) is added, at an ice-bath temperature, a solution of isoproshmagnium chloride (0.2 mol) 25 in ether.  The reaction mixture is stirred for 2 hours at room temperature, anhydrous acetone (5.8 g, 0.1 mol) is added to it and refluxed for 5 hours, cooled, carefully acidified with aqueous sulfuric acid and extracted with ether .  The combined organic layers were extracted with 10% sodium carbonate solution.  The alkaline layer is acidified with hydrochloric acid and extracted with ether.  The ether extract is dried (NartSO) and evaporated.  Get Fluorine-methoxy-, / 3-dimethylatropic acid.  A solution of 4-trifluoromethoxy- / 3, -dimethylatropinic acid (13.9 g, 0.05 mol) and triethylamine (6.1 g, 0.06 mol) in acetone (100 ml) is added to metaphenoxybenzyl bromide (13.2 g, 0.05 mol) at the temperature of the ice bath, after which the mixture is refluxed for 4 hours.  The mixture was poured into cold dilute hydrochloric acid and extracted with ether.  The ether layer is washed with 10% hydrochloric acid and water, dried (NagSO L and evaporated to obtain the hydroxy acid ester, which is dehydrated as sol at 18 h.  The crude ester is obtained by filtration and removal of the solvent.  Purification of the material by chromatography on dry silica gel (50:50 methylene chloride - hexane as solvent) gives a product in the form of a pale resin and resin.  Example 13  Preparation of cyOC-metaphenoxybenzyl ester of C (C) -JpcT butyl-4-trifluoromethoxyphenylacetic acid.  Neopentyl chloride is converted to Grignard H reagent by carbonation according to the method of Weinstein and Morse.  A 2-7 pp-butyl-4-trifluoromethoxyphosphonic acetic acid is obtained in the form of a white solid.  Example 14  Preparation of meta-feioxybenzene ester of about -isopropyl-Zbrom-4-difluoromethoxyfeschacetic acid A mixture of OC -isoproxyl-4 hydroxyphenylacetic acid (20 g, 103 mol) in chloroform (250 ml) is cooled to OH and. , e. Bromine (16.5 g, 0.103 mol) is added to hpropof (15 ml) for 30 warn.  The reaction solution was stirred at 0 ° C for 30 minutes and then allowed to warm to a temperature of 25 ° C.  Zvstvst {Shtel vsharivshrt, and the residue is recrystallized from al &amp; g hexane-benzo.  Obtain monobromide Obzoprs 101L-4-oxf of acetic acid (22.1 g) Art. square  PZ-PL.  2 Oi - Isopropyl-3-bromo-4-hydroxyphenylacetic acid (18.0 g) is converted to the corresponding difluoromethoxy acid.  o-Isopropyl-3-bromo-4-difluoromethoxyphenyl acetic acid is obtained as a waxy solid (4.7 g) by separating the unreacted starting material by chromatography on silica gel (eluent 3, 5% methanol in chloroform).  Using 0-isopropyl-3-bromo-4-difluoromethoxyphenylacetic acid, analogously to examples 3 and 4, a product is obtained in the form of a pale yellow resin.  NMR (SORSC) S 6.8-7.7 (t, 12H, aromatic H); 6.45 (t, J 7.4 Hz, 1H, OCHf); 5.10 (bs, IH, CH); 3.18 d, J 9 Hz, W, CH - CH (CH3) 2); 1.0 and 0.71 (2d.  J 6 Hz, 6H, isopropyl CH).  Example 15  Preparation of β-cyano-metaphenoxybenzyl ester of b6-taopropyl-3-bromo-4-difluoromethoxypheneacetic acid.  Using v-Isopropyl-3-bromo-4-difluoromethoxyphenyl acetic acid, as in Examples 3 and 4, the product is obtained as a yellow gum.  NMR (CDCCl) 6.9-7.7 (m, 12H, aromatic H); 6.50 (t, J 74 Hz, W, OCHD); 6.33 and 6.36 (2 S, W, CH-CN); 3.25 (oi, CH-CH (CH)); 0.6-1.1 (4d, 6H, isopropyl CH).  Example 16  Preparation of a cyano-metaphenoxybenzyl ester of about -isopropyl-3-chloro-4-difluoromethoxyphenylacetic acid.  The mixture of oC-isopropyl-4-hydroxyphenylacetic acid (30 g, 0.154 mol) in chloroform (600 ml) is cooled to a temperature, chlorine gas (12.0 g, 0.169 mol) is slowly bubbled, and the solvent is distilled off. chloro-4-hydroxyphe-1 nil acetic acid by recrystallization from a mixture of benzene-hexane.  T.  square  125-128 C.  Using aJ-isopropyl-3-chloro-4-hydroxyphenyl acetic acid, similarly to examples 9, 3 and 4, the product is obtained in the water resin.  NMR (CDCC1) 5 6.8-7.5 (m, 12H, aromatic); 6.50 (t, J 74 Hz, W, OCHF); 6.33 and 6.30 (2s, IH, -CH-CN); 3.25 (d.  J 10 Hz, W, CH-CH (CH) 2).  Calculated,%: C 64.26; H 4.56; N 2.88; C1 7.30; F 7.82 C2BH22C1P2 NO4.  Found,%: C 64.27; H 4.70; N 2.94; C1 7.20; F 7.78.  Example 17  Preparation of metafeioxy benzyl ester on isopropyl-3-chloro-4-d11 fluoromethoxyphenylacetic acid.  Using α-isopropyl-3-chloro-Foxyfenil hydrochloric acid, similarly to Examples 9, 3 and 4, the product is obtained as a yellow oil.  NMR (CDCC1. 2) 8 6.8-7.6 (m, 12H, aromatic If); 6.47 (t, J 74 Hz, OCHF), 5.07 (bs, 2H, CH).  Calculated,%: C 65,16; H 5.03; Cl 7.69; F 8.24 Ci H ClfyO Found:%: 65.46;  H 5.05; Cl 7.73; Example 18  Preparation of C-daano-metafeioxybenzyl ester of α-isopropyl-3-bromo-4-difluoromethoxyphenylacetic acid.  A mixture of oC-isoprop-1-4-hydroxyphenoacetic acid (30 g, 0.155 mol) in chloroform (SCO ml) was cooled in an ice-salt bath.  Chlorine gas (approximately 30-35 g) is bubbled into 1 FIF 0-5 ° C for 90 minutes.  The solution was stirred at -5 ° C for 1 h and allowed to warm to room temperature.  The solvent is evaporated.  Et-isopropyl-3,5-dichloro-4-hydroxyphenylacetic acid is obtained as a white solid (29.8 g) by recrystallization from hexane.  T.  square  152-154 ° C.  i Using the obtained OL-isopropyl-3,5-dachloro-4-hydroxyphenylacetic acid, analogously to Example 9, you will get oC-isopropyl-3, 5D1IyOyr-4-difluoromethoxyphenylacetic acid in the form of an oil with a content of 15 mol% of the starting material.  Using c6-isopropyl-3,5-dichloro-4-dipht {p tags, phageloxyacetic acid, similarly to measures 3 and 4, the product is obtained in the form of a yellow resin.  NMR (COC1) 8 6.9-7.7 (t, 1W, aroma chesC1N H); 6.67 (t, J «74 Hz, Sh.  OCHg) 6.33 H 6.40 (28, H, CH-CN); 3.23 (оС, J - 10 Hz, Ш, СН-СН (СНз) 2) 0.6-4.1 (4с, 6Н, isoprosovol SNL.  Determined,%: C 60.01; H 4.07; N 2.69.   NO Naide%: C 59.78; H 4.30; N 2.31.  PRI me R 19.  Preparation of o-isopropyl-3,3-dichloro-4-difluoromethoxyphenylacetic acid meta-hydroxy-ester ester.  Using ot-isopropyl-3,5-dichloro-4-difluoro-acetoxy-phenylacetic acid, analogously to examples 3 and 4, the product is obtained in the form of a gum.  Calculated,%: C 60.61; H 4.48; C1 14.32; F 7.67; Found,%: C 60.50; H 4.60; C1 14.13; F 7.52 Example 20.  Preparation of sL-cyano-metaphenoxybenzyl ester of about -isopropyl-3-methyl-4-difluoromethoxyphenylacetic acid-eta.  3-Methyl-4-methoxyphenylacetonitrile is converted to uL-isopropyl-3-methyl-4-difluoromethoxyphenylacetic acid.  The product is contaminated with ot-isoproxy-3-megyl-4-hydroxyphenylacetic acid.  The final ester is purified by chromatography.  The ester has the appearance of a viscous oil.  NMR (CDCl1) 6.8-7.6 (m, 12H, aromatic H); 6.45 (t, J 74 Hz, W, OCHF); 6.48 and 6.53 (2s, III, CH-CN); 2.25 (s, 3N, CH).  Calculated,%; C, 69.66; H 5.41; N 3.01 Found,%: C 70.05; H 5.86; N 2.83 Example 21.  Preparation of α-cyano-metaphenoxybenzyl ester of oC-isopropyl-3-fluoro-4-difluoromethoxyphenylacetic acid.  Starting from about -isoproxy-3-fluoro-4-difluoromethoxyphenylacetic acid, analogously to examples 3 and 4, the desired ester is obtained in the form of: kelta oil. .   NMR (CDCClj) 6.8-7.5 (m, 12H, aromatic H); 6.63 (t, J 74 Hz, 1H, OCHF4), 6.33 and 6.37 (2s, W, CH-CN).  Calculated,%: C, 66.52; H 4.72; N, 2.98; Found: C, 66.27; H 4.87; N 2.99 Example 22.  Preparation of OC-cyano-metaphenoxybenzyl ester of about -isopropyl-3-nitro-4-difluoromethoxyphenylacetic acid.  Using the OS-isopropyl-3-nitro-4-hydroxyphenyl acetic acid, as in Example 9, oi-isopropyl-3-nitro-4-difluoromethoxyphenylacetic acid is obtained in the form of a crude material containing unreacted starting material.  However, by repeating the reaction with Freon-22 three times, the product is obtained in the form of small beige solid particles (hex-.  san), t.  square  88-90 C.  Using Sb-isopropyl-3-nitro-4-difluoromethoxyphenylacetic acid, as in Examples 3 and 4, the product is obtained as a yellow oil.  Calculated: C 62.90; H 4.47; N, 5.64; Found: C, 62.51; H 4.77; N 5.58.  Example 23  Preparation of -1-o-w-metaphenoxybenzyl ester of оС, -isopropyl-3-methoxy-4-difluoromethoxyphenylacetic acid.  Using ε-isopropyl-3-methoxy-4-dimethoxy-phenyl acetic acid, analogously to examples 3 and 4, the product is obtained in the form of a gum.  Example 24  Preparation of substituted (cyano-metaphenoxybenzyl esters of fluoroalkoxyphenane acetic acids.  From either c-isopropyl-4-difluorometh oxyfeschuacetic acid or from c6 -isopropyl-4-trifluoromethoxyphenylacetic acid cyanohydrin of the corresponding substituted alhydride, in analogy to examples 3 and 4, esters are presented in Table.  2  Example 25  Preparation of M-ethynylmette of phenoxybenzyl complex zfnr about -isopropyl-4-tr fluoromethoxyphenylacetic acid. .  Acetylene is dried in three traps: dry: ice-acetone, concentrated sulfuric acid and calcium chloride, and then bubbled under a pressure of 0.35 atm into anhydrous tetraprofrofuran (100 ml) for 10 minutes.  BrOAgate ethylmagnesium (0.14 mol) is added dropwise over 2 hours at such a rate that the ethane production is slow and steady.  Then acetylene is bubbled for 15 minutes.  Metafene oxybenzahdehyde (27.7 g, 0.14 mol) in tetraprofrofuran (25 ml) is added to the reaction site at 15-20 C.  The reaction mixture is allowed to warm to room temperature and is stirred overnight. The complex is decomposed by dilution of ammonium chloride.  The product is extracted with ether, washed with water and dried ().  Evaporation of the solvents, followed by vacuum distillation using the Kuelgel apparatus, yields the desired (ethynylmetaphenoxybenzyl alcohol (21.5 g).  Using the specified alcohol n oi-isoprosha 4-trifluoromethoxy phenylacetic acid, similarly to examples 3 and 4, sex) 1 product in the form of a yellow resin.  The NMR spectrum shows a characteristic alkynyl proton in the form of a multiplet at about 2.52 and benzyl protrnes at 8 6.35.  Vychnsleno,%: C 69,22; H 4.95 Found. %: C 68.17; H 4.11. In a similar manner, hg of a tbnbenzo benzyl ester of Cc-isopropsh-1-4-difluoromethoxyphenylacetic acid are obtained using alcohol nb6-isoprosh-4-difluoromet.  hydroxyfex acetic acid.  Calculated: C 71.99; H 5.37 C2iH24F204 Found: C H 5.53 P and 1YGE p 26.  Preparation of (4) -6-shanovem hydroxybenzyl ester of (f) is ct-isopropyl-4-difluoromethoxyphenylacetic acid.  A warm solution (60 ° C) (-) - 2-phenylamine (4.96 g) in aqueous ethanol (60% ethanol, 20 ml) is added to a warm solution (60 C) of racemic acid (20 g) in aqueous ethanol ( 60% ethanol, 50 mp) with magnetic stirring.  Since the solution is allowed to cool slowly to room temperature, the salt precipitates as a white crystalline solid.  The mixture was left to stand overnight and the solids were collected by filtration, washed with aqueous ethanol (JO ml) and dried (9.5 g).  T.  square  184-188 seconds  The higher acid obtained from this salt has a rotation of ot J.  + 37.1 ° (CHCIj, C 1.439 g / 100 ml).  Two subsequent crystallizations of this salt from aqueous ethanol (60% ethanol) give white needles with tonnes.  square  185-187s, with oi being isopropyl-4-difluoromethoxyphenylacetic acid, which has a rotation of O + 40.4 ° (CHClj, C 1.353 g / 100 ml).  The selected (+) - acid is converted to an ester, similarly to Examples 3 and 4.  NMR (CDCCli) S 6.8-7.5 (m, 13H, aromatic H); 6.43 (t, J 74 Hz, 1H, OCHFj); 6.30 and 6.23, (23, W, CH-CN); 3.27 (o. , J W Hz, W, CH-CH (CH)).  I Example 27.  Preparation of (+) - (z6-Cyano1 of (+) and (-) - 0 -isopropyl-4-trifluoromethoxyphenyl acetic acid) metaphenoxybenzyl ester.  A mixture of racemic acid (26.2 g) and (-) - b6-phenethylamine (12.1 g) in aqueous ethanol (60% ethanol, 2 l) is heated until dissolved on a steam bath and allowed to slowly cool to room temperature.  The salt is collected by filtration and dried (16.9 g).  T.  square  189-193 C.  The salt is recrystallized twice from aqueous ethanol (60% ethanol, 1 l and 600 ml, respectively).  T.  square  194-19bs (8.0 g).  (+) - OC-isopropnl-4-trifluoromethoxyfenesoux) the acid is obtained by neutralizing the salt with dilute hydrochloric acid, followed by extraction with ether and evaporation of the solvent, ot 1: + 35.5 (СНС1), С 6.0 g / 100 ml) .  Using (+) - ot -isopropyl-4-trifluoromethoxyphenyl acetic acid, analogously to examples 3 and 5, the product is obtained in the form of a pale yellow oil: ctj5) 6.1 (CISC, C 5 g / 100 ml).  Example 28  Insecticidal activity.  The insecticidal activity of the proposed compounds was tested on the following insect species: tobacco caterpillar Heliotlus viresce (Fibr1cnus); Zapadna potato bar vadka Empoasca abrupta (Delong) and tl bean Aphis fabac (Skopoli).  Tobacco Budworm Heliotlus virescens (Fabricius).  The first age stage.  A cotton sprout with two loose leaves was lowered for 3 s while stirring in a solution (35% water and 65% acetone) containing 3 (S; 100 or 30 ppm of the test compound.  Each sheet was placed in a cup with a tampon and before closing the cup with a lid a piece of gauze infested with 50-100 larvae just added was added.  After 3 days  at 30 F and relative humidity of 50%.  In the study, the cups noted the death of the newly hatched castings.  The results are shown in Table.  3  T bean (Bean.  Aphid) Aphis fabac (Skadjuli). .  Five centimeter fiber pots, each containing a 2-inch-high nasturtium sprout and infected 2 days before with 100-150 aphids, were placed on a rotating table, turning at 4 rpm and sprayed with a solution (35% water w 65 % acetone) containing 100; ten; 1.0 and 0.1 ppm of the test compound for 2 vol,. using a Devibiss Atomizez sprayer and an air pressure of 20 pounds per day about 15 cm from plants.  The optic solution was directed in such a way as to completely cover the plant aphids.  Sprayed plants were placed on the respective winding sides of white enamelled blowers.  Mortality was assessed after one day at 70 F of 50% relative humidity.  The results are shown in Table.  3  West potato puller Empoasea abrupta (Delong).  Lima bean sprout with dissolved 3-4 inch primary leaves was immersed in a solution (35% water and 65% acetone) containing 100; 10 or 1 ppm of the test compound is connected; .  Submerged plants were placed in a ski cabinet to dry, and then cut off 2.5 cm of the tip of one sheet and placed in a 4-inch Petri dish with a damp filter paper on the bottom.  3-10 nymphs in the SECOND transformation stage were placed in a Pet {{cup], then the cup was closed.  Mortality.  evaluated after melting, prepared by melting in cups for 2 days at 80® F and 50% relative humidity.  The results are shown in Table. 3  In the experiments, permethrin was used as a standard or control.  Example 29  Insecticidal activity.  The proposed compounds are also active in relation to mosquito larvae, as well as to the ladybird Epilachna varivestis and the southern marching worm.  Malaria mosquito Anopheles quadrimaen- latus (S hey) 1 ml solution (35% water and 65%.  acetic acid) containing 300 ppm of the test compound was pipetted into a 400 ml beaker containing 250 ml of deionized water and mixed with a pipette to obtain a concentration of 1.2 ppm.  Equal parts of this solution were diluted to concentrations of 0.4; 0.04 and 0.004 ppm.  A ring of wax paper 0.6 cm wide was inserted into the beaker so that it floated on the surface of the test solution and did not allow the eggs to float along the meniscus curvature and dry at the edges of the beaker.  A gridled spoon was used to collect and transfer approximately 100 eggs (0-24 hours old) into a beaker.  After 2 days at 80 F and a relative humidity of 50%, incubation was observed.  The registered mortality rate is presented in table.  four.  Ladybug Ephilachha varivestis (M) w Seedlings of lima beans (2, in a pot) with primary leaves of 7.5 x 10 cm long were immersed in a test solution with a concentration of 300; 100; 10 or 1 ppm and placed in a hood for drying.  One sheet is separated.  They were removed from the plant and placed in a 10 cm Petri dish containing wet filter paper on the bottom and 10 larvae in the last age stage (13 days after hatching).  The next day after treatment, another leaf was separated from the plant and given to the larvae to be eaten after the remnants of the previous leaf were removed.  2 days after the treatment, the third leaf is given to the larvae to be eaten, as a rule, with more leaves; not required.  The fourth leaf is used on the third day after treatment in the event that: if the larvae have not finished eating.  The cups were kept until the adults hatched (usually, 9 days after the start of treatment).  Upon completion of the transformation, each cup was examined for the presence of dead larvae, pupae, or adult individuals, ugly. x pupae or adults; intermediate forms of larva-pupa or intermediate forms of pupae in an individual; or any deviations from the normal larva, the transformation or hatching of the pupa or adult.  The results are presented in Table.  four.  Southern marching worm Spodoptera eridama (Kramer).  Lima-bean seedlings with two loose primary leaves, 7.5–10 cm long, were immersed for 3 s with stirring in the treatment solutions and then placed in a scraper for drying.  Leaf after vys1khii cut off.  Each cut leaf was placed in a 10 cm Petri dish containing a piece of wet filter paper and 10 larvae of the southern marching worm in the third age stage approximately 1 cm long. The Petri dishes were closed and kept at 2 F at 80 F and 50% relative humidity.  The percentage of mortality was determined after 2 days. The results obtained are presented in Table.  four.  Example 30  Insecticide activity Mites spider two-spotted Tetranych usticae (Koch).  Lima-bean seedlings with three primary leaves, 7.5–10 cm long, were infected with 100 adult phosphate-resistant mites on one sheet 4 hours before the start of the experiment in order to allow egg laying before processing.  Infected plants were immersed for 3 s with stirring in a solution with endant 1000; 300; 100 or 10 ppm and then placed in a hood for drying.  After 2 d at 80 F, the mortality of adult ticks on one sheet was evaluated under a stereomicroscope with a magnification of 10 times.  Another leaf was left on the plant for another 5 days, and then examined at a magnification of 10 times, in order to estimate the death of the eggs and re-infiltrated. IX nymphs, while receiving a measure of ovicide (egg toxicity) and residual effect, respectively.  The results of experiments P {I1veshd in table.  five.  .  Tabachna kidney caterpillar, scoop Hel iotlus, virescens (Fabricius).  Third stage of age.  Three cotton sprouts with freshly dissolved seeds were immersed in a solution with a concentration of 1000 or 100 ppm and placed in a hood for drying.  After drying, each seed was cut in half and, together with 10 leaf slices, a plastic medical jar containing 1.25 cm of a dental tampon saturated with water was placed in 28 g, after which one larva of the renal suspenza was added at the third age.  The jar was closed and kept for 3 di at 80 F and a relative humidity of 50%, after which the death rate was calculated.  The results of the experiments are summarized in table.  five.  Scoop nor Trichoplusia ni (Eubier).  Third stage of age.  The leaves of a cotton plant were immersed in a solution containing 1000, 100, or JO ppm of the test compound, mixed for 3 seconds, and dried in a hood.  After drying, the sheet was placed in a 9.0 cm Petri dish with wet filter paper at the bottom.  Ten larvae were added in the third age stage and the cups were closed.  The percentage of mortality was podstatyvali after 3 days at 80 F (26.7 C) and a relative humidity of 50 + 10%.  The results are summarized in table.  five.  Example 31  Soil insecticidal activity.  South eleven-point flea Diabrov, tica undecimpunetate howardi (Barber).  10 mg of the compound was diluted to 10 ml of ace-.  tone to prepare the initial solution A.  2 ml of this solution was then diluted to 10 ml with acetone to obtain solution B.  An example of 0.7 g of talcum powder (Rugs ABB) was placed in a 28 g long-necked jar and 1.25 ml of solution was added to the talcum powder.  1.25 ml of solution A - 56 kg / ha.  1.25 ml of solution B - 11.2 kg / a.  The test solution was mixed with talc to moisten it evenly before drying and in an air drier for 10-15 minutes.  25 ml of moist sterile potted soil and approximately 0.6 g of dried grains (food for larvae) were then added to jars containing the test compound.  The cans were closed and the contents were mixed on a vibration mixer.  Each jar was placed in 10 larvae of the southern eleven-point flea, which age is 6-8 days.  The cans were tightly closed and stored under HSRr (26.7 ° C), 50% relative humidity and constant illumination.  The mortality rate was calculated after 6 days.  In this experiment on (-cyanb-metaphenoxybenzyl ester of isoprosh-4-trifluoromethoxyphenylacetic acid, it provided 100% mortality of the southern one-spot flea at 56 kg / ha and 70% mortality at 11.2 kg / ha.  Example 32  Residual insecticidal activity obtained by treating cotton leaves.  Young cotton plants with less than two leaves, grown in 10 cm plastic peas, were immersed for 3 seconds in a solution (65% acetone and 35% water) containing 30; 100; 300 or 900 ppm.  active ingredient.  After drying and the leaves, two sheets from each plant were cut and placed in Petri dishes (90 x 10 mm) on wet filter paper (9 cm drawing paper No. 1).  Five 35 tobacco kidney larvae in the third age stage were placed on each sheet and Petri dishes were closed.  Infected cups were then stored under constant illumination, 80 ° F and 50% relative humidity.  Counting larvae produced in 72 hours  The rest of the plants were placed under high-intensity lighting conditions in a greenhouse adapted to provide 14 light.  h / d  Leaf samples were tested with tobacco buds in the third. age stage through 3J 7; 10 and 14 days stay in the greenhouse.  The results are shown in Table.  6  Example 33  Ixodicidal activity (against ticks).  The larva of the single farm of the Ixodes tick, Boophilus microplus, which can remain in a single host during its three stages of life (larvae, nymph and adult).  Used solution (10%.  acetone and 90% water) containing 0.025; 0.1; 0.5; 2.5 or 12.5 ppm of the test compound, 20 by a larva, were put into a pipette, closed at one end with a porous material.  The solution containing the test compound was injected through a pipette with a vacuum tube with a hose, whereby the spray system was simulated.  Ticks were kept for 48 hours at room temperature and the percentage of mortality was determined.  The experiments were repeated at a concentration of the test compound of 0.1; 0.25; 0.005 or 0.001; 0.1; 0.01; 0.001; 0.0001 or 0.00001; and 100 ppm.  The results of the experiments are given in table.  7  In tab.  8 shows the ixodicidal activity of the compound with various radicals at the indicated concentration.  Example 34  The effectiveness of the proposed compound control of adult Ixodes ticks of Boophilus microplus was also determined in the following experiments, in which solutions containing 125 were used; 52.6; 31.2, 15.6 or 7.3 ppm of the test compound.  Adult blood tied females were loaded into the test solution for 3 s, placed in separate containers and kept for 48 hours at 80 F and 50% relative humidity. At the end of the drying period, the ticks were examined and the number of eggs deposited was counted.  Eggs were then left for incubation and cohesive results expressed as a percentage reduction in the number of viable eggs.  Blood is poured on females who have not laid aside their eggs,. h} 1 they are dead.  82 The results are shown in Table.  9 and 10.  Example 35  The efficacy of the proposed compounds for controlling the larvae of the Cah Note I and Hominivorux fly fly is a harmful insect for livestock.  Cochliomyia hominivorux larvae received a mixture of crushed meat (8.0 g), blood (7.0 ml), (2.1 ml) and a solution (0.9 ml) containing 1.5 or 25 ppm of the test compound.  Conducted two experiments on 20 larvae at each dose value.  The larvae were allowed to feed their fill on the formulated medium for 24 hours, after which the number of dead larvae was determined for each composition in each repeated experiment.  The results are presented in Table.  eleven.  Example 36, Determination of the concentration of the test compounds, resulting in the death of 50% of the tobacco larvae of the Heliotlus virescans scoop on cotton.  Young cotton sprouts with at least two loose leaves, grown in 10 cm plastic pots, were immersed under stirring in a 3rd solution (65% acetone and 35% water) containing 1.1; 2.8; 7.5; 20; 60 or 150 ppm of active ingredient.  After drying, two sheets were cut from each plant and placed in Petri dishes (90x10 mm) on wet filter paper (9 cm drawing paper No. 1).  Five tobacco kidney larvae in the third age stage were placed on each sheet and the petri dishes were closed.  Infected cups were stored under continuous illumination, 80p (26.7 ° C) and 50% relative humidity.  Counting larvae produced in 72 hours  Each process was repeated four times; The results are summarized in table.  12.  As the view from the table.  12 of the proposed compounds are 2–5 times more effective for controlling tobacco buds than the known compounds 1 tested in this experiment, Example 37.  Determination of the concentrations of the test compounds, resulting in the death of 50% of the adult mosquitoes.  Anopheles quatrimaculatus (Sy).  For aerosol application, insecticidal solutions were transferred with a pipette (0.15 ml) into the upper part of the nozzle and passed through a spray nozzle.  The droplets were re-energized by the air flow (4 mph) to the mosquitoes in the cage (25 adult females per cage) with an exposition of 4–5 s.  3710 Then the mosquitoes were leached (3-4s) with carbon dioxide and transferred to cages.  Cages with treated mosquitoes were stored at 85 + 1 and relative humidity 46. t 2%.  The mortality rate was calculated after 24 hours.  The results are shown in Table.  1 As can be seen from Table.  13 suggested connections are 4 times more effective for dl. fight with  older mosquitoes Anopheles guatripi aculatu than the famous fj.  Example 38  Residual insecticidal activity, determined by the low-volume deposition of the test compounds.  The compounds under study were dispersed in mixtures of 65% acetone and 35% water in sufficient quantities in order to obtain 0.08 kg / ha of compound in 19.3 L of water.  The cotton sprouts were then placed in a spraying chamber and sprayed with an upper moving sprinkler, while the sprouts passing under it.  After drying, two sheets were cut from each of the two plants and placed in a tea-pot Pet | t (90 x 10 mm) on wet filter paper (9 cm paper number 1).  Five tobacco brooch larvae scoops Heliothis virescens In the third age stage, each leaf was placed and the petri dishes were closed.  Infected cups are stored in continuous light and at a relative humidity of 50%.   - - -.  - Counting larvae produced after 72 h.  The remaining plants were placed under high-intensity lighting conditions in a greenhouse.  Leaf samples were biologically tested with tobacco kidney larvae in the third age stage through 3; 7; 10 and 14 days  The best results n | in the table. 14 C p and me 39.  Ixodicidal activity.  : Analogously to Example 33, the ixodicidal activity of the proposed compounds was determined at a concentration of 12.5; 2.5; 0.5; 0,1,0,02 or 0,004 ppm.  The results are summarized in table.  15.   . .  Example 40  The effectiveness of the proposed compounds for the control of adult moths of the tick mites Rhipicephalus sanquins (R.  S. ) and Dermacentor ver rabi1 is (D. V. a) dogs were determined, the test substance according to example 33 with a concentration of 100, 10 or 1 ppm.  Adult blood-filled female ticks were immersed in the test solutions for 3 s, placed in separate containers and kept for 48 h.  at and relative humidity of 50%.  At the end of the period, ticks were examined and the number of deposited eggs was counted.  They blame blood sam2 mok who have not laid aside their eggs, they consider you yours.  The results are shown in Table. sixteen.  Example 41  Adult cat flea Ctenopephalites fel is in vitro.  10 adult cat fleas of the Ctenocep-halites fetis species were sprayed for 30 seconds with a solution (acetone / water) containing 100, 50, 10 or 1 ppm of the test compound, and then kept at 48 hours at room temperature and 80% relative humidity; After 24 hours and 48 hours, fleas were examined and mortality was calculated.  noj emoiie results are presented in table.  17  The experiment was repeated with the coiccentric Hccnejdye of my compound 80; 40; 20; ten; 5 or 2.5 ppm.  Reductions are the average overlap of two repeated experiments with each.  concentrations and lead to table.  18.  Example 42  The ixodiotic activity of the compounds proposed was determined in analogy to example 40 prt concentration 1.0; 0.1; 0.01 or 0.001% of the active ingredient.  The mortality rates were calculated after 24 hours and 48 hours after treatment.  The results are shown in Ta &amp; i. l9 (a series of two experiments).  pr meper 43.  Effectiveness of predlagaejv; t -. . . -. -.  jii. . ". -my compounds for the fight against dew Musca antumnalis.  One-day wilderness flies fed on the bark.  remove manure "with a treated solution containing 0.13; 0.25 mln 0.50 ppm investigated for compound.  About the results (d d t for two opgam, is; benefit; at the same time, 10 larvae for each concentration.  An acetone solution of the appropriate amount of the test compound was added to 1 kg of fresh cow manure and mixed for 1 min with an electric stirrer.  An avos used for control experiments was treated similarly, but only acetone was added.  Manure samples are divided into 4 paper cups.  (For each concentration value and for control experiments).  Two glasses were infected with one-day fly larvae.  The glasses were kept for 7 di at 80 and relative humidity of 50%.  Then the glasses were examined for the presence of pupae.  The pupae were counted, weighed and pressed into plastic pro &amp; fki, where they hatched and died.  The results are shown in Table.  20 (average of two experiments).
    39
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    权利要求:
    Claims (1)
    [1]
    ; 2-haloalkyl (oxy-, thio-, sulfinyl * or. Sulfonyl) phenylalkanoic acids of the general form X — Y and Z are in the metal or in the ηαρα position with respect to the carbon atom to which the alkanoic acid ester group is attached;
    X is O, S, SO or SO ^;
    Y and Z — individually H, Cl, F, Br, NOg, CH, or OCH <j;
    - H, F, Cl, CHFfl HJraCfy “
    - ethyl ', i-propyl, isopropyl, isopropyl or tert-butyl;
    R3 is H, CN or-C = CH;
    R4 - H, F, C1, ^ CH, or OCH |, .li (£> optical isomers, provided that Y and Z is hydrogen, R f -ί H or F; .X - O or S; Eg- ethyl , i-propyl or 'isopropyl, exhibiting insecticidal and ixodicidal activity ;
    Priority by signs:
    * 01.10.76 at X — S or / O; 1C - H or F;
    R g is ethyl, propyl or isopropyl; R- j is H, CN or C »CHu r 4 is H, F, C1, CH- or OCHj.
    07/11/77 at XS ^ O, SO or SO 3 ; Z and YH, CT, F, Br, NO 2 , CH 3 or OCHj; R I ~ H, Cl, F, CHFg or CF ; R g is ethyl, propyl, isopropyl, 7-butyl or isopropenyl; R 3-H, CN or -C = CH; R 4 ~ H, F, C1, CHjj or OCHj.
    S and ..., 1082782
    The invention relates to the synthesis of biologically active chemical compounds, in particular metaphenoxybenzyl or ob-cyano-metaphenoxybenzyl esters of 2haloalkyl (hydroxy Thio-, sulfinyl- or 5
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    SU1082782A1|1984-03-30|Beta-phenoxybenzylling condensatiobeta-phenoxybenzoyl esters of 2-haloalkyl | phenylalkanic acids having insecticidal and ixocidal effect 2-hydroxy-3-n,n-|aminomethyl-5-tert-butyl-phenylnonyl sulfide as inhibitor of hydrogen sulfide corrosion of steel
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    US4039635A|1977-08-02|Soil fungicidal phosphorothioate
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    同族专利:
    公开号 | 公开日
    IL52973A|1983-10-31|
    BG28695A4|1980-06-16|
    DK434777A|1978-04-02|
    GB1604875A|1981-12-16|
    BG28238A3|1980-03-25|
    DE2743416A1|1978-04-06|
    GR72107B|1983-09-14|
    GB1596903A|1981-09-03|
    CH638774A5|1983-10-14|
    PL114067B1|1981-01-31|
    YU40906B|1986-08-31|
    YU233577A|1983-02-28|
    TR22094A|1986-04-02|
    GB1582775A|1981-01-14|
    JPS5344540A|1978-04-21|
    BR7706474A|1978-06-06|
    PL201198A1|1980-02-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2450517C2|2006-05-17|2012-05-20|Байер Кропсайенс Аг|Paper saturated with insecticidal substances|
    GR74446B|1978-03-20|1984-06-28|American Cyanamid Co|
    DE2837524A1|1978-08-28|1980-03-20|Bayer Ag|Phenylacetic acid ester derivs. from pyrethroid alcohol - useful as insecticides and acaricides, and new intermediates|
    US4284643A|1978-08-28|1981-08-18|Bayer Aktiengesellschaft|Combating arthropods with novel fluorine-containing phenylacetic acid esters|
    JPS56133253A|1980-03-24|1981-10-19|Sumitomo Chem Co Ltd|Optical isomer of cyanohydrin ester, its production and insecticide and acaricide containing the same as effective ingredient|
    JPS60174599U|1984-04-27|1985-11-19|
    JPH04720Y2|1984-10-24|1992-01-10|
    JPS6174399U|1984-10-24|1986-05-20|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US72881776A| true| 1976-10-01|1976-10-01|
    US72881876A| true| 1976-10-01|1976-10-01|
    US81460077A| true| 1977-07-11|1977-07-11|
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