Method of producing isomeric sustituted cyclopropanecarboxalic acids or their functional derivatives

专利摘要:
The invention relates to the method of preparation of the isomeric substituted cyclopropancarbonic acids or their functional derivatives that can be used as the remedies actioned on the weeds, detriments on insects and parasites in agriculture.The purpose of the invention is widening the class of such compounds.The method forsees the preparation of new substituted isomeric cyclopropancarbonic acids of general formulawherein X1 - atom hydrogen, fluorine, chlorine or bromide, X2 - coincided with X1 or unlike and present itself atom of fluorine, chlorine or bromine, X3 - atom of chlorine. bromine or iodine; Z - hydroxyl, halogen or esteric group IR, wherein R either benzylic radical that can be substituted by one or some radicals selected from group: alcyl C1-C4 alkenyl C2-C6, oxyalkenyl C2-C6, alkidienil C4-C8, dioxymethylen, benzyl, or halogen or group of formula IIwherein R1 - atom hydrogen or methyl; R2 - phenyl or group -C2-CşCH, mainly methylfuryl, or group of formula IIIwherein R3 - vinyl, propen-1-il, buta-1,3-dienil, or buten-1-il or group of formula IVwherein R4 - atom of hydrogen, nitrilic or ethinilic group; R5 - atom of chlorine or methyl; n-number egual 0,1 or 2 mainly 3-phenoxybenzilic, X - ciano-3-phenoxybenzilic or L-ethynil-3-phenoxybenzilic group or group of formula Vwherein R6, R7, R8, R9 - hydrogen, atom of chlorine or methyl; S/1-phenyl or dihydro or tetrahydrophenyl by interaction of compound of general formula VIwherein X1, X2 and X have mentioned values with chlorining, bromining, iodining reagent on the double bond as which can be used chlorine, bromine or iodine.
公开号:SU858559A3
申请号:SU772522552
申请日:1977-09-15
公开日:1981-08-23
发明作者:Мартель Жак；Тессье Жан；Демут Жан-Пьер
申请人:Руссель-Юклаф (Фирма)；
IPC主号:

专利说明:

methyl 3,4,5,6-tetra-raphidrophthalimide pan-1-carboxylate. 21.1 "-trans-2,2-dimethyl-3- (2 2-dichloro-1, 2-dibromoethyl) -cyclopropane -1-carboxylate 5-benzyl-3-methylfuryl. 22. IK-trans-2,2-Dimethyl-3- (2,2-dibrrm-, 2-dichloroethyl) -cyclopropane -1-carboxylate 5 -allethrolone. 23.1 K-cis-2, 2-Dimethyl-3- (2, 2-difluoro-1J 2-dibromoethyl) -cyclopropane-1-carboxylate s-tcyano-s-phenoxybenzyl. 24 I K- | Trans-2, 2-Dimethyl-Z- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane -1-caroxylate 3-phenrxivenzyl. 25. (K-trans-2,2-Dimethyl-3- (2,2-difluoro-1i2-dibromoethyl) -cyclopropane -1-carboxylate cs -ob-cyano-3-phenox benzyl. 26.tK-cis-2.2 -Dimethyl-3-Rsl-2-fluoro-2-chloro 2,1-dibromoethyl) -cyclopropane-1-carboxylate 3-phenoxybenzyl. Obtained by the proposed method, acids or hydroxyanhydrides can, if necessary, be esterified with appropriate alcohols in the presence of a catalyst. The halohydroxyconducting process is usually carried out in an inert solvent, such as acetic acid, carbon tetrachloride, chloroform, and milene chloride. Obtaining substances described by the General formula 1. Example 1. S-ci-Cyano-Stphenoxybenzyl ester (K-cis-2,2-dimethyl-3- (l, 2, 2, 2-tetrabromoethyl) -cyclopan-1-carbon acids (isomers A and b). 7.57 g of S-ot-Cyano-3-phenoxy-benzyl ester tR-cis-2,2-dimethyl-3- (2, 2-dibromvinyl) - are dissolved in 100 ml of carbon tetrachloride. cyclopropane -l-carboxylic acid, add 2.4 g of bromine in solution in 15 ml of tetrachloromethane, shake for 45 min at 20 ° C, concentrate to dryness under reduced pressure, separate the components of the residue (10 g) by silica gel chromatography eluir from a mixture of 1: 1 benzene and petroleum ether (T c 35-75 C) and isomer A is first obtained (4.12 g and then isomer B (4 g) S-ot-cyano-3 -phenoxybenzyl ester 1H-cis- 2, -dimethyl-3-l, 2, 2, 2-tetrabromoethyl-cyclopropane-1-carboxylic acid. Isomer A has the following characteristics. IC // P-53С (with 0.5% benzene). Analysis: S.-N. "In Gd NO:} (665,037). Calculated,%: C 39.73; H 2.88; Br 48.06; N 2.11. Found,%: C 39.9; H2.9; In g I N 2.1. ICB (chloroform) and NMR confirm the structure of the named ester. NMR spectrum. Peak at 1.25-1.33 hours / million methyl radicals in position 2 “cyclopropane); peak at 1.75 2, 17 ppm. (hydrogens in positions 1 and 3 of cyclopropane); peak 5.195, 55 ppm (hydrogen at position 1 of the side chain),;, peak at 6.38 ppm. (basil hydrogen); peaks from 6.91 to 7.59 h / ppm, corresponding to the hydrogens of the aromatic region. Isomer A is the most mobile in thin layer chromatography. Circular dichroism (dioxane). l -3 at 224 mmk; A € - 4.5 at 237 MMK; D - 0.05 with 290 MMK. Isomer B has the following characteristics. +111 С (with 0.6%,. Benzene). Analysis: NO, (665, 037). Calculated,%: C 39.73; H 2.88; Br 48.06; N 2.11. Found,%: C 39.8; H 3.0; Br 48, 48; N 2.0. The X (chloroform) and NMR confirms the structure of the indicated ester. NMR spectrum. Peaks at 1.24-1.40 h / mln. (methyl radicals in the 2-cyclopropane position); peaks from 1.83 to 2.25 ppm (hydrogens in the 1- and 2-cyclopropane position); peaks at 3.98-5.20 ppm (hydrogen at position l of the side chain); peak at 6.39 ppm (benzyl hydrogen); peaks from 6.92 to 7.52 ppm, corresponding to the aromatic hydrogens. Isomer B is the least mobile in thin layer chromatography. Circular dichroism (dioxane). l s-4,7 at 223 MMKJ - 4,2 at 247 MMK. Example i. S-ot-Cyano-3-phenoxybenzyl ester I p-11 s-2, 2-dimethyl-3- (2, 2-DICHLOR-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid (Isomers A and B). 17.06 g of 5-o-cyano-3-phenoxy-benzyl IK-cis-2,2-dimethyl-3- (2, 2-dichl-Orvinyl) -cyclopropane-1-carboxylic acid are dissolved in 200 ml of carbon tetrachloride, 6 55 g of bromine in solution in 20 ml of carbon tetrachloride and for about 10 minutes, shaken for 48 hours, concentrated to dryness by distillation under reduced pressure, and the components of the crude residue (23.8 g) are separated by chromatography on a sample gel, eluting with benzene - cyclohexane (7: 3), and get 10.4 g of isomer A (the most mobile during chromatography in a thin layer) and 10 g of isomer B (the least mobile n and thin layer chromatography) 5- cyano-3-phenoxybenzyl ester .vogo I K: iis-2,2-dimethyl-3- C2, 2-dichloro-1, 2-dibromoethyl J-cyclopropane-1-carboxylic acid. Isomer A has the following characteristics. - 61 ° С (with 0.5% benzene). Analysis: C1, „N.„ Br9 CljNO (576.125). Calculated; C45.85; NZ, 3; Br 27.74; Ct 12.3; N 2.4. Found,%: C45.8; H3.3; Br 27.7; d 12.3; N 2.3 X-ray (chloroform) and NMR confirms the structure of the indicated ester. NMR spectrum. Peaks at 1.29.1, 37 ppm (hydrogens of cyclopropane doubles); peak at about 2.05 ppm (hydrogens in the positions of the 1st 3-cyclopropane); peaks at 5.20 5.29-5.37-5.45 ppm (hydrogen, attached to an asymmetric carbon de side chain); peak at 6.45 ppm / ml (benzyl hydrogen); peaks from 7.0 d 7.6ch./million (hydrogens of aromatic der). Circular dichroism (dioxane). l 6 -3 at 221 MMK (kink); d +0, at 289 mmk (max.). Isomer B has the following characteristics. /ot/.p + (with 1%, in benzene). Analysis: ,,, (576,125). Calculated,%: C 45.86; H 3.3; Br, 7; cr 12.3; N 2.4. Found,%: C46.2; H3.4; Br 27.6; C 12.2; N 2.3. IKS and NMR confirm the structure of the said ester. NMR spectrum. Peaks at 1.25-1.38 parts / ml (hydrogens of cycloproducts doubled methyl); peaks from 1.87 to 2.3 ppm (hydrogens at the 2- and 3-cyclo propane positions); peaks at 4, 97-5, 01-5, 115, 16 ppm hydrogen asymmetric carbon side chain); peak at 6.46 ppm (benzyl hydrogen); peaks from .7 to 7.67 ppm (hydrogens of aromatic der). Circular dichroism (dioxane) .L +9 at 220-221 MMK (max};, 23 at 289 mmk (max). Example 3. 5-o-Cyano-3-phenoxybenzyl ester IK-cis-2,2-dimethyl-3 - 11, 2, 2, 2-tetrabromoethyl-1-cyclopropane-1-carboxylic acid. Step A. IK-cis-2,2-Dimethyl-3-ir 2, 2, 2-tetrabromoethyl-cyclopropane-1-carboxylic acid. -ISO ml of carbon tetrachloride were added 19.4 g of I K-cis-2,2-dimethyl-3- (2, 2 | dibromovinyl) -cyclopropane-1-carbonic acid, 10.4 g of bromine was added in a solution of 22 ml of carbon tetrachloride, shake for 1 hour at 20 ° C, concentrate to dryness by distillation under reduced pressure and obtain 31.4 crude product (T 145 ° C). This crude product is recrystallized in 110 ml of methane tetrachloride to obtain 22.12 g of 1Н-cis-2,2-dimethyl-3- (1, 2, 2, 2 tetrabromoethyl) -cyclopropan-1 -carboxylic acid. ISOC. This product is a mixture of isomers A and B, which is detected by an NMR spectrum, which allows to detect a compound (corresponding to approximately 2/3 of the mixture) that exhibits peaks at 1.31-1.43 hours. / million, corresponding to the hydrogen of doubled methyls, and peaks from 5.33 to 5.66 ppm, corresponding to hydrogen on monobrominated asymmetric carbon, and another compound ( corresponding to about 1/3 of the mixture), giving peaks at 1.28-1.48 ppm, corresponding to the hydrogen of doubled methyls and peaks from 4.24 to 5.34 ppm, corresponding to hydrogen on monobrominated, asymmetric carbon. In addition, the mixture gives peaks from 1.67 to 2.17 ppm (the hydrogens in the 1- and 3-cyclopropane positions) and a peak of about 11.25 ppm. (acidic mobile hydrogen). The analysis of the mixture obtained (MP 150 ° C) is as follows: C H Br 4 O, (457, 804). Calculated,% C 20.99; H 2.20; Br 69.82. Found,%: C 20.9; H 2.2; Vg 70.2. Stage B. 1K-cis-2,2-dimethyl-3-d, 2, 2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid chloride. In 179 ml of petroleum ether (Tr, d 35-75s), 0.2 ml of dimethylformamide, 8.5 ml of thionyl chloride are introduced, the mixture is heated with a Reverse cooler, 35.76 g of IK-cis-2.2- dimethyl-3- (1,2,2 2-tetrabromoethyl) cyclopropane-1-carboxylic acid in 150 ml of methylene chloride, shaken with heating for 2 hours under reflux, then cool, dry and concentrate by distillation, add toluene, again concentrated to dryness by distillation under reduced pressure and get 38 g of crude acid chloride (T l 88c), which is used in the next herd and. Step B. S-oi-Cyano-3-phenoxybenzyl ester IB-cis-2,2-dimethyl-3- (l, 2, 2, 2-tetrabromoyl) -cyclopropane-1-carboxylic acid. 7.5 ml of pyridine is introduced into a solution of 18.4 g of Sc-cyano-3-phenoxybenzyl alcohol in 100 ml of benzene, and then at 10 ° C in an inert atmosphere the 38 g of crude acid chloride obtained in step B is stirred for 15 hours at 20 ° C, water is added, shaken, the organic layer is separated by decantation, extracted with benzene, washed with water, benzene layers, and then with sodium bicarbonate, water, normal hydrochloric acid, water, dried, concentrated by distillation under reduced pressure, purified residue by chromatography on silica gel and floor 5-c / -cyano-3-phenoxybenzyl ester IR-uHc-2,2-dimethyl-3- (1, 2, 2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid as a mixture of measures A and B Similarly to the previous example number 1, the compounds described in the following examples are prepared. Example 4. I $ -.- Cyano-3-fen IK-trans-2,2-dimethyl 3- (1 2, 2, 2-tetrabromoethyl) cyclopropane-1-carboxylic acid oxybenzyl ester. This compound receives the action of bromine on K5 -, - cyano-3-phenoxybenzyl ester IK-trans-2,2-dimethyl-3- (22-dibromovinyl) -cyclopropane-1-carboxylic acid. A mixture of isomers A and B is obtained. IR spectrum (chloroform). Absorbance at 1740, 1586 and 1485 cm. NMR spectrum. Peaks at 1.20-1.261, 35 ppm (methyls hydrogen at the position of 2-cyclopropane); peaks at 4.3-4.48-4.67 ppm (hydrogen in 1 ethyl chain in the 3-cyclopropane position); peak at 6.48 ppm. (hydrogen on the same carbon as CSN); peaks from 6.97 to 7.17 ppm (hydrogens of aromatic der). Example 5. RS -ct-Cyano-3-phenoxybenzyl ester of 1-trans-2,2 dimethyl-3- (2j 2-dichloro-1,2-dibromoethyl) -cycl6propan-1-carboxylic acid. This compound is prepared by brominating K5 -.- cyano-3-phenoxybenzyl IK-trans-2,2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropane-1-carboxylic acid ester. A mixture of isomers A and B is obtained. IR and NMR correspond to the structures of the substance indicated. NMR spectrum. Peaks at 1.20-1.26-1, 32-1.35 ppm. (methyls hydrogen in the 2-cyclopropane position); peak at 1.68-1.77 ppm. (hydrogen at the position of 1-cyclopropane); peaks at 1.95-2.42 ppm (hydrogen in the position of 3-cyclopropane); peaks at 4.23–4, 25–4.40–4.42–4.57 ppm. (hydrogen and l-ethyl chain in the 3-cyclopropane position); peak at 6.48 ppm (hydrogen on the same carbon as); peaks from 7.0 to 1.67 ppm. (hydrogens of aromatic der). Example 6. 5-1-Oxo-2-allyl-3-methylcyclopent-2-en-4-yl ester I R-TpaHc-2, 2-dimethyl-3- (1.22, -tetrabromoethyl) -cyclopropan-1 carboxy acid Step A. IR-TpaHc-2,2-Dimethyl-3- (2, 2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid. This compound is prepared by brominating IR-TpaHC-2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropane-1-carboxylic acid as a mixture of A and B isomers. NMR spectrum. Peaks from 1.30 to 1.40 ppm (methyls in the 2-cyclopropane position); peaks at 1.65-1.47 and 1.97 at 2.37 ppm of hydrogen in the 1- and 3-cyclopropane positions; peaks at 4.30-4.47 and at 4.47 4.65 h.mln. (hydrogen in position 1 of ethyl); peak at 9.53 ppm (carboxyl hydrogen). Stage B. IR-trans-2, 2-dimethyl-3- (1,2; 2,2-tetrabromoethyl) -diklopropan-1-carboxylic acid chloride. The action of thionyl chloride on | y-trans-2,2-dimethyl-3- (1 2 2 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid, obtained in stage A, gives the acid chloride, which is used in the next stage. IKS corresponds to the structure of the specified substance. Stage B. Sl-OKco-2-allyl-3-methylcyclopent-2-ene-4-ylide I K-trans-2,2-dimethyl-3- (l, 2, 2, 2-tetrabromoethyl) -cyclopropan-1 -carboxylic acid. Under the action of 5-1-oxo-2-allyl-3-methylcyclopent-2-ene-4-ol in the presence of pyridine on an acid chloride, obtained in stage B, Sl-OKco-2-allyl-3-methylcyclopent-2- is formed En-4-yl ester I of R-trans-2,2-dimethyl-3- (l, 2 / 2,2-tetrabromoyl) cyclopropan-1-carboxylic acid, mixture of isomers A and B. X-ray and NMR confirm the structure of this substance. NMR spectrum. Peaks at 1.30-1.32 | 1, 36 ppm (methyls 2-cyclopropane); peaks at 1.98-2.05 ppm (methyl 3-allerolone hydrogens); peaks at 4.83-5.25 ppm. (hydrogens of the final methylene of the allyl chain of allethrolone); peaks at 4.30-4.48 and at 4.48-4.67 ppm. (hydrogens in position 1 of the ethyl 3-cyclopropane side chain); peaks at 5.33–6.17 ppm (hydrogens at position 2 of the alletrolone allyl chain). EXAMPLE 7. 5-Benzyl-3-methyluryl IR-cis-2,2-dimethyl 3- (1,2,2,2-tetrabromoethyl) -cycloproane-1-carboxylic acid. Isomers of AV. By esterification in the presence of pyriin obtained in Step B of Example 5 5-benzyl-Zetilfuryl acid chloride is obtained a) with the p A 5 o-benzyl 3-methylfuric IR-cis-2,2-dimethyl-3 isomer (1, 2,2,2-tetrabromoethyl) -cyclopropane-carboxylic acid. loilj) -104 ° С with 0.5%, benzene). The most mobile isomer in chromatography in the tosh layer. NMR spectrum. Peaks at 1.23, 37 ppm (Methols of methyl 2-cy of clopropane); peaks at 1.65-2.03 hours / ml (hydrogens of 1- and 3-cyclopropane); peak at 3.92 ppm, (benzyl methylene hydrogens); peak at 4.92 ppm {methylene hydrogens); peaks at 5.275, 67 ppm (hydrogen in 1 chain of ethyl 3-cyclopropane); peak at 5.96 ppm (hydrogen 4-furyl); peak at 7.25 ppm / ml (phenyl hydrogens); peak at. 7.35 hours / mdn (2-furyl hydrogen). Circular dichroism (dioxane). l 6 - 6.5 with 2.17 mcc. b) isomer B 5-benzyl 3-methylfuryl ester IЯ-cis-2,2-dimethyl-3- (1, 2, 2, 2-tetrabromoethyl) -cyclopropane -1-carboxylic acid, / cX / l + 84 ° C (with 0.5% benzene). NMR spectrum. Peaks at 1.20-1.42 ppm (methyl 2-cyclopropane hydrogens); peaks from 1.67 to 2.17 ppm / ml (hydrogens of 1- and 3-cyclopropane); peak at 3.92 ppm (methylene benzyl hydrogens); peak at 4.95 ppm (methylene hydrogens CO-2. -CH2); peaks from 4.95 to 5.18 ppm. (hydrogen in 1 chain of ethyl 3-cyclopropane); peak at 7.25 ppm (aromatic benzyl hydrogen); peak at 7.33 ppm (hydrogen of 2-furyl). Circular dichroism (dioxane). l + 4.30 with 247 mmk. PRI me R 8. Sl-OKCO-2-allyl-3-methylcyclopent-2-ene-4-yl ester I R-cis-2, 2-dimethyl-3- (2-tetrabromoethyl) -cyclopropane 1-carboxylic acid. (Isomers A and b). 5-1-oxo-2-allyl-3-methylcyclopent-2-en-4-ol, prepared in Step B of Example 3, is esterified with the acid chloride R-cis-2, 2-dimethyl-3- (1-2, 2, 2-tetrabromoethyl) -cyclopropane-1-carb nova acid in the presence of pyridine and get about. a) isomer A 5-1-oxo-2-allyl-3-methylcyclopent-2-ene-4-yl ester I R-uHc-2, 2-dimethyl-3 (2, 2, 2-tetrabromoethyl) cyclopropane -1-carboxylic acid. loi / x) - (from 0.6%, benzene). NMR spectrum. Peaks at 1.281, 39 ppm (methyls 2-cyclopropane); peak at 1.96 ppm (methyl 3-allerolone hydrogens); peaks at 4.83-5.16 ppm. (hydrogens of the final methylene of the allyl chain); peaks from 5.33 to 6.16 ppm (hydrogen in the ethyl chain in the 3-cyc41 propane position and hydrogen in 2-allylic CIPI). Circular dichroism (dioxane). ut + 1.84 at 332 mmk; D +2.06 at 320 mmk; L - 19 at 225 MMK. Isomer A is the most mobile in thin layer chromatography. b) isomer B Sl-OKCO-2-allyl-3-methylcyclopent-2-ene-4-yl ester I R-cis-2,2-dimethyl-3- (1, 2.2, 2-tetrabromoethyl) -cyclopropane -1-carboxylic acid. Mpd 110 ° C. ) 81 ° С (from 0.6%, benzene). NMR spectrum. Peaks at 1.271, 47 ppm (methyls 2-cyclopropane); peak at 2.07 ppm (methyl 3-allerolone hydrogens); peaks from 4.83 to 5.33 ppm (hydrogen in 1 side chain of 3-cyclopropane and methylene hydrogens in 2-allyl chain); peaks at 5.5-6.16 ppm (2-allyl chain hydrogens); peak at 5.15 ppm (hydrogen 4-allerolone). Circular dichroism (dioxane). Afc + 2.46 at 332 mmk; le + 2.76 at 320 mmk, D + 3.79 at 250 mmk; DE - 14.7 at 225 MMK. Example 9. IK-cis-2,2-dimethyl-3- (1,2, 2,2-tetrabromoethyl) cyclopropane-1-carboxylic acid 3-phenoxybenzyl ester. (Isomers A and B). By esterification in the presence of pyridine hydrochloride IK-cis-2,2-dimethyl-3- (1, 2 {2,2-tetrabromoethyl) -cyclopropane-1-carboxylic acid 3-phenoxybenzyl alcohol get a) isomer A 3-phenoxybenzyl ester IK -cis-2, 2-dimethyl-3 - (, 2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid. Spd 90 ° c. (with 0.5% benzene). NMR spectrum. Peaks at 0.92 1, 37 h / Million (2-cycl-Q methyl hydrogen of lopropane); peaks at 1.67-2.08 ppm (hydrogens at the 1-st 3-cyclopropane positions); peak at 5.08 ppm (methylene hydrogens CO "CH2); peaks at 5.38-5.56 ppm. Hydrogen in position 1 of ethyl 3-cyclopropane); peaks from 6.67 to 7.58 ppm (hydrogens of aromatic core). Circular dichroism (dioxane). BOS. - 10 at 218 MMK. Isomer A is the most mobile in thin layer chromatography. b) isomer B H. -Phenoxybenzyl ester I of K-cis-2, 2-dimethyl-3- (l, 2, 2, 2-tetrabromoethyl-cyclopropane-1-carboxylic acid. + 61, (with 2.3% benzene NMR spectrum. Peaks at 1.221, 42 ppm (2-cyclopropane methyls); peaks from 1.67 to 2.08 ppm (1-and 3-cyclopropane positions); peaks from 4.93 to 5.33 ppm (hydrogen in the 1-ethyl position of 3-cyclopropane); peak at 5.15 ppm (methylene hydrogen j,); peaks from 6.75 to 7.58 ppm (aromatic hydrogens). Circular dichroism (dioxane) .J f +4.6 at 247 micron. Example 10. Sl-OKCO-2-allyl-3-3-methylcyclopent-2-en-4-silt ether, 1R-TpaHC-2,2-dimethyl-3- (2,2-D Chloro-1, 2-dibromoethyl) -cyclopropane-1-carbonyl oh acid.
Step A. IR-trans-2,2-Dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.
The action of bromine on I K-trans-2,2-dimethyl-3- (2, 2-dichlorovinyl) -cyclo lopropan-1-carboxylic acid gives I K-trans-2, 2-dimethyl-Z-12, 2-dichloro -l, 2-dibromoethyl) -cyclopropane-1-carboxylic acid, a mixture of isomers A and B
NMR spectrum. Peaks at 1.17.1, 37 ppm (methyls 2-cyclopropane); peaks from 1.65-1.73 to 1.93-2.03 ppm (1-cyclopropane hydrogens); peaks at 4.23-4.45 and at 4.45-4.62 ppm (hydrogen of 1-ethyl 3-cyclopropane).
Stage B. The acid chloride IR-t ans-2, 2-dimethyl-3- (2, 2-DICHLOR-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.
By the action of thionyl chloride on the acid obtained in the previous step A, an acid chloride IR-trans-2, 2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid is obtained.
IR spectrum (chloroform). Absorption at 1777
Stage B. 5-1-Oxo-2-allyl-3-methylcyclopent-2-en-4-yl ester IR-trans-2, 2-dimethyl-3- (2, 2-dichloro-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid.
By esterification in the presence of pyridine, obtained in stage B, of the acid chloride Sl-oKco-2-allyl-3-methylcyclopent-2-en-4-ol, Sl-OKCo-2-allyl-3-methylcyclopent-2-en-4- sulphate, IL-trans-2,2-dimethyl-3- (2, 2-DICHLOR-1 2-dibromoethyl) -cyclopropane-1-carboxylic acid ester as a mixture of isomers A and B,
NMR spectrum. Peaks from 1.30 to 1.34 ppm (hydrogens of methyl cyclopropane); peaks from 1, b 3 to 3, O h. ppm (1- and 3-cyclopropane hydrogens); peak at 2.05 ppm (methyl hydrogens in position 3-allerolone); peaks at 1 95-3.03 ppm (methylene hydrogens of the 1-allyl chain); peaks at 4.254, 43–4.61-ppm. (hydrogen of 1-ethyl 3-cyclopropane); peak at 4.25 ppm (methylene chloride in the final position of the allyl chain); peaks from 4.83 dr 5.41 ppm (hydrogen at the 2-allyl chain position); peak at 5.83 ppm. (hydrogens 4-allelo6lon).
Paragraphs and measures 11. RS-c gCiano-3-phenoxybenzyl ester |
Stage A. 1R-uHC-2,2-Dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.
In 30 cm of carbon tetrachloride are introduced by bubbling at (-15) ° С 11 g 8 g of chlorine, and then slowly added at (-10) with 24 g of solution I R-cis-g, 2-dimethyl-3- (2, 2 -dibromovinyl) -cyclpropane-1-carboxylic acid 37 ml of methylene chloride, shaken for 1.5 hours at and 2 hours at, concentrated under reduced pressure, purified by crystallization from carbon tetrachloride, and 7.4 g of IR-cis-2, 2- dimethyl-3 (2, 2-dibrom-11 2-dichloroethyl) -cyclopropane-1-carboxylic acid. T 134 ° C (A mixture of isomers A and B).
NMR spectrum, Peaks 1.32-1.44 and at 1.28-1.48 ppm. (methyls 2-cyclopropane); peaks at 5.08 5, 45 and at 4.67-5.0 ppm (hydrogen 1-ethyl chain in position 3-cycle opropane); peak at 10.1 ppm (carboxyl hydrogen).
Stage B. The acid chloride | K-cis-2,2-dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) cyclopropane-1-carboxylic acid.
By the action of thionyl chloride in the presence of pyridine on the acid obtained in the previous step A, the acid chloride IR-cis-2,2-dimethyl-3- (2, 2-dibromo-1,2-dichloroethyl) -cyclopropane-1-carboxylic acid is taken in this form in the next stage.
Stage in. K $ -CC Cyano-3-phenoxybenzyl ester tЯ-cis-2,2-dimethyl-3- (2, 2-dibromo-1,2-dichloroethyl) -cyclopropane-1-carboxylic acid.
By esterification of RS-ct-cyano-3-phenoxybenzyl alcohol in the presence of pyridine, obtained in the preceding stage B with acid chloran-HYDRIDE, is obtained β5-g; (- 2-dibromo-l, 2-dichloroethyl) -cyclopropane 1-1-carboxylic acid, mixture of isome. A and c.
NMR spectrum. Peaks at 1.23.1, 52 ppm (methyls 2-cyclopropane); peaks FROM 1.77 to 2.11 ppm (hydrogens of 1- and 3-cyclopropane); peaks at 4, and at 5.02 5, 21 ppm. (hydrogen in the G side of the chain in the 3-cyclopropane position), peaks from 6.40 to 6.43 ppm. (hydrogen on the same carbon as); peaks from 6.94 to 7.66 ppm (aromatic hydrogens).
Example 12. S-1-Oxo-2-allyl-3-methylcyclopent-2-en-4-yl ester I R-cis-2, 2-dimethyl-3- (2, 2-dibromO-1, 2-dichloroethyl ) - cyclopropane-1-carboxylic acid.
 By esterification of the acid chloride Sl-OKCO-2-allyl-3-methylcyclopent-2-en-4-olone obtained in stage B of Example 11, S-1-oxo-2-hyplyl-3-methylcyclopent-2-en-4-yl is obtained IR-cis-2,2-dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid ester, mixture of isomers A and B.
NMR spectrum. Peaks at 1.25 - 1.45 and at 1.29 - 1.40 ppm. (methyls 2-cyclopropane); peak at 1.96 ppm (methyl hydrogen 3-1l bullet): - peaks prk 2,96, 03 h / ml. (methylene hydrogens of 1-allyl chain); peaks at 4.83 - 5.16 ppm (hydrogens of the final methylene of the al.yl chain); peaks at 5.25-5.36 ppm (hydrogen in the 1-ethyl chain and 3-cyclopropane); peaks from 5.5 to 6.0 h / ml (hydrogens of 4-allerolone and hydrogen of the 2-allyl chain).
Example 13. RS-hX-Diano-3-phenoxybenzyl ester of Gk-trans-2,2-dimethyl-3- (2, 2-dibrbm-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.
The action of chlorine on 1B-trans-2,2-dimethyl-3- (2, 2-dibromovinyl) -cyclopropane-1-carboxylic acid gives 1 K-trans-2, 2-dimethyl-3- (2,2-dibrom-1, 2-dichloroethyl) -2-cyclopropane-1 carboxylic acid, which is converted into an acid chloride by the action of thionyl chloride, and then esterified as before RS-ot-cyano-3-phenoxybenzyl alcohol and get RS-oi-diano-Z-phenoxybenzyl ester iR -TpaHc-2,2-dimethyl-3- (2 2-dibromo-11 2-dichloroethyl) cyclopropane-1-carboxylic acid, a mixture of isomers A and B.
NMR spectrum. Peaks at 1.22-1.271, 37-1.4-1.45) ppm (methylrv hydrogen 2-cyclopropane); peaks from 1.67 to 2.5 ppm {1- and 3-cyclopropane hydrogens); peaks from 3.67 to 4.5 h. / million (hydrogen of 1-ethyl chain of 3-cyclopropane); peak at 6.52 ppm. (hydrogen on the same carbon as); peaks from 7.0 to 7.67 ppm (aromatic hydrogens). Example 14. 5-1-Oxo-2-allyl-3-methylcyclopent-2-ene-4-yl ester 1 R-TpaHc-2, 2-dimethyl-3- (2, 2- difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.
Stage A. IR-TpaHc-2,2-Dimethyl-3 (2, 2-difluoro-1, 2-dibromo-ethyl) cyclopropane-1-carboxylic acid.
The effect of bromine on IR-TpaHc-2,2-dimethyl-3- (212. difluorovinyl) -cyclopropane-1-carboxylic acid at (-6 (} C get I R-TpaHc-2,2-dimethyl-3- , 2, -difluoro-1/2-dibromoethyl) -cyclopropane-1-carboxylic acid with Tpl. 122c in the form of a mixture of isomers A and B.
Cglctr NMR. Peaks from 1.33 to 1.36 ppm (methyl 3-cyclopropane hydrogens); peaks from 1.60 to 2.23 ppm (hydrogens of 1- and 3-cyclopropane); peaks from 3.75 to 4.37 ppm (hydrogen of 1-ethyl chain of 3-cyclopropane); peak at 10.96 ppm (carboxyl hydrogen).
Step B. Chloride I R-TpaHC-2,2-dimethyl-3- (2, 2-difluoro-1) 2-Dibromoethyl) -cyclopropane-1-carboxylic acid.
By the action of thionyl chloride on the acid obtained in the previous step A, an acid chloride IR-trans-2, 2-dimethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid is used in the next stage .
Stage B. 5-1-Oxo-2-allyl-3-methylcyclopent-2-en-4-yl ester I-trans-2, 2-dimethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.
The esterification of the acid chloride Sl-OKCo-2-allyl-3-methylcyclopent-2-en-4-ol obtained in the preceding B stage in the presence of pyridine gives Sl-OKCo-2-allyl-3-methylcyclopent-2-en-4-yl 1 R-TpaHc-2, 2-dimethyl-3- (2 2-difluoro-l, 2-dibromoethyl) -cyclopropane-1-carboxylic acid ester, a mixture of isomers A and B.
NMR spectrum. Peak at 1.32 ppm (methyls 2-cyclopropane); peaks from 3.26 to 1.68 and from 1.73 to 2.19 ppm / mln. (1-cyclopropane hydrogens); peak at 1.20 ppm (methyl 3-allerolone hydrogens); peaks from 2.93 to 3.05 ppm / mln. (methylene hydrogens of 1-allyl chain); peaks from 4.83 to 5.25 ppm / mln. (hydrogens of the final methylene of the allyl chain); peaks from 3.58 to 4.33 ppm. (hydrogen of an ethyl chain in the 3-cyclopropane position); peaks from 4.83 to 5.25 ppm (hydrogen of the 2-allyl chain); peak at 5.83 ppm / mln. (hydrogen in 4 allerolone).
Example 15. RS-ci-cyano-3-phenoxybenzyl ester IR-cis-2,2-dimethyl-3- (2, 2-dichloro-1 2-dibromo) -cyclopropane-1-carbonose acid.
Stage A.) R-cis-2, 2-dimethyl-3- (2, 2-dichloro-1 2-dibromoethyl) -cyclopropan-1-carboxylic acid.
The action of bromine on IK-cis-2,2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropane-1-carboxylic acid is obtained. I R-u.iic-2, 2-dimethyl-3 (2 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid, a mixture of isomers A and B.
NMR spectrum. Peaks at 1.26-1.30 and at 1.41-1.42 Ch. / MLN. (methylene hydrogens of 3-cyclopropane); peaks at 1.832, 17 ppm / mln. (hydrogens of 1- and 3-cyclopropane); peaks from 4.83 to 5.58 ppm (1-ethyl hydrogen 3-cyclopropane); peak at 8.17 ppm / mln. (carboxyl hydrogen).
Stage B. Chloride 1H-cis-2,2-dimethyl-3- (2,2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid ..
This acid chloride is obtained by the action of thionyl chloride on the acid obtained in the previous step A.
Stage B. RS - (- Cyano-3-phenoxybenzyl ester IR-cis-2,2-dimethyl-3- (2, 2-dichloro-1, 2 dibromoethyl) -cyclopan-1-carboxylic acid. Esterification in the presence of pyri lina obtained in the precursor stage B, the acid chloride RS-t-cyano-3-phenoxybenzyl alcohol gives a mixture of isomers A and B. PRI meper 16. RS-o cyano-Z-phenoxybenzyl ester 1st-cis-2, 2-dimethyl-3- (2,2,2,1-tetrabromoethyl) -cyclopr9pan-1-carboxylic acid. Stage A. Chloride IR-cis-2, 2-dimethyl-3 (2, 2, 2, 1-tetrabrmethyl -cyclopropane-1-carboxylic acid. In a mixture of 40 ml of petroleum ether (T, d, "35-70 C), and 10.9 g of thionyl chloride were injected with 8.9 g of 1K-cis-2,2-dimethyl-3- {2, 2, 2,1-tetrabromoethyl) cyclopropane-1-carboxylic acid, heated under reflux and heated for 3 h. , petroleum ether and excess thionyl chloride are removed by distillation to obtain crude IR-UHC-2, -dimethyl-3- (2, 2, 2, 1-tetrabromoethyl) cyclopropane-1-carboxylic acid Chloride. Stage B. RStai-Cyano-3-phenoxybenzyl 1H-cis-2,2-dimethyl-3- (2,2, 2,1-tetrabromoethyl) cyclopropane-1-carboxylic acid ester. In a mixture of 5 ml of benzene and 10 ml of pyridine, 7 g of α-cyano-3-phenoxybenzyl alcohol was added, and a crude acid chloride obtained in solution A in 40 ml of benzene was added at about 0 ° C for about 15 minutes, shaken at 16 h, acidified to pH 1 with a dilute aqueous solution of hydrochloric ACID is extracted with benzene, the organic layer is washed with water, the sulfuric acid is dried with magnesium and the benzene solution is concentrated to dryness. The remainder of the chromium is chromatographed on silica gel eluting with benzene to obtain 7.33 g of ano-3-phenoxy-benzyl ester IR-cis-2, 2-dimethyl-3- {2.2, 2, 1-tetrabromoethyl) -cyclopropane-1-carbon acid. dialysis: CJl.OyN Vg (665.05). Calculated (,%: C 39.73; H 2.88; M 2.10; Br 48.06. Found,%: C 39.7; H 3; N 2.2; Br 44). Infrared spectrum ( chloroform). Absorption at 1743, absorption of carbonyl carbon at 1613, 158 1477 cm, characteristic of aromatic drama. UV spectrum (ethanol). Kink at 230 mmk (E; 194); Kink at 270 mmk (f, 36); Maximum at 278 MMK (E 37); Bend at 285 MMK (E, 28) 1 NMR spectrum (deuterochloroform). Peaks at 1.23-1.5 ppm, characteristic of double methylated hydrogen, peaks at 1.83-2, 16 ppm, characteristic of cyclopropyl / 1 hydrogen at 4.82-5.5 ppm, characteristic of hydrogen in position l of the substituted side e J chain J peaks at 6.37-6.42 ppm, characteristic of hydrogen, are carbon as the group of peaks at 6.83 7, 58 ppm, characteristic of the hydrogens of the aromatic village. Consumption in A IR-cis-2, 2-dimethyl-3- (2, 2 J 2,1-tetrabromoethyl) -cyclopropane-1-carboxylic acid can be prepared as follows: In 30 ml of tetragislormethane, 5 g of I-cis-2 , 2-dimethyl-3- (2, 2-dibromoviyl) -cyclopropane-1-carboxylic acid, for 30 minutes a solution of 0.9 ml of bromine in 10 ml of carbon tetrachloride is added, shaken up for 1.5 hours, concentrated to dryness under reduced pressure and floor 8.9 g of crude I R-cis-2, 2-dimethyl-3- (2, 2, 2,1-tetrabromoethyl) -cyclopropane-1-carboxylic acid are added. Example 17. IR-trans-2,2-dimethyl-3- (2, 2 J 2,1-tetrabromoethyl) -cyclopropan-1-carbrnic acid 3-phenoxybenzyl ester, 20 g of benzene is dissolved in 5 g of the acid chloride F R- trans-2,2-dimethyl-3- (2 2.2, 1-tetrabromoethyl) -cyclopropane-1-carboxylic acid, 2.4 g of 3-phenoxybenzyl alcohol, cooled until 4 ml of pyridine are gradually introduced, shaken in 48 hours at 20 ° C, pour the reaction mixture into an aqueous solution of hydrochloric acid, extract with benzene, wash with sodium bicarbonate, water, dry with sodium sulfate and concentrate to dryness by distillation under reduced pressure. This gives 6.2 g of residue, The latter is chromatographed on silica gel, eluting with a mixture of petroleum ether (Tzip 35-75c) and ethyl ether (9/1), and 3.68 g of 3-phenoxy-benzyl ester I R-TpaHc-2,2-dimethyl- 3- ( 2, 2, 2, 1 -tetrabromoethyl) -cyclopropane-1-carboxylic acid, (mixture of isomers A and B). Analysis: .O (640.03). Calculated), G: C 39.41; H 3.15; Br 49.94. H 3.2; Found,%: C 39.9; Вг 50, g. IR spectrum (chloroform). Absorption at 1728 cm, characteristic of carbonyl,: absorption at 1615-1590-1490 cm, characteristic of aromatic dr. NMR spectrum (deuterochloroform). Peaks at 1.26-1.29-1.35 ppm, characteristic of doubled methyls; peaks at 2.00-2.33 ppm characteristic of hydrogen in the 1-cyclopropyl position; peaks at 1.70 1, 79 ppm, characteristic of hydrogen in the 3-cyclopropyl position, peaks at 4.31-4.38-4.50-4, -67 ppm: with hydrogen in the position of the X-substituted., side ethyl chain; peaks at 5.17–5.20 ppm, characteristic of methylene hydroxide benzyl, peaks at 6.92–7.58 ppm: characteristic of hydrogen in the aromatic regions.
The starting acid chloride IR-trans-2, 2-dimethyl-3- (2, 2 | 2, 1-tetrabromoethyl-) cyclopropane-1-carboxylic acid was prepared as follows.
Step A. IR-TpaHc-2,2-Dimethyl-3- (2, 2, 2, 1-tetrabromoethyl) -cyclopropane-1-carboxylic acid.
The interaction is subjected to bromine and I K-trans-2, 2-dimethyl-3- (2, 2-dibromovinyl) -cyclopropane-1-carboxylic acid as in Example 16 and get I K-trans-2j 2-dimethyl-3- (2 , 2,2,1-tetrabromoethyl) -cyclopropane-1-carboxylic acid, (mixture of isomers A and B).
NMR spectrum (deuterochloroform). Peaks from 1.30 to 1.40 ppm (methyls 2-cyclopropyl); peaks at 1.65-1.74 and at 1.94-2.37 ppm (hydrogens of 1- and 3-cyclopropyl); peaks at 4.30-4.47 and at 4.47-4.65 ppm (hydrogen, 1-ethyl); peak at 9.63 h / ml (carboxyl hydrogen).
Stage B. IR-trans-2, 2-dimethyl-3- (2 {2, 2, 1-tetrabromoethyl-cyclopropane-1-carboxylic acid chloride).
By the action of thionyl chloride on the acid obtained in Test A, analogously to Example 16, K-trans-2, 2-dimethyl-3- (2.22, 1-tetrabromoethyl) -cyclopropane-1-carboxylic acid chloride 1 is obtained.
Example 18. 3-phenoxybenzyl ester I K-cis-2, 2-dimethyl-3- (2, 2, 1-tetrachloroethyl) -cyclopropane-1-carboxylic acid.
Stage A. IK-cis-2,2-Dimethyl-3- {2, 2, 2, 1-tetrachloroethyl) cyclopropanecarboxylic acid.
In 30 ml of tetrachloride, chlorine is bubbled through to saturation (11.8 g is dissolved), rastor is introduced for about 30 min. 16.7 g of 1K-cis-12,2-dimethyl-3- (2,2-dichlorovinyl)-diclopropane -1-carboxylic acid in 40 ml of methylene chloride at a temperature below, shaken for 24 hours, at 0, the temperature of the mixture (reaction) is brought to 25 ° C, shaken for 3 hours at this temperature, removing excess chlorine by bubbling nitrogen, purify the residue by chromatography, silica gel, eluting with a mixture of cyclohexane - ethyl acetate (8: 2), crystallized from petroleum ether a (T, „„ 35-75 C) and get 3.14 g of | K-cis-2,2-dimethyl-3- (2 J 2, 211-tetrachloroethyl) -cyclopropane-1-carboxylic acid, T.p. 144 ° C.
Analysis: .O g (279, 98).
Calculated,%; C 34.3; H 3.6; C1 50.6.
Found,%: C 34.4; H 3.7, cr 50.3.
NMR spectrum (deuterochloroform). Peaks at 1.26-1.42 and at 1.30 1, 42 ppm, characteristic of doubled methyls; peaks at 4.675, 17 ppm and from 5.08 to 5.43 h. / ml characteristic of hydrogen in the position of the 1-substituted ethyl side chain; peaks from 1.67 to 2.0 ppm, characteristic of cyclopropyl hydrogens; peak at 10.2 ppm, characteristic of carboxyl hydroxyl.
Stage B. IK-cis-2,2-dimethyl-3- (2,2,2,1-tetrachloroethyl) -cyclopropane-1-carboxylic acid anhydride chloride.
In a mixture of 60 cm n
m of petroleum ether) and 8.7 cm of chlorisra (35-70 of that thionyl, 6.75 g of IR-cis-2, 2-dimethyl-3- (2 J 2, 2,1-tetrachloroethyl) -cyclopropan-1- carboxylic acid, the reaction mixture is heated under reflux, maintained at boiling for 4.5 hours, concentrated to dryness by distillation under reduced pressure, benzene is added, concentrated to dryness to obtain the (crude) acid chloride IR-cis-2, 2-dimethyl-3 - (2, 2, 2, 1-tetrachloroethyl) cyclopropane-1-carboxylic acid, used in the next stage.
Stage B. I-K-cis-2, 2-dimethyl-3- (2) 1-tetrachloroethyl) -cyclopropane-1-carboxylic acid 3-phenoxybenzyl ester.
The crude acid chloride is dissolved in 60 ml of benzene, injected at 75 ° C with 5.2 g of 3-phenoxy-n: ester in solution in 50 ml of benzene, and then 2.6 ml of pyridine, shaken for 16 hours at poured the reaction mixture into a mixture of water and hydrochloric acid, extracted with ethyl ether and after concentration of the ethereal solution to dryness, 11 g of residue is obtained, which is chromatographed on silica gel, eluted with benzene-cyclohexane (1: 1), crystallized from ether and the first fraction is obtained in 4, 6 g of 3-phenoxybeneyl ester I of an R-cis-2, 2-dimethyl-3- (2, 2, 211-tetrachloroethyl) -cyclic Opropane-1-carboxylic acid.
Trl 86 C. K / T) -86.5C (, 5% benzene).
Analysis: C H (462.20).
Calculated,%: C 54.56; H 4.36; CE 30.68.
Found,%: with 54.9; H 4.5; CE 30.3.
UV spectrum (ethanol). ,
The bend at 226 mmk E 228;
Bend at 266 mmk EJ 36, Maximum at 271 mmk E 41 Maximum at 277 mmk E (40. NMR spectrum (deuterochloroform). Peaks at 1.27 - 1.4 ppm, inherent to the hydrogenated methyl isomer A; peak at 5.13 ppm, characteristic of the hydrogens of the –C-OC group of isomer A, peaks at 5, 27–5, 43 h / ml of hydrogen in the 1-side position of these isomer A chains, peaks at 1.23 1.40 ppm, characteristic of hydrogen of doubled methyls of isomer B, a peak at 5.18 ppm, characteristic of hydrogen of the group —C-OCHj of isomer B; O peaks at 4.83–5.17 h. / million, characteristic of hydrogen in position 1 of the side chain ethyl isomer ; peak at 1.61-2.03 ppm, characteristic of cyclopropyl hydrogens; peaks at 6.92-7.58 ppm, characteristic of aromatic hydrogens. This NMR spectrum shows that the compound contains about 9 / 10 isomers A and 1/10 isomer B. Continuing the chromatography, after crystallization from the vtoric ether, a fraction of 3.3 g of 3-phenoxybenzyl ether IK-cis-2,2-dimethyl-3- (2, 2, 2,1 -tetrachloroethyl) -cyclopropan-1-carboxylic acid. Tld 62S. / rf | p - 9 ° С (with 1%, benzene). Infrared spectrum (chloroform). The absorption at 1725 is characteristic of carbonyl; absorption at 1615 1590-1490 cm characteristic of the aromatic hydrogens. NMR spectrum (deuterocloroform). Peaks at 1.23–1.41 ppm; properties peculiar to doubled methyl bromides of isomer B; peaks at 4.83-5.17 ppm characteristic of hydrogen at position 1 of the ethyl side chain of isomer B; peak at 5.2 ppm, characteristic of the hydrogens of the group —C — O — CH — isomer B; peaks at 1.28-1.4 ppm, characteristic of the hydrogen of the doubled methyl isomer A; peaks at 5.27-5.43 ppm, characteristic of hydrogen at position 1 of the ethyl side chain of isomer A; pi at 5.13 ppm, characteristic of the hydrogen group —C — O — CHj, —isomer A; I ° peaks at 1.58-2.08 ppm, characteristic of cyclopropyl hydrogens; peaks at 6.9-7.16 ppm, characteristic of the aromatic hydrogens. The NMR spectrum shows that the compound contains about 3/5 of the isomer B and 2/5 of the isomer A. Example 19. RS-ol-Cyano-3-phenoxybenzyl ester IK-cis-2,2-dimethyl-3- (2, 2, 2) 1-tetrachloroethyl) -cyclopropane-1-carboxylic acid. Stage A. 1B-cis-2,2-dimethyl-3- (2 2.2, 1-tetrachloroethyl) cyclopropane-1-carboxylic acid chloride. 5.4 g of the corresponding tR-cis-acids are used and act in a similar manner to Example B of Example 18. Stage B. RS-ot-Cyano-3-phenoxybenzyl ester IK-cis-2,2-dimethyl-3 (2, 2 , 1-tetrachloroethyl) -cyclopropane-1-carboxylic acid. Obtained in stage A of this example, the acid chloride is dissolved in 50 ml of benzene, injected with a solution of .4.6 g of RS-o-cyano-3-phenoxybenzyl alcohol in 30 ml of benzene, and then 2.2 ml of pyridine, shaken in 48 hours at room temperature, pour the reaction mixture into a mixture of water and hydrochloric acid, extract the solution to dryness, chromatograph the residue on silica gel, eluting with a mixture of benzene - cyclohexane (1: 2), and 4.7 RS-o-cyano-3-phenoxybenzyl IR-cis-2,2-dimethyl-3- (2, 2, 2,1-tetrachloroethyl) -cyclopropane-1-carboxylic acid ester. (o (.ljj -56.5 ° С (with 0.4%, benzene). Analysis:, (487.22). Calculated: T%: C 54.2, 23; H C2 29.11; N 2 ,. 87. Found,%: C 54.3; cg 29.0; N 2.8. UV spectrum of ethanol.) Bend at 227 mmk Bend at 268 mmk Bend at 272 mmk Maximum at 278 mmk Peogib PRN 284 mmk, NMR spectrum ( deuterochloroform) iki at 1.22-1.43 ppm, peculiar to the hydrogen of doubled methyls; iki at 1.67-2.08 ppm, peculiar to the cyclopropyl hydrogen; peak of 4.83-6, 47 ppm, peculiar to odorod in the position of 1-substituted ethyl okol chain, peaks at, 38-6,46 ppm, peculiar to water on the same carbon as the peaks at 6.92-7, 58 ppm, in Hydrocarbons of the aromatic nucleus. Example 20. RS-allethroloic IR-cis-2,2-dimethyl-3 (2,2,2,1-tetrachloroethyl) -cyclopropane 1-carbonoyl acid Stage A. 1K-cis-2 acid chloride , 2-dimethyl-3- (2, 2, 2, 1-tetrachloroethyl) cyclopropane-1-carboxylic acid. It is prepared, as in Step B of Prier 18, starting from 7 g of the corresponding IR-cis-acid. Step B. RS-Alletrolone ester I R-cis-2, 2-dimethyl-3- (2,2,2, 1-tetralorethyl) -cyclopropan-1-carboxylic acid. Dissolved acid chloride in 20 ml of benzene is dissolved in solution A of the above example. A solution of 4 g of allerolone is introduced into this solution.
in 15 ml of benzene, and then 2.55 ml of pyridine, shaken for 18 hours at, poured into a mixture of water and hydrochloric acid, extracted with ether, concentrated to dryness, the ether solution is chromatographed on silica gel, eluting with a mixture of cyclohexane ethyl acetate (9 : 1) and get 8 g of RS-allethrolone ester I K-cis-2, 2-dimethyl-3- (2, 2, 2,1-tetrachloroethyl) -cyclopropane-1-carboxylic acid j
IdlS - 54.7 C (with 0.5%, chloroform
Analysis:, (414,15).
Calculated,%: C 49.30; H 4.87; All 34.24.
Found,%: C 49.5; H 4.9; CE 34.1.
UV spectrum (ethanol). Maximum at 227 MMK (EJ 334).
NMR spectrum (deuterochloroform). Peaks at 1.31-1.42 ppm, characteristic of doubled methyls for hydrogens, peaks at 1.67-2.17 ppm, characteristic of cyclopropyl hydrogens; the peaks at 4.82–6.17 ppm are characteristic of hydrogen in the 1 – 3 position of the bounded new ethyl chain.
Example 21, K5-o (1C-trans-2-, 2-dimethyl-3- (2j 2 2, 1-tetrachloroethyl) -cyclopropane-1-carboxylic acid hCiano-3-phenoxybenzyl ester.
Stage A. IK-trans-2,2-Dimethyl-3- (2, 21 2 11-tetrachloroethyl) -cyclopropane-1-carboxylic acid.
I
13.25 g of chlorine are dissolved in 30 ml of carbon tetrachloride at -10 ° C, 18.8 g of jR-trans-2, 2-dimethyl-3- (22-dichlorovinyl) -cyclopropane-1-carbonrvo are added in about 15 minutes acid in solution in 30 ml of methylene chloride, and on the reaction vessel he finds a cooler, in which liquid circulates, for condensation of chlorine that has not reacted, shake for 1.5 hours at -10 ° and then for 1.5 hours - at O C, remove excess chlorine at 20 ° C, sparging nitrogen, concentrate to dryness under reduced pressure, purify the residue by chromatography on silica barely eluted with a mixture of cyclohexane-ethyl acetate (7: 3), and get 23 g of I R-TpaHc-2, 2-dimethyl-3 (2, 1-terachlochloetil) -cyclopropane-1-carboxylic acid, in this form in the next stage,
 B. R-trans-2, 2-dimethyl-3- (2 21211-tetrachloroethyl) cyclopropane-1-carboxylic acid chlranhydride I.
12.276 g of the acid obtained in Stage A was added to a mixture of 30 ml of petroleum ether (boil 35-75 ° C) and 16 ml of embryo chloride and heated under reflux for 4.5 hours, concentrated
distilled to dryness under reduced pressure, benzene is added, the mixture is concentrated again to dryness and receive hlorang RS-trans-2,2-dimethyl-3- (2, 2, 2,1-tetrachloroethyl) -cyclopro, pan-1-carboxylic acid used in this form in the next stage.
Stage B., α-Ciano-5-phenoxybenzethyl ester IR-TpaHc-2,2-dimethyl-3- (2,2,2,1-tetrachloroethyl) -cyclopropane-1-carboxylic acid.
25 ml of benzene was added to the acid chloride obtained in stage B, a solution of 10.5 g of RS-c-cyano-3-phenoxybenzyl alcohol in 20 ml of benzene was quickly added, 4.5 ml of pyridine were rapidly added, and 16 h at, pour the reaction mixture into a mixture of water, ice and hydrochloric acid, extract with ethyl ether, wash the ether layers, dry them, concentrate to dryness by distillation under reduced pressure, chromatograph the residue on silica gel, eluting with a mixture of cyclohexane - ethyl acetate ( 90:10), and get 14,18 g RS-D-cy ano-3-phenoxybenzyl ester of I-R-TpaHc-2, 2-dimethyl-3- (2, 2, 2, 1 -tetrachloroethyl) -cyclopropane-1-carboxylic acid ester. ldl - 22,. (with 0.5%, benzene).
Analysis: C CE4. “Oz (487.21). Calculated,%: C 54.2; H 3.9; N 2.9; g 29.1
Found,%: C 54.0; H 4.0; N 2.7;
e 29, o;
IR spectrum (chloroform). Ri absorption 1742 cm, characteristic of carbonyl; The garrets at 1610, 1584, 1484 are intrinsic to aromatic dramas.
UV spectrum (ethanol). ,
The bend at 230 MMK (E - 230);
The bend at 267 MMK (E .41);
The bend at 271 MMK (Elj 44J;
Maximum at 277 MMK (B 49);
The bend at 283 MMK (E 37);
The bend at 305 MMK (E 4).
NMR spectrum (deuterochloroform). iki at 1.22-1.42 h, / million, characteristic of the hydrogens of the methyl group; peaks t 1.50 to 2.50 ppm attributable to cyclopropyl hydrogens; peaks from 3.66 to 4.41 h, ppm, peculiar to hydrogen in position 1 of the side chain, peak at 6.5 ppm, peculiar to hydrogen on carbon at at-peaks from 7.00 to 7.66 h ./million. characteristic of the hydrogens of the aromatic der.
Example 22. IR-TpaHc-2,2-dimethyl-3- (2, 2, 21 l-tetrachloroethyl) -cyclopropane-1-carboxylic acid 3-phenoxybenzene ester.
Stage A.  The acid chloride IR-trans-2, 2-dimethyl- 3- (2, 2, 211-tetrachloroethyl) -cyclopropane-1-carboxylic acid.  Preparing, as in Example 21, starting from 10.4 g of acid, the resulting acid chloride is dissolved in 30 ml of benzene and 37.2 ml of benzene solution of acid chloride are obtained.  Stage B.  3 I-phenoxybenzyl ester I I-trans-2,2-dimethyl-3- (2,2,2, 1 -tetrachloroethyl) -cyclopropane-1-carboxylic acid.  At 18,, 6 ml of the resulting solution.  acid chloride is introduced at OC 4 g of 3-phenoxybenzyl alcohol in solution in 15 ml of benzene, add 2 MP of pyridine, shake for 18 h at 20 ° C, pour the reaction mixture into a mixture of water, ice and hydrochloric acid, extract with ethyl ether, washed with water, the organic layer, dried with magnesium sulfate, filtered and concentrated to dryness by distillation under reduced pressure.  The residue (8.6 g) was purified by chromatography on silica gel, eluting with a mixture of cyclohexane: ethyl acetate (95: 5), and then with a mixture of cyclohexane and benzene (5: 5).  Analysis: (462.20).  Calculated 4: C 54.6; H 4.4; C1 30.7.  Found  %: C 55.2; H 4.5, Sit 29.4. J IR spectrum (chloroform).  The absorption at 1728 cm, characteristic of absorption at 1615-1587, is characteristic of the hydrogens of the aromatic spectrum of the UV spectrum (ethanol).  , The bend at 227 NWK ((Ejl 245); The bend at 266 mmk (TE) 36); Maximum at 272 MMK (Elf 42); Maximum at 277 MMK (40); | NMR spectrum (deuterochloroform).  Peaks at 1.19-1.33 hours / million , intrinsic hydrogeng1M doubled methyl; Peaks 1.66-2.25 h. / million characteristic of cyclopropyl hydrogens; peaks 4, 04, 41 h / million characteristic of hydrogen in position 1 of the substituted ethyl side chain; peak at 5.18 hours / million  characteristic of methylene benzyl radical; peaks at 6.83-7.67 hours / million characteristic of the hydrogen of the aromatic der.  Example 23  S-allethrolone ester of IR-trane-2,2-dimethyl-3- (2, 2, 2, 1-tetrachloroethyl) -1-carboxylic acid cycloprop.  Stage A.  The acid chloride IR-trans-2, 2-dimethyl-3- (2.2 2, 1-tetrachloroethyl) -cyclopropane-1-carboxylic acid.  A yield of 10.4 g from corresponding I of R-trans-acid is obtained as in Step B of about 21.  Stage B.  I-trans-2, 2-dimethyl-3- (2, 2, 21-tetrachloroethyl) -cyclopropan-1-to-carboxylic acid S-allethrolone ester.  The acid chlorohydride obtained in stage A is dissolved in 30 ml of benzene and 36.2 ml of the acid chloride solution (solution A) are obtained.  .  In ml cooled to solution A, 3.2 g of S-appletrolone are introduced in solution in 15 ml of benzene, shaken, 2 ml of pyridine are added, shaken for 16 hours at 20 ° C, the reaction mixture is poured into a mixture of water, ice and hydrochloric acid, extracted with ether, concentrated to dryness by distillation under reduced pressure, purified residue by chromatography on silica gel extracted with ether, concentrated to dryness by distillation under reduced pressure, purified residue by chromatographic method on silica gel, eluting with cyclohexane - ethyl ether ir uksus1noy acid (80:10) to give 4.56 g of S-ester alletrolonovogo tR-trans-2, 2-dimethyl-Z- (1 2,2,2-tetrachloroethyl) -tsiklopropan- 1-carboxylic acid.   85 C.  Analysis: C (414.16).  Calculated, H: C 49.3; H 4.8; CE 34.2.  Found,%: C49.0; H4.8; C 35.5.  Infrared spectrum (chloroform).  The absorption at 170 1730 cm, characteristic of absorption at 1655 and 1538 C1 "G, characteristic of Cj absorption at 9. 18, 992 cm cBoffcTeffective.  UV spectrum of ethanol).  Maximum-at 227-228 MMK (E, 357). , Maximum at 270 MMK (K 8) NMR spectrum (deuterochloroform).  Peaks at 1.32-1.37 hours / million characteristic of hydrogens of doubled methyl; peak at 2.08 hours / million characteristic of methyl hydrogen in the 2-allerolone position; peaks at 2.98 3, 08 h. / million characteristic of the hydrogens of the methylene allyl chain of allethrolone adjacent to the CYCLE; peaks at 4,, 23 I1 4.28-4.39 h. / million intrinsic to hydrogen in the 1-substituted ethyl side position; peaks at 4.83-5.25 hours / million  peculiar to the final methylene allyl chain of allethrolone; Spoke from 5.5 to 6.17 h. / - million, characteristic of hydrogen on carbon in the position of 1-allerolone and hydrogen carbon in the position of the | 3-allyl chain of allethrolone.  Example 24  3-phenoxybenzyl ester IR-cis-2V2-dimethyl-3- (1 2-dibromo-2,2-dichloroethyl) -cyclopropane-1-carboxylic acid.  In a solution of 4.65 g of acid chloride I R-cis-2,2-dimethyl-3- (1, 2-dibrom-2, 2-dichloroethyl) -cyclopropane-1-carboxylic acid and 2.40 g of 3-phenoxybenzyl alcohol in 20 ml of benzene is gradually introduced at 0 ° C with 4 ml of pyridine, shaken for 17 hours, the reaction mixture is poured into an aqueous solution of hydrochloric acid, extracted with benzene, the organic layer is washed with a saturated solution of sodium bicarbonate and water, and dried with magnesium sulfate and concentrated to dry repression under reduced pressure.  The residue is chromatographed on silica gel, eluting with a mixture of petroleum ether (T,-35-75 C) - ethyl ether (9: 1). , and 2.37 g of the 3H-cis-2,2-dimethyl-3- {1, 2-dibromo-2, 2-dichloro) -cyclopropan-1-carboxylic acid 3-phenoxybenzyl ester are obtained (. a mixture of isomers A and b;, (.  Analysis: C – H Br CEjtO (551.11).  Calculated. %: With 45.76; H 3.65; In g 29.0; CE 12.86.  Found,%: C 45.8; H 3.6; Br 28.5; every 12.9.  IR spectrum (chloroform).  Absorption at 1725 cm, characteristic of carbonyl; absorption at 1615-15901492 cm characteristic of aromatic drama.  NMR spectrum (deuterochloroform).  Peaks at 1.25 - 1.37 and 1.22 1, 39 h. / ml. characteristic of hydrogen doubled methyl; peaks at 1.75 2, 17 h. / million characteristic of hydrogen cyclopropyl; peaks at 5.1-5, 16h. / million Hydrogen benzyl hydrogens characteristic. radical; peaks at 5.0–5.42 and 5.35– 5.53 h. / million characteristic of hydrogen at the position of the l-substituted ethyl side chain; peaks at 6j83 - 7.59 h. / million peculiar to the roots of the aromatic der.  The NMR spectrum shows that the compound consists of 2/3 of isomer A and 1/3 of isomer B.  Example 25  IK-cis-2,2-dimethyl-3- (1,2-dibro -2, 2-dichloroethyl) -cyclopropane-1-carboxylic acid S-allethrolone ester.  Stage A.  Chloride 1K-cis-2, -dimethyl-3- (1, 2-dibromo-2, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.  The acid chloride was prepared analogously to example 24, starting from 3.6 g of | R-cis-2, 2-dimethyl-3- (2-dibromo-2, 2-dichloroethyl) -cyclopropane-1-carboxylic acid (. 4 g of acid chloride 7 are obtained.  Stage B.  S-allethrolone ester I K-cis-2, 2-dimethyl-3- (1,2-dibromo-2, 25-dichloroethyl) -cyclopropane-1-carboxylic acid.  4 g of the acid chloride obtained in stage A and 1.75 g of S-allerolone are dissolved in 40 ml of benzene, introduced with a mixture of 2 ml of pyridine and 2 ml of benzene, shaken for 24 hours at 20 ° C, the reaction mixture is poured into a mixture of water, ice and caustic acid is extracted with benzene, the organic layer is washed with a saturated WATN151M solution of sodium bicarbonate, water, dried with sodium sulfate and concentrated to dryness by distillation under reduced pressure.  The residue of 5.1 g is purified by chromatography on silica gel, eluting with benzol mixing. -. acetic acid ethyl ester (97: 3), and 4.25 g of 1H-cis-2,2-dimethyl-3- (2-dibromo-2, 2-dichloroethyl) -cyclopropane-1-carbonyl S-alleletrol ester are obtained. acid.  Analysis:, (503.07).  Calculated,%: C 40.58; H 4.0; Br 31.76; From 14.09.  Found,%: C 41.3; H 4.1; Br 31.0; From 14.2.  IR spectrum (chloroform).  The absorption at 1718 cm, characteristic of absorption at 1655, 1638, is characteristic of venous absorption at 918-997 cm, characteristic. .  NMR spectrum (deuterochloroform).  Peaks at 1.25-1.28 and 1.39-1.42 h. ppm, characteristic of doubled methyl; peaks at 1. 95-2.07 hours / million characteristic of the hydrogens of methyl 3-allerolone; peaks at 4.83–6.17.  h / million characteristic of the hydrogens of the final methylene allyl side chain of allerolone; peaks at 4.83-6.17 h. / million characteristic of hydrogen in the 1-substituted side of the ethyl chain /, the peak at 5.75 hours / million characteristic of hydrogen in the 4-allerolone position.  Example 26  I-5-cis-2,2-dimethyl-3- (2, 2 dichloro-1 2-dibromoethyl) -cyclopropane-1-carboxylic acid 5-benzyl-3-furyl methyl ester.  Stage A.  Chloride 1K-cis-2,2dimethyl-3- (2, 2-dichloro-1 2-dibromoethyl) -cyclopropane-1-carboxylic acid.  The acid chloride was prepared in analogy to Example 24, starting from 10 g of IR-cis2, 2-dimethyl-3- (2, 2-dichloro-1, 2-diromethyl) -cyclopropane-1-carboxylic acid.  Stage B.  5-Benzyl-3-furylmethyl ester I K-cis-2,2-dimethyl-3- (2,2dichloro-1, 2-dibromoethyl) -cyclopropane 1-carboxylic acid.  The acid loranhydride obtained in the previous step A is dissolved in an enzene and 27 ml of an acid loranhydride solution is obtained (solution A).  In a solution of 2.9 g of 5-benzyl-3-furylethyl alcohol in 15 ml of benzene, water of 12 ml of solution A of chlorohydric acid is cooled to 0 ° C, ml of pyridine is introduced, shaken for 48 hours at, poured onto a mixture of , ice and hydrochloric acid, extracted with benzene, then, after usual treatments, concentrated to dryness by distillation.  The residue is purified chromatorically on silica gel, eluting; Petroleum ether {T. mixture p35-75c ether (95: 5), and then 2.2 g of 5-benzyl-3-furylmethyl ester IR-uHc-2.2-2 are obtained with a mixture of petroleum ether (Tzip35-75 C) - ether 19: 1) dimethyl-5- (2 J 2-dichloro-1, 2 dibromoethyl) -cyclopropane-1-carboxylic acid.  | o1 | - 57, (with 0.4%, benzene) Analie: W, 539,104).  Calculated,%: C 44.56; H 3.74; Br 29.04; Ct 13.15.  Found,%: C 44.9; H 3.8; Br 29.1; From 13.3. , UV spectrum (ethanol).  , The bend at 252 MMK (E 20); The bend at 258 MMK (E 15); The bend at 264 MMK (E, 11); The bend at 268 MMK (E 9).  IR spectrum (chloroform).  Absorption.  at 1720, characteristic of carbonite lu; absorption at 1600.1522.1493 cm peculiar to aromatic and other.  NMR spectrum (deutrochloroform).  Peaks at 1.23-1.35 and 1.20-1.38 hours. / ppm, characteristic of methyl hydrodes in the 2-cyclopropyl position; peaks at 1.67-2.17 h. / million characteristic of cyclopropyl hydrogens; peak at 3.93 h. / million peculiar to the hydrogens of methane benzyl radkala; peaks at 4.93-5.0 hours / million characteristic of hydrogens on carbon adjacent to the carboxyl; peaks at 6.02-6.1 h. / million characteristic of hydrogen in the position of a 3-furan core; peaks at 4.83-5.165, 33-5.58 h. / million characteristic of the abdominal position in the 1-ethyl side of the chain; peak at 7.3 hours, mln. peculiar to the hydrogens of the phenyl radical peaks at 7.37 hours / million characteristic of hydrogen at position 5 of the furan core.  PRI me R 27.  3,4,5,6-Tetrahydrophthalimidomethyl ester I R-cis-2, 2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.  Stage A.  Chloride 1K-cis-2,2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.  The acid chloride is prepared in the same manner as in Example 24, starting from 10 g of I K-cis-2,2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.  Stage B.  3,4,5,6-Tetrahydrophthalimidomethyl ester 1 I-cis-2, 2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.  The acid chloride obtained in stage A is dissolved in benzene and 27 ml of benzene solution (solution A) are obtained.  In a solution of 1.4 g of 3,4,5,6 -tetrahydrophthalimidomethyl alcohol, 15 ml of benzene are added with 7.5 ml of solution A of the acid chloride, and then with 2 ml of pyridine, shaken for 36 hours at 20s; the reaction mixture is poured onto a mixture of water, ice and hydrochloric acid, e, constructed with benzene, washed with organic force with saturated sodium bicarbonate water and then with water, dried with sodium sulfate and concentrated to dryness by distillation under reduced pressure.  The residue is purified by chromatography on silica gel, eluting with a mixture of benzene and ethyl ester of acetic acid (9: 1).  1.89 g of 3,4,5,6-tetrahydrophthalimidomethyl ester IR-cis-2, 2-dimethyl-3- (2, 2-dichloro-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid are obtained.   - 53.5 s (from 0.98%, benzene).  Analysis: S. . H „Vg.  (532.07).  Calculated,%: C 38.37; H 3.6; N 2.63; Br 30.03; cr.  13.32.  Found,%: С 139.0vf Н З, 6; N 2,6; Br 28.3; From 12.7.  IR spectrum (chloroform).  Absorption at 1778 cm - 1735-1723 cm, characteristic of carbonyl; absorption at 1665 cm, peculiar.  NMR spectrum (deuterochloroform).  Peaks at 1.21-1.22-1.39 hours / million characteristic of hydrogens of doubled methyls, peaks at 1.67-1.83 h. / million characteristic of cyclopropyl hydrogens and methylenes at peak at 2.37 h. / million , peculiar to methylenes in peaks at 5.0-5.5 i. / million characteristic of hydrogen in the 1-ethyl side chain; peaks at 5.5-5.75 hours / million  characteristic of methylene hydrogens in the cL-carboxyl.  Example 28  ftS-ot-Cyano-3-phenoxybenzyl di-cis-trans-2, 2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid ester.  RS-cC-cyano-3-phenoxybeneyl d1-cns-trans-2,2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropane-1-carboxylic acid RS is used, the properties of which are as follows.  UV spectrum (ethanol).  , The bend at 226 MMK (E-f 522); The bend at 267 MMK (B 43); The bend at 272 MMK (EJ 47); Maximum at 278 MMK (E 52); NMR spectrum (deuterochloroform).  Peaks from 1.20 to 1.30 h. characteristic of the hydrogens of the methyl group; peaks at 5.60-5.75 h. / million characteristic of hydrogen in position 1 of the dichlorovinyl chain, corresponding to the trans-isomer; peaks at 6,206, 31 h. / million , | characteristic of hydrogen in position 1 of the vinyl chloride chain, corresponding to cis-eesader; peaks at 6.41-6.46 h. / million characteristic of carbon hydrogen in s-function peaks from 7.0 to 7.66 hours. / million characteristic of the hydrogens of the aromatic der.  In 30 ml of carbon tetrachloride, 6.7 g of VZ-c-cyano-3-phenoxybenzyl d1-cis-trans-2,2-dimethyl-3 - (2, 2-dichlorovinyl) -cyclopropane-1-carboxylic acid are introduced. , whose properties are given above, and then for 1 h, add a solution of 0.85 ml of bromine in 10 ml of carbon tetrachloride, stir for 2 hours at 20 ° C, concentrate to dryness under reduced pressure and obtain 10 g of crude product, which is chromatographed on silica gel eluted with a mixture of cyclohexane ethyl ester of acetic acid (9: 1), and 7.5 g of ftS-H-cyano-3-phenoxybenzene d-cis-trans-2,2-dimethyl-3- ( 2, 2-D Chloro-1, Y-dibromoethyl) klopropan rj-1-karbonoeoy acid.  Analysis; C H OjNCtjBriCalculated,%: C 45.86; H 3.32; N 2.43; From 12.30, Br27.74.  Found  %: C 46.2; H 3.6; N 2.4; cr 12.5; Вг 27,5.  UV spectrum (ethanol).  j Bend at 267 g. TN (34); The bend at 272 Imk (Ei 35); Maximum at 277 MMK (E | 38).  NMR spectrum (deuterochloroform).  Peaks at 1.20-1.44 h. / million , property of the hydrogens of the methyl groups; peaks from 1.54 to 2.40 h. / million characteristic of the hydrogens in positions 1 and 3 of the cycle / yupropane cycle; peaks from 4.21 to 4.51 H; / million characteristic of hydrogen in the l-dichlorovinyl chain position and trans-isomer are peaks from 4.97 to 5.40 4. / NuiH. characteristic of hydrogen at position 1 of the dichlorovinyl chain and the cis isomer; peaks from 6.42 to 6.50 h. / million characteristic of hydrogen on carbon in the o-grouping-C; M; peaks from 7.0 to 7.55 h. / million characteristic of aromatic hydrogens o Example 29.  5-Benzyl-3-furyl IU. thyl 1 st ester of I-trans-2, 2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.  7.6 g of chlorine anhydride IL-trans-2,2-dimethyl-3- (2, 2 dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid, 3.2 g of 5- benzyl-3-furylmethyl alcohol, 5 ml of pyridine are added dropwise, stirred for 48 hours at, water is added, the organic layer is separated by decantation, and extracted. the aqueous layer is benzene, the organic layers are combined, dried, concentrated to dryness by distillation under reduced pressure, and the residue is chromatographed on silica gel, eluting with benzene-cyclohexane (7 :. 3), and get 6.1 g of 5I-benzyl-3-furylmethyl ester IЯ-trans-2,2-dimethyl-3- (2, 2-dichloro-1,2-dibromoethyl) -dicallo propane-1-carboxylic acid.  L1 19 s (with 0.5%, benzene).   WITH . FeO (539.09).  Analysis; Calculated, 1-7%: (D 44.565 H 3.74; Br 29.65; C1 13.15.  Found,%: C 44.2; H 3.7; Br 29.4; From 13.5.  IR spectrum. Absorption at 1725 her / characteristic of carbonyl; absorption at 1555, 1540, 1498, 1495 cm is characteristic of –С С and aromatic drams.  UV spectrum (ethanol).  g Bend at 216 MMK (B 265); Bend at 251 mmk (v) 10.5) Maximum at 257 mmk (El, 8.5); The bend at 261 MMK (E 7); The bend at 263 MMK (E 6); Maximum at 268 MMK (El 4,5); NMR spectrum (deuterochloroform).  Peaks at 1.22-1.25-1.28 h. / million peculiar to hydrogens of doubled methyls, peaks at 1.6-2.32 hours. / million characteristic of cyclopropyl hydrogens; peak at 3.93 h. / million characteristic of the methylene hydrogens of the benzyl radical; peaks at 4.25-4.37-4.54 hours / million characteristic of hydrogen at position 1 of a substituted ethyl side chain; peaks at 4.95-4.97 and 6.0-6.05 h. / million characteristic of the hydrogens of methylene adjacent to the carboxyl; peak at 7.33 hours / million peculiar to hydrogen in the 4-furil core position; peak at 7.25 hours / million peculiar to phenyl hydrogens.  Example 30 3-Phenoxybenzyl ester I K-trans-2, 2-dimethyl-3- (1,2-dibrom-2, 2-dichloroethyl) -c clopropane-1-carboxylic acid.  In a solution of 9 g of 3-phenoxybenzyl alcohol in a mixture of 50 ml of benzene and 10 ml of pyridine, a solution of 19.35 g of IR-trans-2, 2-dimethyl- chloride is introduced. 3- (1, 2-dibromo-2, 2-dichloro-ethyl) -cyclopropane-1-carboxylic acid, stirred for 18 h at 20 s, poured the reaction mixture into water, extracted with benzene, dried with magnesium sulfate, concentrated to dryness by distillation .  The residue is purified by chromatography on silica gel, eluting with a mixture of petroleum ether (T, C) ethyl ether (95: 5), and 8.1 g of 3-phenoxy-ethyl ester I «-trans-2,2-dimethyl-3- (2, 2 are obtained) -dibromo-2, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.  Idl -20,5 ° C (with 0.6%, benzene).  Analysis: Cj Hj rjCEaOa (551.11).  Calculated,%: from 45,17; H 3.66; Br 29.0; SL 12.87.  Found,%: 45.7; H 3.7; Br 28.5; From 13.0.  IR spectrum (chloroform).  Absorption at 1730 cm, characteristic of carbonyl; absorption at 1618, 1590 cm, characteristic of the hydrogens of the aromatic nucleus.  UV spectrum (ethanol).  ,, Bend 228 MMK (E 216); Bend 267 MMK (EV, 34); Maximum at 272 MMK (E 37.5); Maximum at 278 MMK (E 36).  NMR spectrum (deuterochloroform).  Peaks at 1.22-1.27-1.29 hours / million characteristic of hydrogens of doubled methyl; peaks at 1.66-1.75 and 1.92 2, 13 h. / million characteristic of hydrogen in the 1-cyclopropyl position; peak at 1.92-2.33 hours / million characteristic of hydrogen at position 3 of cyclopropyl; peaks at 4.22-4.38 and 4.38-4.57 h. / million characteristic of hydrogen in position 1 of the substituted ethyl side chain peaks at 5.12-5.13 hours. / million characteristic of methylene hydrogens of the benzyl radical; peaks at 6.83-7.53 hours / million characteristic of the hydrogens of the aromatic der.  Example 31  3,4,5,6-Tetrahydrophthalimidomethyl ester IR-trans-2, 2-dimethyl-3- (1, 2-dibromo-2, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.  In 20 MP of benzene, 2 g of IK-trans-2,2-dimethyl-3- (1, 2-dibromo-2, 2-dichloroethyl) -cyclopropane-1-carboxylic acid chloride are dissolved and 0.930 g of oxymethyl-3,4, 5,6-tetrahydroftaigimide, add 2.5 ml of pyridine dropwise, shake for 48 hours at, add water, decant, extract with benzene, concentrate to dryness, chromatograph the residue on silica gel, eluting with a mixture of benzene - ethyl acetate (9: 1) and get 2, D7 g of 3,4,5,6-tetrahydrophthalimide methyl ester 1K-trans-2,2-dimethyl-3- (1, 2-dibromo-2,2-dichloroethyl) -cyclopropane 1-carboxy acid Ota.   M / 20 6.5 ° С (with 0.9%, benzene).  Analysis: C-Hr SEGMODE (532.066).  Calculated,%: C 38.38; H 3.60; Br 30.04; cr 13.32; N 2.63.  Found,%: C38,5; H3.5; Br 29.9; C1 13.4; N 2.5.  IR spectrum (chloroform).  Absorption at 1783 CM, intrinsic absorption at 1728 cm and 1750 cm; intrinsic and ester functions, absorption at 1669 cm, intrinsic.  UV spectrum (ethanol).  , Maximum at 223 mmk (E 301); Maximum at 229-230 mmk (E 293) ;, Bend at 236 mmk (4 172); The bend at 272 MMK (E 8); Example 32.  3-Phenoxybenzyl ester I K-trans-2, 2-dimethyl-3- (2, -dibromo-1, 2-dichloroethyl) -cyclopropane -1-yarboxylic acid.  Sthshchi A.  The acid chloride IR-trans-2, 2-dimethyl-3- (2,2-dibromo-1,2-dichloroethyl) -cyclopropane-1-carboxylic acid.  Act similarly to example 16, the outcome of.  4.5 g of IK-trans-2,2-dimethyl-Z- (2 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid and get hlrangidrid l, R-TpaHc-2,2-dimethyl- 3- (2, 2-dibromo-1 {2-dichloroethyl-cyclopropane-1-carboxylic acid.   Stage B.  3-phenoxybenzyl.  1R-TpaHc-2,2-dimethyl-3- (2 2-dibromo-1, 2-dichloroethyl) cyclopropane -1-carboxylic acid ester.  To a solution of 2.7 g of 3-phenoxybeneyl alcohol in 7 ml of benzene was added with a solution of acid chloride in 7 ml of benzene, 1.5 ml of pyridine was added, shaken for 16 hours, the reaction mixture was poured into a mixture of water, ice and hydrochloric acid, extracted with ethyl ether, the organic layer is washed with water, dried with magnesium sulfate and concentrated to dryness by distillation under reduced pressure.  The residue (6.37 g) is purified by chromatography on silica gel, eluting with a mixture of cyclohexane-ethyl acetate (90:10), and 2.09 g of 3-phenoxy-benzyl-hydrogen fR ether are obtained.  -trans-2, 2-dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.  Analysis: (551.12).  Calculated,%: With 45.7; H 3.6; Br 29; cr 12.8.  Found,%: C46.0; NZ, 8; Br 29.4; From 12.6.  IR spectrum (chloroform).  Absorption at 1730 peculiar absorption at 1615-1590 cm peculiar to aromatic dramas.  UV spectrum (ethanol).  , The bend at 220 MMK (E 205); The bend at 266 MMK (E 33); Maximum at 271-272 mmk (E 36); Maximum at 278 MMK E 34); NMR spectrum (deuterochloroform).  Peaks at 1.25-1.28-1.33 hours / million characteristic of hydrogens of doubled methyl; peaks at 1.7-2.42 hours ppm, characteristic of cyclopropyl hydrogens; peaks at 3.98-4.35 h. / million characteristic of hydrogen at position 1 of the substituted ethyl side chain; peaks at 6.85-7.5 hours / million characteristic of aromatic hydrogens; peak at 5.13 hours / million characteristic of the methylene hydrogens of the benzyl radical.  1 R-TpaHC-2, 2-Dimethyl 3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropan-1-carbonoBic acid is prepared as follows.  24 g of (I-trans-2,2-dimethyl-3- (Z, 2-dibromovinyl) cyclopropane-1-carboxylic acid is introduced into a mixture of 20 ml of carbon tetrachloride and 20 ml of methylene chloride, and then at, (- 10) C chlorine is bubbled into the reaction solution, a refrigerator is installed on the reaction vessel, in which methanol circulates at {-60) ° C, shaken for 2.5 hours. at (-10) Civ for 1.5 hours at 10 ° C, allow an excess of chlorine to evaporate, remove the solvents by distillation under reduced pressure, remove the residue by chromatography on silica gel, eluting with a mixture of cyclohexane-ethyl acetate - acetic acid (75: 25: 1) and then with a mixture of cyclohexane - ethyl acetate -. acetic acid (80: 20: 1), and 16.3 g of 1R-TpaHc-2,2-dimethyl-3- (2,2-dibromo-1, 2-dichloroethyl) -cyclopropan-1-carboxylic acid are obtained.
NMR spectrum (deuterochloroform). Peaks at 1.33-1.56 ppm, characteristic of doubled methyls; peaks at 1.7-12.25 ppm, characteristic of cyclopropyl hydrogens; peaks at 4.11-4.37 ppm, characteristic of hydrogen in position 1 of a substituted, ethyl side chain; peak at 10.8 ppm attributable to carboxyl hydrogen.
Example 33. S-allethrolone IK-trans-2,2-dimethyl-3- (2j 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid ester.
Stage A. The acid chloride IR-trans-2, 2-dimethyl-3- (2, 2-dibromo-1 J 2-dichloroethyl) -cyclopropane-1-carboxylic acid.
The process is carried out similarly to the previous examples, starting from 4.5 g of IR-trans-2, 2-dimethyl-3- (2, 2 - dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid and get the acid chloride I R -TpaHc-2, 2-dimethyl-Z- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.
Stage B. S-allethrolone ester I K-trans-2, 2-dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.
To a solution of 2.05 g of S-allethrolone in 7 ml of benzene was added with a solution of the acid chloride obtained in stage A in 7 ml of benzene, 1.5 ml of pyridine was added, shaken for 16 hours at 20 ° C, the reaction mixture was poured in a mixture of water, ice and hydrochloric acid, the mixture is extracted with ether, the organic layer is washed with water, dried with magnesium sulfate and concentrated by distillation. The residue (5.15 g) is purified by chromatography on silica gel, eluted with a mixture of cyclohexane and ethyl acetate (80:20), crystallized from isopropyl ether, and 1.8 g of S-Alt-olon O io ester I R-TpaHC-2, 2 are obtained -dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid. Mp 126C.
IR spectrum (chloroform). The absorption at 1713-1730 CMJ is characteristic of absorption at 1658-1642 cm, characteristic of -C C-; absorption at 923995 cm; peculiar to.
UV spectrum (ethanol).
Maximum at 229 mmk (Ei 315);
The bend at 330 MMK (E 1);
NMR spectrum (deuterochloroform). Peaks at 1.32-1.35-1.38 ppm, characteristic of doubled methyls; peaks at 4.23–4.4 and at 4.14, 27 ppm, characteristic of hydrogen in position 1 of the substituted ethyl side chain; peaks at 2.08-2.15 ppm, characteristic of methyl hydrogen in the 3-allerolone position; peaks at 2.98i3, 08 ppm, characteristic of methylene in the 5-allerolone position; peaks at 4.83-5.25 ppm, characteristic of the hydrogens of the final methylene allerolone; peaks at 5.5–6.17 ppm, characteristic of hydrogen in the position of the p-radical of allyl burstrolone; peak at 5.83 ppm, ({hydrogen-hydrogen at position 4. -allethrolone.
Example 34. IP-cis-2,2-dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid 3-phenoxybenzyl ester.
Stage A. 1K-cis-2,2-dimethyl-3- (2 2-dibrom-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid acid chloride.
5 g of IK-cis-2,2-dimethyl-3- (2, 2-dibrom-1, 2-dichloroethyl) -cyclopropane-1 are added to a mixture of rHZO ml of petroleum ether (Ur35-70 C) and 10 ml of thionyl chloride. -carboxylic acid, the reaction mixture is heated under reflux, maintained at boiling point. for 4 h, concentrated to dryness by distillation under reduced pressure, benzene is added, concentrated again to dryness under reduced pressure, and 5.4 g of acid chloride is obtained, I K-cis-2, 2-dimethyl-5- (2,2-dibrom-1 , Dichloroethyl) -cyclopropane-1-carboxylic acid.
Stage B. IK-cis-2,2-dimethyl-3- (2 2-dibromo-1,2-dichloroethyl) -cyclopropane-1-carboxylic acid 3-phenoxybenzyl ester.
5.4 g of the acid chloride obtained in the previous step A, 38 ml of benzene were added to 3.2 g of 3-phenoxybenzyl alcohol, and then, gradually, 8.35 g of pyridine in a solution of 10 ml of benzene was poured in at 8s, shaken for 17 at 20 ° C, poured into a mixture of water and ice, extracted with benzene, dried with magnesium sulfate and concentrated to dryness, benzene solution, the residue purified by chromatography on silica gel, eluted with a mixture of benzene - ethyl acetate (7: 3), crystallized from petroleum ether (Tcmp35 -70 ° C) and get 4.7 g of 3-phenoxybenzyl ester of the K-I cis-2,2-dimethyl-3- (2, 2-di6poM-l, 2-dichloroethyl) -cyclopropane-1-carboxylic acid. T PL 68 ° C. - З4с (with 1%, chloroform Analysis: (551.21). Calculated,%: 45.76; H 3.66; Br 29.00; C 12.86. Found: C 46.0; H 3.6; Br 29.3;, 7. Infrared spectrum (chloroform). Absorption at 1725 cm-t characteristic of carbonyl; absorption at 1615 1588 1490 cm characteristic of aromatic drama. UV spectrum (ethanol). Bend at 227 mmk ( En 214 Bend at 266 mmk (E 33) Maximum at 272 mmk (E 35) Maximum at 278 mmk (E 36) NMR spectrum (deuterochloroform). Peaks at 1.22-1.39 and at 1.26 | l, 42 hours / million, characteristic of hydrogen doubled methyls, peaks at 1,662, 08 hours / million, characteristic of hydrogen cyclopropyl, peaks at 4, 8--5, 37 hours / million properties hydrogens of the -C-OCH group; peaks at 6.83-7.58 ppm. Hydrocarbons characteristic of aromatic nuclei Example 35 5-Alletrolone esters GK-cis-2,2-dimethyl-3- ( 2, 2-diphl -l, 2-dibromoethyl) -cyclopropan-1-carb new acid. Stage A. IC-cis-2,2-dimethyl-3- (2, 2-DIFTOR-1, 2-dibromoethyl) - cyclopropane-1-carboxylic acid. Step A. GK-cis-2,2-Dimethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid. In 120 ml of methylene chloride, the introduction of 17 g of IR-cis-2,2-dimethyl-3- (2, 2-difluoro-vinyl) -cyclopropane-1-carboxylic acid at -65 s for 2 h, 15.2 g of bromine are introduced into solution in 40 ml of carbon tetrachloride, shaken for 2.5 h at (-65) s, allowed to rise to temperature, concentrated to dryness under reduced pressure, dissolve the residue in hot form in 50 ml of tetra chloromethane, cool to 0 ° C, shake at this temperature for 45 minutes, remove the insoluble matter by filtration, concentrate the filtrate to dryness by distillation under reduced pressure, dissolve The residue is taken up in 40 ml of carbon tetrachloride, shaken for 30 minutes at (-10) ° C, the insoluble matter is removed by filtration, the filtrate is concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica gel, cyclohexane is ethyl acetate ethyl acetate (75:25), crystallized from petroleum ether (Bp35-75 and obtain 1.465 g of IR-cis-2,2-dimethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid . TPA. NMR spectrum (deuterochloroform). Peaks at 1.28-1.38 ppm, characteristic of doubled methyls; peaks at 1.67-2.0 ppm; characteristic of cyclopropyl hydrogen; peaks at 4.67-5.3 ppm attributable to hydrogen in the substituted ethyl side chain. Stage B. 1L-cis-2,2-dimethyl-3- (2 {2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid acid chloride. 1.43 g of IR-cis-2,2-dimethyl-3- (2,2-difluoro-1, 2-dibromoethyl) -cyclopropane are introduced into 15 ml of petroleum ether (T., c.35-75 C). 1-carboxylic acid, add 2.5 ml of thionyl chloride, heat at boiling for 1.5 hours, remove the excess of thionyl chloride and solvent by distillation under reduced pressure, add benzene to the residue, concentrate to dryness by distillation under reduced pressure and get 1K-cis-2,2-dimethyl-3- (2, 2-difluoro-1 J 2-dibromoethyl) -cyclopropane-1-carboxylic acid chloride (crude), which is used in the following acid. Stage B. S-allethrolone ester I K-cis-2,2-dimethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid. To a solution of the acid chloride obtained in stage Bi in 10 ml of benzene are introduced at 2 ° C with 0.7 g of S-allerolone in solution in 5 ml of benzene, 0.5 ml of pyridine is added, shaken for 16 hours at 20 ° C , pour the reaction mixture into a mixture of water, ice and hydrochloric acid, extract with ethyl ether, wash the organic layer with water, dry with magnesium sulfate and concentrate to dryness. This gives a 2.02m-sparse ester, which is purified by chromatography, eluting with a mixture of cyclohexane and ethyl acetate (80:20). Obtain 1.224 g of S-allethrolone) ester I R-cis-2,2-dimethyl-3- (2, 2-DIFTOR-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid. - Analysis: С Н, (470,162). Calculated: C 43.4; H 4.3; Br 34.0; F 8.1. Found,%: C 43.2; H 4.4; Br 33.7; f 8.1. UV spectrum (ethanol). Maximum at 227-228 mmk () NMR spectrum (deuterochloroform). Peaks at 1.25-1.36 ppm, characteristic of doubled methyls; peaks at 2.0-2.06 ppm, characteristic of methyl hydrogens in the 2-gshletrolone position; peaks from 4.83 to 5.25 ppm, characteristic of the hydrogens of the final methylene of the side chain of allerolone; peaks from 5, 5 to 6,17 ppm, characteristic of hydrogen in the position of% of the side chain of allerolone and hydrogen on carbon in the position of 1-allerolone; peaks from 4.83 to 6.17 parts per ml of hydrogen characteristic of the 1-substituted ethyl side position; peaks from 1.67 to 2.16 ppm, characteristic of cyclopropyl hydrogens; peaks at 2.95-3.05 ppm, characteristic of methylene hydrogens in position c (allerolone side chain; peaks from 1.67 to 3.17 ppm, characteristic of the methylen allerolone cycle. Example 36 K5-O (α-Cyano-3-phenoxybenzylLovine ester 1C-cis-2,2-dimethyl- 3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid. Stage A. IR chloride -cis-2, 2-dimethyl-3- (2,2-difluoro-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid. In 15 ml of petroleum ether (T 75 C), 2.5 g of the resulting step In Example 35 of the IR-cis-acid, 7 ml of thionyl chloride is added, the reflux is heated It is kept at boiling for 13.5 hours, concentrated to dryness by distillation under reduced pressure, benzene is added, and the concentrate is dried and a crude acid chloride I of K-cis-2, 2-dimethyl-3- (2, 2-dif then -1, 2-dibromo-ethyl) -cyclopropane-1-carboxylic acid, used in the next stage. Stage B. RS-ci-Cyano-Z-phenoxybenzyl ester IR-cis-2,2-dimethyl-Z- ( 2, 2-DIFTOR-1, 2-dibromoethyl) -cyclopr-1-carboxylic acid. The acid chloride obtained in step A is dissolved in 15 ml of benzene, RS-oi.-cyano-3-phenoxybenzyl alcohol is added at 2 ° C in 10 ml of benzene in solution, 1 ml of pyridine is added, and shaken for 16 hours with, pour the reaction mixture into a mixture of water, ice and hydrochloric acid, extract with ether, concentrate to dryness by distillation, purify the residue by silica gel chromatography, eluting with a mixture of cyclohexane and ethyl acetate (90:10), and obtain 1.972 g of RS -c.-cyano-3-phenoxybenyl ether IR-CYN-2,2-dimethyl-3- (2,2-difluoro-1, 2-1 cybrome thyl) cyclo17 propane-1-carboxylic acid. Analysis: (543.22). Calculated,%: C 48.6; H 3.5; Br 29.4; F 7.0; N 2.6. Found: C 48.9; H 3.5; Br 29.6; F 7.1; N 2.5. IR spectrum (chloroform). Pogloade | Niya at 1735, characteristic: absorption at 1588-1610 cm and 1487 cm is characteristic of aromatic dramas. UV spectrum (ethanol). , The bend at 230 MMK (E 208); Bend at 268 mmk (E 34) Bend at 273 mmk (E 37) Maximum at 278 mmk (E 40) Bend at 285 mmk (E, 29). NMR spectrum (deuterochloroform). Peaks from 1.03 to 1.45 ppm, characteristic of doubled methyls; peaks of 1.75-2.0 ppm, hydrogen characteristic of cyclopropyl; peaks from 4.42 to 5.17 ppm attributable to hydrogen in the 1-ethyl side chain position; peaks at 6.4-6.47 ppm, characteristic of hydrogen in CSN; peaks from 6.92 to 7.67 ppm, characteristic of hydrogen 1 M aromatic der. Example 37. IK-trans-2,2-dimethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid 3-phenoxybenzyl ester. Stage A. IYa-trans-2, 2-dimethyl-3- (2,2-difluoro-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid chloride. in 40 ml of petroleum ether (T J575 ° C), 11 g of IR-trans-2.2-d lmethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid is added, 10 ml of thionyl chloride, the reaction mixture is heated under reflux, reflux is held for 4 hours, the excess methylene chloride and solvent are removed by distillation under reduced pressure, benzene is added and the mixture is concentrated again to dryness to give IR-trans-2,2-hydrochloride. dimethyl-3- (2, 2-difluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid, used in the next stage. Step B. 3H-Phenoxybenzyl ester I R-TpaHc-2,2-dimethyl-3- (2,2-drfluoro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid. The acid chloride obtained in step A is dissolved in 50 ml of benzene and 56 ml are obtained (solution A). 18.5 ml of solution A is injected at 2 seconds. 2.4 g of 3-phenoxybenzyl alcohol in solution in 2.5 ml of benzene, add 1 ml of pyridine, shake for 16 hours at 20 ° C, pour the reaction mixture into a mixture of water, ice and hydrochloric acid, extract with ether, and rinse water, the organic layer, tub with magnesium sulfate, is concentrated to dryness, the residue is purified by chromatographic silica gel, the mixture is cyclohexane-benzene (95: 5), and 3.204 g of 3-phenoxyenzyl ester IK-trans-2,2-di-meyl-3- ( 2, 2-DIFFOR-1, 2-dibromoethyl) cyclopropane-1-carboxylic acid.
Analysis: C (518.206).
Calculated with G%: C 48.7; H 3.9; Br 30.9; F 7.3.
Found,%: C 48.9; H 3.9; Br 31.0; F 7.1.
UV spectrum (ethanol).
(E
 225);
The bend at 225 MMK (E 33);
The bend at 265 MMK (Ei 37);
Maximum at 271 MMK (4 36);
Maximum at 271 MMK
NMR spectrum (deuterochloroform). A peak at 1.27 ppm, characteristic of doubled methyl methylodes j peaks at 1.58-2.17 ppm, characteristic of cyclopropyl hydrogens; peaks at 3.67-4.35 ppm, characteristic of hydrogen in position 1 of the substituted ethyl side chain; peak at 5.13 ppm, characteristic of methylene in oi. carboxyl; peaks from 7.58 to 7.75 ppm, characteristic of the aromatic hydrogens.
Example 38. B5-o (.- Cyano-3-phenoxybenzyl ester I | -trans-2, 2-dimethyl-3- (2,2-DIFTOR-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid
Ic-trans-2,2-dimethyl-3- (2I2-DIFTOR-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid chloride is prepared from 11 g of acid, as in Example 37, and then the resulting acid chloride is dissolved in 50 ml of benzene to give 56 ml of the acid chloride solution (solution A). In 37.5 ml of solution A were injected at 0 ° C with 6.4 g o (α-cya; u-3-phenoxybenzyl alcohol in a solution in 5 ml of benzene, added 2% pyridine Yush, shaken for 16 hours at - poured the reaction, cMecb of water, ice and hydrochloric acid, extracted with ethyl ether and after usual treatments are concentrated to dryness by distillation under reduced pressure. The residue is purified by chromatography on silica gel, eluted with cyclohexane - ethyl acetate with acetic acid (90:10). 46 Ya5-o-cyano-3-phenoxybenzyl ester I B-trans-2; 2-dimethyl-3- (2,2-difluoro-1, 2-dibromoethyl) -cycloprop -1-carboxylic acid.
Analysis:, FgNO (543.22).
Calculated,%: C 48.6; H 3.5; Br 29.4; N 2.6; F 7.
Found,%: C 49.1; H 3.5; Br 28.8; N 2.5iF 6.7.
IR spectrum (chloroform). The absorption at 1745 cm peculiar to carbonyl absorption at 1615-1590 is characteristic of the hydrogens of the aromatic nucleus.
UV spectrum (ethanol).
(E;
 192);
Kink at 230 mmk
(J 34);
The bend at 269 MMK
(E 36);
The bend at 273 mmk
.one . Maximum at 278 MMK (Eij 39);
The bend at 305 MMK (E 1).
Spectrum. NMR (deuterochloroform). The peaks at 1.2–1.33 ppm are characteristic of the hydrogen of doubled methyls, the peaks at 1.9–2.25 ppm are characteristic of cyclopropyl iodides; peaks at 3.66–4. / million characteristic of hydrogen in position 1 of the substituted side-i
 howl ethyl chain; the peak at 6.45 ppm / million, characteristic of hydrogen on the same carbon as the radical of the peak at 6.91-7.58 parts per million, characteristic of the hydrogens of the aromatic region.
Example 39. I-R-cis-2, 2-dimethyl- 3-) -fluoro-2-chloro-1, 2-dibromoethyl-cyclopropane-carboxylic acid phenoxybenzyl ester I (isomers A and b).
Stage A. IL-cis-2,2-Dimethyl-3- 2- (RS) -fluoro-2-chloro-1,2-dibromoethyl 3-cyclopropane-1-carboxylic acid,
8.9 p of IK-cis-2,2-dimethyl-3- (2-chloro-2-fluorvinyl) -cyclopropane-1-carboxylic acid (mixture of E + Z isomers) are dissolved in 100 ml of carbon tetrachloride, added at ( -10) ° C for 30 min. 2.4 ml of bromine in solution in 20 ml of carbon tetrachloride, shaken for 4 hours at, concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica gel, eluted with ethyl acetate, and 13 are obtained , 7 and 1 "-Cis-2.2-dimethyl-3-f2- (RS) -fluoro-2-chloro-1, 2-dibromoethyl-3-cyclopropane-1-carboxylic acid.
IR spectrum (chloroform). Absorption at 1710 cm peculiar absorption at 3510 cm peculiar
ON. .
NMR spectrum (deuterochloroform). Peaks at 1.30-1.32-1.42 ppm, characteristic of doubled methyls; peaks at 1.75-2.08 ppm,
characteristic of hydrogen cyclopropyl / peaks at 4.67-5.50 ppm, characteristic of hydrogen in position 1 of the substituted ethyl side chain; peak at 10.75 ppm, characteristic of carboxyl hydrogen.
Stage B. 3-Phenoxybenzyl ester 1H-cis-2, -; imethyl-3-C2- (K5) -fluoro-2-chloro-1, 2-dibromoethyl 3-cyclopropan-1-caronic acid.
3.5 g of the obtained in Stage A I, .2-dimethyl-3- {2- (K $) -fluoro-2-chloro-1, 2-dibromoethyl-cyclopropane-1-carboxylic acid, 3.5 g 3 are mixed. -phenoxybenzyl alcohol, 3.5 g of neopentyl acetal dimethylformamide, 35 ml of benzene, heat the reaction mixture to, maintain it at this temperature for 17 hours, cool, concentrate to dryness by distillation under reduced pressure, chromatograph the residue on silica gel, elute the mixture with benzene - cyclohexane (1: 1), and on the one hand get 1,050 g of isomer A 3-phenoxybenzyl "pvogo ester I R-cis-2, 2-dimethyl-3-C2- (K5) -fto p-2-chloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid. T silt 50 ° C.
Analysis: s (534.65).
Calculated,%: C 47.17; H 3.77, C 6.63; F 3.55; Br 29.89.
Found,%: C47.4; H3.8; ce 7.2; F 3.7; Br 29.4.
IR spectrum (chloroform). Absorption at 1735 cm, characteristic of C O; absorption at 1675-1590-1490 cm, characteristic of aromatic drama.
NMR spectrum (deuterochloroform). Peaks at 1.23-1.39 ppm, characteristic of doubled methyls; peaks at 1.73-2.01 ppm, characteristic of cyclopropyl hydrogens; peak at 5.08 ppm, characteristic of methylene hydroxyl benzyl radikgsha; peaks from 5.08 to 5.50 ppm attributable to hydrogen at position l of a substituted ethyl side chain; peaks at 6.83-7.58 ppm, characteristic of aromatic hydrogens.
On the other hand, 0.62 g of isomer B is collected.
Calculated,%: C 47.17; H 3.77; ce 6.03; f 3.55; Br 29.89.
Found,%; C 47.5; H 3.8; ce 6.2; F 3.6; Br 29.6.
IR spectrum (chloroform). Same with the spectrum of isomer A.
NMR spectrum (deuterochloroform). Peaks at 1.22-1.34 ppm, characteristic of doubled methyls; peaks at 1.75-2.0. hours / million, characteristic of cyclopropyl hydrogen; a peak at 15.12 ppm, characteristic of hydrogen and methylene of the benzyl radical; peaks. from 4.83 to 5.33 ppm, characteristic of a garden in position 1 of a substituted side ethyl chain; peaks from 5.85 to 7.5 ppm, characteristic of the aromatic hydrogens.
Example 40 3,4,5,6-Tetrahydrophthalimidomethyl ester (1R, cis-2, 2-dimethyl-3- (1,2,2 2 2-tetrabromoethyl) cyclopropane-1-carboxylic acid.
Stage A. (1k, cis) -2., 2-Dimethyl-3- (l,., 2-tetrabromoethyl) -cyclopropan-1-carboxylic acid.
19.4 g of (1P, cis) -2, 2-dimethyl-3- (2, 2-dibromovinyl) -cyclopropane-1-carboxylic acid are added to 150 cm of carbon tetrachloride; 10.4 g of bromine in a solution of 22 cm of carbon tetrachloride, stirred for 1 h at 20 s, end of it. Dry it by distillation under smart 1} Shennli pressure and get 31, of the solid product (Tp 145 C). This crude product recrystallizes in 110 cm of carbon tetrachloride to give 22.12 g of (1B, cis) -2,2-dimethyl-3- (1/2, 2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid. .
This product is a mixture of isomers A and B, which are detected by means of the NMR spectrum, allowing the compound to be detected (corresponding to
approximately 2/3 of the mixture), exhibiting peaks at 1.31-1.43 ppm, corresponding to hydrogens of paired methyls and peaks from 5.33 to 5.66 ppm, corresponding to hydrogen, located on monobrominated asymmetric carbon, and another compound (corresponding to about 1/3 of the mixture), exhibiting peaks at 1.281, 48 ppm, corresponding to paired methyl, and peaks from 4, 5.34 ppm, correspond to hydrogen on monobromylated asymmetric carbon.
The mixture also contains peaks from 1.67 to 2.17 ppm. (hydrogens at positions 1 and 3 of cyclopropane) and one peak at 11.25 ppm. (acidic mobile hydrogen).
Analysis of the mixture obtained (TPd150 with the following: С „Н ВгдО ,,, (457, 804).
Calculated,%: C 20.99; H 2.20; Br 69.82.
Found,%: C 20.9; H 2.2; Vg 70.2.
Stage B. Chloride (1I, cis) -2,2-dimethyl-3- (1, 2, 2 2-tetrabromoethyl -} - cyclopropane-1-carboxylic acid.
In 179 cm of petroleum ether (t = 35-75 s) 0.2 cm of dimethylformamide, 8.5 cm of thionyl chloride are introduced, the mixture is heated under reflux, 35.76 g (lR, cis) -2, 2 are introduced. -dimethyl-3- (1, 2.21 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid in 150 cm of methylene chloride, stirred for 2 hours with reflux, cooled, concentrated to dryness by distillation, added toluene, again concentrated to dryness by distillation under reduced pressure, 38 g of crude acid chloride (TPA 88 ° C), used in this form in the next stage, are obtained.
Stage B. 3,4,5,6-Tetrahydrophthalimidomethyl (IK, cis) -2,2-dimethyl-cCH1J 22,2-tetrabromoethyl) -cyclopropane-1-carboxylic acid.
7.7 g of the acid chloride obtained in the previous step are stirred in 50 cm3 of anhydrous benzene with 2.9 g of neopinamine, cooled until 3 g of pyridine are added with stirring, allowed to rise to room temperature, agitation is stirred for 18 hours, the reaction mixture is poured the mixture is diluted with hydrochloric acid, extracted with benzene, washed with an aqueous solution of sodium bicarbonate, rinsed with water until neutral, the organic layer is separated, dried over magnesium sulphate, bottled and concentrated under reduced th pressure. 10 g of crude product are obtained, which is purified by chromatography on silica (eluant: benzene ethyl acetate (95: 5; collected 3.3 g of 3,4,5,6-tetrahydrophthalimidomethyl ester (1R, cis; -2,2-dimethyl - C- (1,2,2,2-tetrabromoethyl) -cyclopropan-1-carboxylic acid in the form of a mixture of isomers A and B and 0.5 g in the form of isomer B. Properties of the product obtained as a mixture of isomers A and B. -21.5 ± 1 ° С (with 1%, benzene). Analysis: N04 (620, 982). Calculated,%: C 32.88; H 3.08; N 2.25; Br 51.47; Found %: C 33.8; H 3.2; N2.1; Br 50.2. UV spectrum (ethanol). Bend. 218 mmk (E 243); Max. 223 mmk (EJ Max. 223 mmk (EJ f 17100; 229 mmk (E 269); Max 16700 Bend 238 mmk (E 170) 10500 ;, Bend mmk (E 8). NMR spectrum (deuterochloroform). Peaks at 4.98-5.15 ppm, characteristic for hydrogen in position 1 of the ethyl side chain of isomer B; peaks at 1.2–1.45 ppm; characteristic of hydrogens of paired methyl isomer B; peaks at 5.17–5.38 h / m hydrogen characteristic of l is the side of the ethyl chain of the isomer A peaks at 1.2-1.38 ppm, characteristic of the hydrogen of paired methyl and measure A; peaks at 1.58-2.08 ppm hydrogens characteristic of cyclopropyl and methylene cyclohexyl; a plate at 2.33 ppm characteristic of methylene hydrogens cyclohexyl; peaks, at 5.33–5.70 ppm, characteristic for hydrogens, SOOS group. Properties of the product obtained as isomer b. U / 2- ° + 72.5 + 2.5 s (with 0.5%, W) A / Analysis: 04 (620.982). Calculated,%: C 32.88; H 3, 08; N 2.25; Br 51.47. Found,%: C 33.5; H 3.3; N 2.2; Br 50.1. UV spectrum. J Bend 218 mmk E 248; Max. 223 MMK E 278; Max. 228-229 MMK E 272; Bend 238 MMK E-172; The bend at 295 MMK 7. NMR spectrum (deuterochloroform). Peaks at 4.98–5.16 ppm are characteristic of hydrogen at position 1 of the ethyl side chain; peaks at 1.2 1.45 h, ppm, characteristic of paired methyl; peaks at 1.52 h. / mpn., characteristic of hydrogen cyclopropyl and for methylenes in the pr-position in cyclohexyl; plateau at 2.38 ppm, characteristic of methylene hydrogens cyclohexyl; peaks at 5.38-5.57 and 5.57-5.75 ppm, characteristic of the hydrogens of the COOCH group N. Example 41. 3,4,5,6-Tetrahydrophthalimidomethyl ether (1R, trans-g, 2-dimethyl-3- (1,2,2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid. Step A. (1K, trans) -2,2-Dimethyl-3- (l, 2, 2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid. This compound was prepared by bromination of (1K, trans) -2,2-dimethyl-3- (22-dibromovinyl) -cyclopropane-1-carboxylic acid as a mixture of isomers A and B. NMR spectrum. Peaks from 1.30 to 1.40 ppm (methyls hydrogen at position 2 of cyclopropane); peaks at 1.65-1.174 and 1.97-2.37 ppm. hydrogens at positions 1 and 3 of cyclopropane; peaks at 4.30-4.47 and 4.474f65 ppm (hydrogen in position 1 of ethyl); peak at 9.63 ppm (hydrogen carboxyl). B. Chloride (1K, trans) -2,2-dimethyl-3- (l, 2, 2, 2-tetrabromoethyl) -cyclopropane-1-carboxylic acid. By the action of thionyl chloride obtained in stage A (1R, trans) - 2, 2-dimethyl-3- (l, 2, 2, 2-tetrabromoethyl) cyclopropane-1-carboxylic acid is obtained in acid chloride, which is used in this form in the next stage. IR spectrum (chloroform). Absorption at 1778 cM-t Stage B. 3,4,5,6-Tetrahydrophthalimidomethyl (1 R, TpaHc) -2, 2-dimethyl-3- (l, 2, 2, 2-tetrabromoethyl) -cyclopropane-1-carbon acid. 7.7 g of the acid chloride obtained in the previous step are treated in the same way as in Step B of Example 1. 9.2 g of crude product are obtained, which is purified by chromatography on silica (eluant: benzene ethyl acetate (9: 1). After crystallization, the product is taken up in petroleum ether (-70 ° C), sucked off, dried and collected 5.4 g of 3,4,5,6-tetracdrophthalimidomethyl ether (1K, trans) -2,2-dimethyl-3- (2-tetrabromoethnl -cyclopropane-1-carboxylic acid. A and B isomer mixture Tr. 124 C. Uli-l ± .l ° C (with 1% benzene). Analysis: С H-Br4NO4 (620.982). Calculated,%: С 32.88; H 3.08; B 51.47; N 2.25. Found: C 33.1; H 3.2; Br; 51.1; N 2.1. UV spectrum (ethanol); Max. 224 mmk 8 17000; Max. 228 mmk 6 16000;
Bend 235 MMK.-167 10400 ;,
Kink 280 MMK E 9, NMR spectrum (deuterochloroform). Peaks at 1.25-1.30-1.31 ppm, characteristic of paired methyl hydrogens; peaks from 1.58 to 2.16 h, ppm, characteristic of cyclopropyl hydrogens and methylenes in the P-position in the hexyl cycle; peaks from 2.16 to 2.5 ppm characteristic for hydrogen methylenes in the oi-position in cyclohexyl; peaks at 4.24–4.41 and at 4.43–; 4.61 ppm, characteristic of hydrogen in the position. 1 side ethyl chain; peaks at 5.51 and 5.55 ppm / ml characteristic of the COOCH N grouping.
Example 42. 3H3 -Cyano-3-phenoxybenzyl ester (1R, trans) -2,2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.
Staci A. (1K.trans) -2,2-dimethyl-3- (2, 2-DICHLOR-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid.
The action of bromine on (1R, trans) -2,2-dimethyl-3- (2 2-dichlorovinyl) -cyclopropane-1-carboxylic acid gives (IR, trans) -2,2-dimethyl-3- (2,2- dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid is a mixture of isomers A and
In
NMR spectrum. Pics at 1.17-1, 37 ppm
(methyls hydrogen in position 2 of cyclopropane); peaks from 1.65-1.73 ppm (hydrogens in position 1 of cyclopropane peaks at 4.23-4.45 and at 4.45 4.62 ppm (hydrogen in l ethyl in position 3 of cyclopropane) .
Stage B. Chloride (1K, trans) -2, 2-dimethyl-3- (2, 2-di.chloro-1, 2-dibromoethnl) -cyclopropane-1-carboxylic acid.
By the action of thionyl chloride on the acid obtained in the previous step A, (iR, trans) -2, 2-dimethyl-3- (2, 2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carboxylic acid chloride is obtained.
IR spectrum (chloroform). Absorption at 1777 cm-1
Stage B. 5 O-Cyano-3-phenoxybenzyl E (1) ir (1R, trans), 2-dimethyl-3- (2, 2-dichloro-1,2-dibrom ethyl-cyclopropane-1-carboxylic acid.
4.45 g of the acid chloride obtained in the previous stage are mixed with 2.6 g of fs3A-cyano-3-phenoxybenzyl alcohol in 100 cm of anhydrous benzene, cooled to + 15 ° C, a solution of 5 cm of pyridine in 20 cm of anhydrous benzene is added, stirring for 3 hours at room temperature, the reaction medium is poured onto 100 cm 2 of a hydrochloric acid solution and the organic layer is separated, washed with water and concentrated to dryness under reduced pressure.
After chromatography on silica (eluent benzene), 4, 9 g, α-cyano-3-phenoxybenzyl refir (lR, trans) -2,2-dimethyl-3- (2,2-dichloro-1,2-dibromoethyl) -cyclopropane is obtained -1-carboxylic acid in the form of a mixture of isomers A and B. o (benzene).
Analysis: (576.12).
Calculated,%: C 45.86; H 3.32; Br 27.74; C1 12.31; N 2.43.
Found,%: C 46.0; H 3.4; Br 27.5; cr 12.2; N 2.2.
Circular dichroism.
Max, at 287 mmk d + 0.12;
Max, at 282 mmk l + 0.11;
Max, at 265 mmk + 0.042.
NMR spectrum. Peaks at 1.20-1.261, 31 ppm, are characteristic of paired methyl hydrogens; peaks at 4.204, 35 and at 4.36–4.52 ppm, characteristic of hydrogen in position 1 of the ethyl chain; peaks from 1.68 to 1.78 from 1.97 to 2.07 and from 1.97 to 2.42 ppm characteristic of cyclopropyl hydrogens; a peak at 6.42 parts / ml characteristic of the COOCHCN hydrogen group; peaks from 6.92 to 7.58 ppm, characteristic of aromatic hydrogens.
Stage G. Separation of isomers A and B 5 o1-cyano-3-phenoxy-benzyl ether (1 I,) - 2,2-dimethyl-3- (2,2-dichloro-1, 2-dibromoethyl) -cyclopropane-1-carbon acid.
4.69 g of a mixture of isomers A and B obtained in S-cyano-3-phenoxybenzyl ester (1R.tran -2, 2-dimethyl-3- (2, 2-DICHLOR-1,2-dibromoethyl)) are chromatographed on silica; ) -cyclopropane 7-1-carboxylic acid, eluted with a mixture of hexane pentane - ether - acetonitrile isopropyl alcohol (30: 12: 0.4: 1.2: 0.03) and is irradiated with 1.385 g of isomer A M12o + 35.54; 2, (( from 0.5%, benzene) and 0.980 g of isomer BY / - 17.5 d2C (from 0.8%, benzene).
Example 43. s Jol-cyano-3-phenoxybenzyl ester (lR, cis) -2, 2-dimethyl-3- (2, 2-dibromo-112-dichloroethyl) -cyclopropane-1-carboxylic acid.
Stage A. (lR,) - 2, 2-Dimethyl-3- (2, 2-dibromo-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid.
In 30 cm of carbon tetrachloride are introduced, sparging at -15 ° C, 11.8 g of chlorine, and then 24 g of a solution of (lR, cis) -2,2-dimethyl-3- (2, 2-dibromovinyl) is slowly added. -cyclopropane-1-carboxylic acid in 37 cm of methylene chloride, stirred for 1.5 h at 0 ° C and for 2 h at, concentrated. under reduced pressure, purified by crystallization in carbon tetrachloride and get 7.4 g (lR, cc) -2,2-dimethyl-3 (2, 2 dibromo-1, 21-dichloroethyl) -cyclopropane-1-carbstoic acid. Tr, Al34 (mixture of isomers A and B).
NMR spectrum. Peaks at 1.32-1.44 and at 1.28-1.48. (methyls hydrogen in position 2 cycrpropane); peaks at 5.08 - 5.45 and at 4, S7.5, 0 h./million, (hydrogen in 1 ethyl chain in position 3 of cyclopropane); peak at 10.1 ppm (carboxyl hydrogen).
Staci B. Chloride (lR.UHic) -2,2-dimethyl-3- (2, 2-dibromo-1,2-dichloroethyl) -cyclopropane-1-carboxylic acid.
The action of thionyl chloride in the presence of pyridine on the acid obtained in the previous step A gives (1B.Tcis) -2,2-dimethyl 3- (2, 2-dibromo-1, 2-dichloroethyl) chloride.) - cyclopropane-1-carboxylic acid used in this form in the following stages.
Step B. 5 Jci-Cyano-3-phenoxybenzyl ester (1K, cis) -2,2-dimethyl-3- (2 2-dibromo-1,2-dichloroethyl) -cyclopropane-1-carboxylic acid.
3.8 g of the acid chloride prepared in the previous stage are mixed with 2.5 g of pZc: cyano-3-phenoxybenzyl alcohol in 100 cm of anhydrous Senzol. Cooled to and added a solution of 4 cm of pyridine in 20 cm of Qesjj aqueous benzene. Stir 4 v. At room temperature and pour the reaction medium into 100 cm 2 of a solution of hydrochloric acid. The organic layer is separated, washed with water, dried and concentrated to dryness under reduced pressure. After chromatography on silica (eluent petroleum ether (40-70 ° C) - isopropyl ether (100: 20),
.-Cyano-3-phenoxybenzyl ester 1R, cis) -2,2-dimethyl-3- (2,2-dibrom-1, 2-dichloroethyl) -cyclopropane-1-carboxylic acid in the form of 1.8 g of isomer A, rf 0.30 and 1.4 g of isomer B, rf 0.25,
For isomer A | dL / |, -21 ± 1 ° С (with 1% benzene),
Circular dichroism
Max, at 300 MMK LE -0.003;
Max, at 288 MMK and + 0.29;
Max, with 264 MMK uk €. + 0.11;
Max, at 232 MMK - 1.8.
NMR spectrum (deuterochloroform). Peaks at 1.28-1.37 h, ppm, characteristic for double methyl hydrogens are peaks at :. 5.05-5.10-5.18-5.23 ppm characteristic of the hydrogens in position l of the ethyl side chain; peaks at 1.83-2.10 hr, characteristic of cyclopropyl hydrogens; peaks at 6.38 h / ppm, characteristic of hydrogen COOCHCN groups; peaks from 6.92 to 7.55 h, ppm, characteristic for hydrogens of the aromatic region. .
For isomer B W + 80 + 2., 5c (with 1%, benzene).
Circular dichroism.
Max, at 288 mmk d - + 0,22;
Pere1 Ib with 263 mmkl € 0.62; ,
Max. at 220 mmk g & + 3.7.
NMR spectrum (deuterochloroform). Peaks at 1.23-1.38 ppm, characteristic of double methyl hydrogens; peaks from 4.6 to 4.95 ppm characteristic of hydrogen at position 1 of the ethyl side chain; peaks from 1.75 to 2.16 h, ppm, characteristic of cyclopropyl hydrogens / peak at 6.38 ppm, characteristic of COOCHCN hydrogen; peaks from 6.88 to 7.57 ppm are characteristic of aromatic hydrogens.
Example 44 BOB-Cyano-3-phen-hydroxybenzyl ester (1K, cis) -2,2-dimethyl-3- (l, 2, 2 2-tetrachloroethyl) -cyclopropane-1-carboxylic acid.
Stage A. (1R, cis) -2,2-Dimethyl-3- (1,2,2,2-tetrachloroethyl) -cyclopropane-1-carboxylic acid,
In 30 cm of carbon tetrachloride they were bubbled to saturation (11.8 g of chlorine was dissolved), injected. about 30 minutes a solution of 16.7 g (1N, cis) -2,2-dimethyl- 3- (2, 2-dichlorovinyl) -cyclopropane-1-carboxylic acid in 40 cm of methylene chloride at a temperature; below 0 ° C, stirred for 24 hours, the mixture is brought to 25 ° C, stirred for 3 hours at this temperature, excess chlorine is removed, nitrogen is bubbled up, concentrated to dryness by distillation under reduced pressure, and the residue is purified chromatographically on silica gel, and the mixture is cyclohexane-ethyl Acetic acid ester (8: 2), crystallized in petroleum ether (TC, “3575 C) and get 3.14 g (1K, cis) - 2, -dimethyl-3- (l, 2, 2, 2-tetrachloroethyl) -cyclopropane-1-carboxylic acid. Tf 144 ° C.
Analysis: (279.98).
Calculated,% C 34.3; H 3.6; From 50.6.
Found,%: C 34.4; H 3.7; cr 50.3.
NMR spectrum (deuterochloroform). Peaks at 1.26 - 1.42 and 1.30.1, 42 ppm, characteristic of double methyl water; peaks from 4, .76 to 5.17 and from 5.08 to 5.43 ppm, characteristic of hydrogen in position 1 of the substituted ethyl side chain; peaks from 1.67 to 2.0 ppm characteristic of cyclopropyl hydrogens; peak at 10.2 h, ppm, characteristic of carboxyl hydroxide.
Stage B. Chloride (1K, cis) -2,2-dimethyl- 3- (1, 2, 2, 2-tetrachloroethyl) -cyclopropane-1-carboxylic acid.
To a mixture of 60 cm of petroleum ether (T cp35-70 C) and 8.7 cm of thionyl chloride, 6.75 g (1, d, cis) -2, 2-dimethyl-3- (l, 2, 2 -tetrachloroethyl) -cyclopropane-1-carboxylic acid, heated the reaction mixture under reflux, refluxed for 4.5 h, concentrated to dryness by distillation under reduced pressure, benzene was added to concentrate to dryness and get (1R, cis) -2, 2-dimethyl-3- (1 2) 2, 2 -tetrachloroethyl) -cyclopropan-1 carboxylic acid (crude), which was used in the following stage. Stage B, C3-3-Cyano-3-phenoxy-benzyl ester (1H, cis) -2,2 dimethyl-3- (2, 2, 2-tetrachloroethyl) -cyclopro-1-carboxylic acid. 3.19 g of the acid chloride obtained in the previous step are mixed with 2.6 g of sJcl-cyano-3-phenoxybenzyl alcohol in 30 cm of anhydrous benzene. Cool in an ice bath and slowly add 3 cm of pyridine. The mixture is stirred at room temperature for 24 hours and then the reaction medium is poured onto diluted and cold hydrochloric acid. Extraction is carried out with benzene, the organic layer is separated, washed with sodium bicarbonate solution, rinsed with water, dried over sodium sulfate, filter; UT; And concentrated under reduced pressure. Purified by chromatography on silica (eluent: benzene - cyclohexane (7: 3) and get s 4.-cyano-3-phenoxybenzyl ether (1K, cis) -2,2-dimethyl-3- (1, 2 2, 2 - tetrachloroethyl) -cyclopropane-1-carboxylic acid in the form of 2.258 g of isomer A and 1.48 g of a mixture of isomers A and B. ... For isomer A) oll + 35.5 + (with 0.6% benzene) . Analysis: C1H (487.213). Calculated,%: C 54.23; H 3.93; N 2.87; C1 29.1. Found,%: C54.4; P 3.8 N 2.8; C g 28.5. NMR spectrum (deuterochloroform). Peaks at 1.28–1.37 ppm, characteristic for double methyl hydrogens, peaks from 1.75 to 2.08 ppm, characteristic of cyclopropyl hydrogens; peaks from 5.07 to 5.25 ppm, characteristic of hydrogen in position 1 of the ethyl side chain; peak at 6.35 ppm for CpOCHCN group species; peaks from 6.92 to 7.58 h / mLn, characteristic of hydrogens of the aromatic nuclei. Physical analysis of the mixture of IS isomers. -33.5 + 2, (with 0.4%, benzene). Analysis: (487, 213), Calculated,%: C 54.23; H 3.93; N 2.87; From 29.1. Found,%: C54,5; H3.9; .N 2.8; cr. 28.8. NMR spectrum (deuterochloroform). Peaks at 1.2–1.35 ppm are characteristic of the double methyl methyl isomer R; peaks at 1.27-1.35 ppm characteristic of double methylated hydrogens isomer S; peaks at 1.75 – i2, 08 ppm, characteristic of cyclopropyl hydrogens; peaks from 4.77 ppm to 4.94 ppm, characteristic of hydrogen at position 1 of the ethyl side chain; peaks from 5.08 to 5.26 ppm, characteristic of hydrogen in position 1 of the ethyl side chain; peaks at 6.35 and 6.37 ppm, characteristic for hydrogen are COOCHCN groups; peaks from 7.93 to 7.58 ppm, characteristic of aromatic hydrogens. Example 45. k "1-Cyano-3-phenrxybenzyl ester (1H, t-ranc) -2, 2 dimethyl-3- (2 2-dichloro-1,2-dibromoethyl) -cyclopropane-1-carboxylic acid. Act as in stage B of example 3, but starting from 2 g of chloride (IR, trans) -2,2-dimethyl-3- (2, 2-dichloro-l, 2-dibromoethyl) -2-cyclopropane-1-carboxylic of the acid obtained in Step B of Example 3 and 1.1 g of α-cyano-3-phenoxybenzyl ester (1R, trans) -2, 2-dimethyl-3- (2,2-dichloro-1,2-dibromoethyl ) -cyclopropan-l-carboxylic acid in the form of a mixture of A isomers foL / D- 28 t (with 0.7%, benzene). Analysis: C ,, ЫОз (576,122). Calculated,%: C 45.87; H 3.32; N 2.43; cr 12.31; Br 27.74. Found,%: With 46.3; H 3.3; N 2.4; 02 12.4; Br 27.4. NMR spectrum (deuterochloroform). Peaks at 1.31-1.35 ppm, characteristic of double methyl hydrogens; peaks from 1.66 to 2.42 ppm, characteristic of cyclopropyl hydrogens; peaks at 4.23-4.42 and at 4.424, 58 ppm, characteristic of hydrogen at position 1 of the ethyl side chain; a peak at 6.47 ppm, characteristic of the COOCHCN hydrogen group; peaks from 6.92 to 7.58 ppm characteristic of aromatic hydrogens. Circular dichroism (dioxane). Maximum at 219 mmk - 5.4; Maximum at 280 mmk - 0.28; The bend at 285 MMK - 0.27; The resulting mixture of isomers A and B is chromatographed on silica, eluting with hexane-pentane ether (7: 2.8: 0.17) and isomers A and B are obtained separately. Isomer A. NMR spectrum (deuterochloroform). Peaks at 1.32-1.37 ppm, characteristic of double methyl hydrogens

权利要求:
Claims (2)
[1]
Claim
1. Method for the preparation of isomeric • substituted cyclopropanecarboxylic acids or their functional derivatives of the general formula 1 or a group of the formula II
nn
CH _g I _g "
where Rj is a hydrogen atom or methyl;
Rg is phenyl or the group —CH ^ —CgCH, predominantly 5-beneyl-3-methylfuryl, or a group of the formula IU /
where R ^ is vinyl, propen-1-yl, buta-1, -3-dienyl or buten-1-yl,. either a group of the formula IV ί (^ ί) η Λ h where Poison is a hydrogen atom, or ethynyl (-sig);
R ζ is a chlorine atom or i η is a number equal to 0 or a group where f
methyl nitrile group;
1 or 2, mainly 3-phenoxybenzyl, ot-cyano-3-phenoxybenzyl or <£ -ethynyl-3-phenoxybenzyl group, of the formula V.
^R 6 ″ ^R 7> ^R in водород ^{R is} hydrogen, chlorine or S / 1-phenyl or tetra- or hydrophenyl, a dangling atom of methyl di40
CH-C ~ 2 sn = sn-sn about t compound of the general formula so that f
an atom of hydrogen, fluorine, chlorine or bromine; an atom of fluorine, chlorine or bromine that is different or the same as X ₄ ;
chlorine, bromine or iodine atom, hydroxyl, halogen or ether group OR, or benzyl radical, which can be replaced by one or more radicals selected from the group C ^ -C ₊ alkyl, alkenyl C-C ₆ ,. "oxyalkenyl C ₂ ~ C ₆ , alkydienyl Cd-Cg, dioximethylene, benzyl, halogen,
VNIIIPI Order 7277/91 Draw 443
Branch PPP Patent, / X n, with si,
50 _G de, x ₂ and Z have the indicated meanings, are reacted with a chlorinating or brominating, or iodinating reagent for a double bond.
[2]
2. The method according to claim 1, characterized in that chlorine, bromine or iodine is used as the chlorinating, armoring or iodinating reagent.

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU858559A3|1981-08-23|Method of producing isomeric sustituted cyclopropanecarboxalic acids or their functional derivatives

---

FI73966C|1987-12-10|Process for Preparation of New Cyclopropane Carboxylic Acid Esters with a Polyhalogen Substituent Useful for Control of Parasites in Warm Blood Animals

---

Coperet et al.1995|Acylpalladation of Internal Alkynes and Palladium-Catalyzed Carbonylation of |-. beta.-Iodoenones and Related Derivatives Producing. gamma.-Lactones and. gamma.-Lactams

---

SU1075970A3|1984-02-23|Process for preparing cis-derivatives of dihaloidvinylcyclopropane

---

DE1468553C2|1971-09-30|

---

SU1200848A3|1985-12-23|Method of producing esters from cis- or trans-cyclopropancarboxylic acids and racemic alpha-cyano-3-phenoxy-benzyl alcohol

---

TW200815336A|2008-04-01|Process for continuously preparing unsaturated carboxylic anhydrides

---

Sato et al.2008|Zn-mediated rhodium-catalyzed α-trifluoromethylation of ketones via silyl enol ethers

---

Citterio et al.1993|Oxidation of diethyl ω-phenylalkenylmalonates by high valent metal salts.

---

Fry et al.1968|Stereoselective electrochemical reduction of geminal dihalocyclopropanes

---

DE1668603B2|1974-01-17|Substituted cyclopropanecarboxylic acid esters and process for their preparation

---

Wang et al.1992|Stereochemical study on the palladium |-catalyzed carbonylation of 3-|-2-methylenealkanoates and analogues

---

Krishna et al.2003|The use of acetylenic aldehydes in Baylis–Hillman reactions: synthesis of versatile allyl propargyl alcohols

---

Kaiser et al.2003|Synthetic analogues of the antibiotic pestalone

---

US3997586A|1976-12-14|Cyclopropanecarboxylic acids and esters

---

Takeda et al.1973|Allylic rearrangement. III. Favorskii-type rearrangemnt of the vinylogs of. alpha.-chloroacetones

---

DD148767A5|1981-06-10|METHOD FOR THE PRODUCTION OF INSECTICIDAL AND ACARICIDAL COMPOUNDS

---

Babler et al.1977|A facile synthesis of the sex pheromone of the red bollworm moth from 10-undecen-1-ol

---

US4277617A|1981-07-07|Process for the preparation of esters

---

Ungur et al.2000|Synthetic studies on natural diterpenoid glyceryl esters

---

Kulkarni et al.2006|A short and efficient synthesis of |-β-cuparenone

---

Singh et al.1996|Synthesis and chiral separation of some antitumor agents

---

Abouabdellah et al.1991|Lewis acid induced ene cyclization of. omega.-olefinic trifluoromethyl ketones: access to bicyclic compounds bearing a trifluoromethyl group

---

Yonemura et al.1986|Reaction of α, β-unsaturated carboxylic acids with manganese | acetate in the presence of chloride ion

---

JPH10509971A|1998-09-29|Halogenated esters useful as intermediates for insecticides

同族专利:

---

公开号 | 公开日

---

MD222C2|1995-12-31|

---

ATA677277A|1979-04-15|

---

MD222B1|1995-06-30|

---

BE858894A|1978-03-20|

---

FR2364884A1|1978-04-14|

---

JPS6243985B2|1987-09-17|

---

ZA775669B|1978-10-25|

---

ZA775668B|1978-10-25|

---

AT350043B|1979-05-10|

---

AT353248B|1979-11-12|

---

PL129488B1|1984-05-31|

---

PL214250A1|1980-02-25|

---

JPS64363B2|1989-01-06|

---

FR2364884B1|1979-01-12|

---

TR20005A|1980-06-11|

---

ATA677377A|1978-10-15|

---

JPS6011404A|1985-01-21|

---

JPS59152349A|1984-08-31|

---

BE858895A|1978-03-20|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB1168797A|1965-12-09|1969-10-29|Nat Res Dev|Cyclopropane Carboxylic Acid Derivatives and their use as Insecticides|PT67634B|1977-02-11|1979-07-17|Ciba Geigy Ag|Process for the preparation of new esters|

---

PT67633B|1977-02-11|1979-07-17|Ciba Geigy Ag|Process for the preparation of new esters|

---

FR2380244B1|1977-02-11|1980-04-25|Ciba Geigy Ag|

---

US4277617A|1977-10-27|1981-07-07|Roussel Uclaf|Process for the preparation of esters|

---

FR2432016B2|1978-07-24|1981-07-10|Roussel Uclaf|

---

EP0015239A3|1979-02-15|1980-09-17|Ciba-Geigy Ag|Esters of cyclopropanecarboxylic acid, process for their preparation and their use as pesticides|

---

FR2484256B1|1979-06-29|1986-10-24|Roussel Uclaf|METHOD FOR CONTROLLING PEST OF HOT BLOOD ANIMALS|

---

OA06730A|1980-01-25|1982-06-30|Roussel Uclaf|3-substituted derivatives of cyclopropane-1-carboxylic acid, their application against parasites of plants and warm-blooded animals, the corresponding compositions as well as the perfume compositions containing them, their meadow|

---

DE3004092A1|1980-02-05|1981-08-13|Bayer Ag, 5090 Leverkusen|SUBSTITUTED 3-- 2,2-DIMETHYL-CYCLOPROPAN-1-CARBONIC ACID ESTERS, METHODS AND INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION AND THEIR USE IN PEST CONTROL|

---

EP0074132B1|1981-08-31|1986-04-30|Shell Internationale Researchmaatschappij B.V.|Protection of crops against soil pests employing an alkylbenzyl cyclopropane carboxylate, novel cyclopropane carboxylates, and compositions containing them|

---

JPH0340181U|1989-08-11|1991-04-17|

---

DE102014107739A1|2014-06-02|2015-12-17|Jacques Tchouangueu|Mosquito net with insect trap|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

FR7628279A|FR2364884B1|1976-09-21|1976-09-21|MD94-0276A| MD222C2|1976-09-21|1994-09-08|Method of preparation of the isomeric substituted cyclopropancarbonic acids or their functional derivatives|