CS270008B1 - Addition Compounds of 2,2-Dimethyl-3- (2,2-dihydro-cyclopropanecarboxylic acid) - Google Patents

Abstract

Addition compounds of 2,2-dimethyl-3- -/2; 2 '-dihalovinyl/cyclopropanecarboxylic acids of the general formula III /lRcis-I/ . /TScis-I/ . /11/, where the component /lRcis-I/ means 2,2-dimethyl 1-3/2', 2Ldihalovinyl/cyclopropanecarboxylic acid of the general formula I in the lRcis configuration, where X means halogen and the component /lScis-I/' means the acid of the general formula I in the lScis configuration, where X means halogen and /11/ is an aromatic compound, where A is a hydrogen atom, methyl or halogen and Y is a group -CH=CH-, oxygen, sulfur or -NH- group,. are in a molar ratio of 1:1:1, are important intermediates in the production of insecticides. The method of their preparation consists in that n^ sqēs of stereoisomers of 2,2-dimethyl-3-/2,2-dihalovinyl-cyclopropanecarboxylic acid of general formula I, where X has the meaning given above, in the configuration 1Rcis and 1Scis, or in the presence of its other stereoisomers, react with an aromatic compound of general formula II, where A and Y have the meaning given above, in the temperature range -20 to 80 °C.

Description

The present invention relates to publishing compounds which are composed of one molar equivalent of 2,2-dichloro-3- (2,2'-dichloroinyl) cyclopropenecarboxylic acid of the general formula wherein X is halogen in the absolute configuration and only one molar equivalent of the acidic acid of formula X in the absolute configuration and of one aeol equivalent of an aroaetic compound of formula II, wherein A is hydrogen, methyl or halogen and Y is -CH2CH2-sulfur, sulfur or -NH-group. III '/ IRclé-I /.

The addition eloučonins of formula III are novel eloučonins; which Izo use in the eynthesis of insecticides. They arise, * in kryetelioké forot; pAeobonia aroaEetic compounds of the general formula II not a mixture of etorooiomoMorAj 2, ^r 2-diaethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acids of the general formula I, provided that the amino acids IRcie-I and iScls-1 are present in this invention. of a non-basic organic solvent, in a wide temperature range, preferably an inlet in the range of -20 to 80 ° C. At the same time, no other crystalline edema compounds of the formulas I t II, other than eo compounds of the formula III etereoieomornia or etechiomotric components, ^{1 are} formed under the stated conditions.

The composition of the addition compounds of the general formula III has been shown to be customary. analytical and physico-chemical procedures; including ·! η! · ο other NMR and iC epectroscopy.

Decomposition of the eyepiece compound of formula III can be determined by the racemic cell of kyeolin of formula i; this is the okviaolar eaee etoreoieomers of IRcie-I or IScie-I, in quantitative yield. Decomposition Izo perform various ·! about oneself known procedures · including ·! for example heating and vacuum.

Eyebrow III addition compounds are important intermediates in the eynthesis of highly insecticides. Due to the fact that the method of their preparation is highly effective, their method of preparation for the separation of vigorous ethereal compounds uses the formulas of the general formula (1) which are an inecticidal substance.

Processes for the preparation of the eyebrows of formula III and their use in the preparation of the various stereoisomeric acids of formula I are further illustrated in the following examples, which, however, do not limit the scope of the invention in any way.

Example 1

Cie-peraethrin / lRScic-I recyclic acid adduct X · C1 / a fluorobenzone / IIj Y · -CHaCH-í A «F / g The racemic acid cie-permethrin was dissolved from the boiling in 2 · 1 fluorobenzene and after cooling the ship, crystallized crystals were precipitated. 1.13 g were obtained. eyebrow addition compounds III; wherein the components IRcie-Ij 18cie-I e II Mjl are as defined above / 92% yield; calculated not starting acid / · The composition of the adduct was ethanated by NMR epotrocopies ·

NMR (COClg) t 1/26 e / 6 HJ 2 CH ₃ / 1/7 to 2J3 and (2HJ cyclopropane); 6.2 d / 1H; -CH-CCyl »10.91 ba / 1 Hj -CO 3

Example 2

Adduct of Racoal cio-poraothrine cyeeline / IRScie-I »X-Cl / and pyrrole / II। Y · A-H / 0/5 g of racoalcic ceperaethrin cyeeline was dissolved from the heat in 1 .mu.l of pyrrole;

after cooling, the precipitated crystals were removed with a mixture of pyrol compounds. 0.475 g of the adduct of eyebrow formula III was obtained; wherein the components 1Rcie-i; Scle-I and II aaji the meaning of ehora given / 80% of theory; calculated on the starting kyeolin.

NMR (COCl ₃ ) 1/27 e / 6 H; 2 CH 2 /j 1, 7 to 2J3 and / 2 H; cyclopropane / i 6/2 d / 1 H, 1'-CH-CCl ₂ /} 10.91 be / 1 H; -CO ₂ H)} 6/15 to 6/38 and / 1 H, * pyrrole (6), * 68 to 6.92 (1 H, pyrrole).

CS 270 008 Bl

Example 3

Racic acid cis-2; 2-dimethyl-3- (2 (2-dibronovinyl) cyclopropenecarboxylic acid adduct) IRScle-I; X-Br) and benzene (II and Y- -CH-CH-, 'A-H)

0.5 g of the acid of the formula I as defined above was dissolved in 1 * 1 of benzene from the heat. After cooling, the precipitated crystals were removed and their composition was determined by NMR spectrocopy.

NMR (COCl 2) 1; 6.72 d / 1H; -CH ₂ CBr 2 /: 7/32 e / 3 H / aro *. /.

Example 4

Separation of the IRcie ieoaer of cie-pormethrinic acid IRcia-Ij X-Cl (from the assigned racemic pair -IRScie-Ij X-Cl) according to the adduct e benzene *

36/3 g of levorotatory pernetrine cyanobacterium, ⁷ D- -9.8 ° (CHCl ₃ ) were dissolved in 44 * 1 benzene at reflux and the solution was cooled in ice with stirring. The precipitated adduct was filtered off with suction, washed with chilled benzene and quenched by heating under vacuum (80 DEG for 24 hours) to give 21.6 g of racemic ciacyanine. From intoxicated inert liquor was evaporated, yielding 13 *, 1 g of the optically active CIE kyeeliny 1 / O · -27 / 22 ° / CHC1 _O /.

Example 5

The procedure was the same as in Example 4, and 36% of pure benzene was used. 24/4 g of a crystalline adduct of racetic acid and thiophene were obtained, the ternic decomposition of which gave 20 g of racemic cis-keelin of the general formula I according to Example 4. Evaporation of the filtrate gave 14/6 g of optically active keelin. 0-29 (17 ° (CHCl 3)).

Example 6

Separation of cle- and trens-pernetic acid / cis- and trane-I; X-Cl / adduct and benzene *.

9; 93 g of racemic cle- e e-transelioners of pernethrinic acid (18% of the trieneone) were dissolved in 30 ml of thiophene from heat and, after cooling in January, the precipitated crystals were filtered off with suction. Decomposition of the starting material was obtained with 7/98 g of a recene cle-acid of the formula I in which X-Cl (98% of theory, calculated on the cis-isoner content of the starting material); which contained less than 1% of trans-ioner.

Example 7

The procedure of Example 6 was followed, but no thiophene of 2-methylfuran was used. Decomposition of the starting material gave cis-psrmsthrinic acid (68% of theory) containing less than 2% of the trans-isomer.

Example 8

The adduct of racemic ces-pernethrin acid (IRScie-Ij X-Cl) with furan (IIt Υ-O-> AH) 2/98 g of racemic pernethrin acid containing 90% cis- and 10% trans-acid was dissolved in 4 nl of ether / the solution was cooled with ice and 1.1 ml of furan was added. After 1/2 hour, the crystalline product was filtered off and washed with cooled ether-furan 2 t 3. 1/07 g of the adduct of the general formula 111 was obtained, which corresponds to 34% of the cie-isomer in the starting mixture. According to gas chromatography, the crystalline adduct contains only traces of trans-acid.

Claims (2)

OBJECT OF THE INVENTION 2. 2/2-Diethyl-3- (2,2 / adihalovinyl) cyclopropanecarboxylic acid addition compounds of the general formula III CS 270 008 B1 (Rcie-I). / IScie-I /. / 11 / / 111 / kd · ingredient by / lRcis I / zněměné 2, ^t 2 diaathyl-3/2, 2-dlhalovinyl / kyaelinu cyclopropanecarboxylic acid of formula I the configuration IrCl wherein X represents a halogen component and / IScis- I) represents a kyaline of the general formula I in the IScle configuration (where X is halogen and (11) is an aromatic alumina, where A is a hydrogen atom, methyl or halogen and Y is a group -CH 2 CH-, oxygen, iron or -NH acupine, the individual components being in a molar ratio of 1: 1: 1. 2. A process for the preparation of compound compounds of the general formula III wherein X and Y o A of the formulas I and II are as defined above according to item 1, characterized in that they are not a mixture of etheromers of 2,2-diethyl-3- (2); dihelovinylcyclopropanecarboxylic acids of formula i; wherein x has the meaning given above (in the IRole and 1 Sele configuration, optionally in the presence of its other ethers) is treated with an aromatic compound of formula II (wherein A and Y have the above meaning) in the temperature range -20 to 80 ° C,