Process for producing esters of substituted cisor trans-cyclopropanecarboxylic acids and alpha-cyano

专利摘要:

公开号:SU969154A3
申请号:SU792774001
申请日:1979-06-05
公开日:1982-10-23
发明作者:Мартель Жак；Тессье Жан
申请人:Руссель Юклаф (Фирма)；
IPC主号:

专利说明:

The resulting product is isolated or, if necessary, an ester of the formula I (I, 3) -c6fuction is treated with an aliphatic amine in a lower aliphatic alcohol at a temperature of from -5 to (S) -configuration. Example 1. K, 8) -o cyano-3phenoxybenzyl ester (lR, TpaHcJ 2; 2-dimethyl-3- (cyclopentylidenemethyl cyclopropane-1-carboxylic acid. In a solution of 2.8 g of SJ, 5) -o-cyano-3phenoxybenzyl alcohol in 10 mg of anhydrous benzene was added 1.5 ml of pyridine. The temperature was kept around and 3.17 g of (1K, trans) -2,2-dimethyl-3 (cyclopentyldenmethyl) cyclopropy-1 carboxylic acid chloride in benzene was added. After stirring for 20 hours, 20 ml of a dilute solution of hydrochloric acid are added, and then extracted with methylene chloride. The layers are separated organically, spread with water, dried After purification by chromatography on silica with ethyl cyclohexa eluate ethyl acetate (9-1. 3.5 g of the expected product is obtained with a molecular weight of 401, 510, ot20, -2b5 + 2 (, 7% in benzene). Elemental analysis: Calculated,%: C 77.78; H 6.78; N 3.48. CjfcHj Q Found,%: C 77.7; H 6.9; N 3.3. For m p 2 (ZZ -o-cyano-3-phene hydroxybenzyl ester (1R, TpaHc) -2,2-dimethyl-3- (cyclopentylidenemethyl) cyclopropane-1-carboxylic acid. 2 g of (R, S) (, -Cyano-3-phenoxybenzyl ester of (lR, trans) -2,2-dimethyl3- (cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid is introduced into 4 cm, isopropanol and added 0.2 cm of ammonium hydroxide. After 24 hours of stirring, add 3 cm of petroleum ether (k.60.80 ° C), re-mix for 48 hours. The crude mixture is triturated in benzene, concentrated under reduced pressure, introduced into 4 cm isopropanol and 0.2 cm ammonium hydroxide.After 5 days of stirring at -5JC, filter off and then wash with icy isopropanol, the crude crystallized product Crystals are dissolved in acetone, concentrated under reduced pressure, and 1.225 g of crystalline target product is obtained, mp oL | p -18 + 1 (in benzene). The NMR spectrum determined on the crystallized product shows that it contains 10% (R) -o6-cyano-3-phenoxybenzyl ester (lR, trans) -2,2-dimethyl-3- (cyc / 10pantylene1 ethyl) -. Cyclopropan-1-cary acid; stock solutions containing non fermented the initial product (R, S) is the “i-cyano-3-phenoxybenzyl ester (lR, TpaHc) -2,2-dimethyl-3- (cyclopentyldenmethyl) .- cyclopropane-1 carboxylic acid, which is defined Helen NMR spectrum and 04% -29. Example 3. (5) - / -cyano-3phenoxybenzyl ester (lR, TpaHc) 2, 2-dimethyl-3- (cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid. 3.1 g (I, 8) -c (-g Cyano-3-phenoxybenzyl ester (1R-, trans) -2,2-dimethyl-3- (ciclopentylidenemethyl) cyclopropane-1-carboxylic acid is introduced into 7 cm of isopropanol, and then 0.2 ml of triethylamine is added. After {24 hours, stirring at | P ° G, and then after 4 days stirring at -5 ° C) and liter, the resulting product is washed with ice-cold isopropanol dissolved in acetone and concentrated under reduced pressure. 1.644 g of crystalline target product are obtained having the same constants as the product described in Example 2. Example 4. (5) -1.-Cyano-3phenoxybenzyl ester (lR, TpaHc) 2, 2-dimethyl-3- ( cyclopentylidenemethyl) cyclopropane-1-carboxylic acid. ; 4.38 g of benzene was introduced into 50 cm; chloride (lR, trance) -2,2-dimethyl-3 (cyclopentylidenemethyl) cyclopropane-. 1-carboxylic acid, 4.8 g- (S) - "i-cyano-3-phenoxybenzyl alcohol tW) -15.5 + 1, to 1.3% in benzene, is slowly added at 5 cm pyridine, stirred in for 20 hours, the reaction mixture is poured into an aqueous solution of hydrochloric acid that has been pre-cooled to 5c, extracted with benzene, the organic layer is washed with sodium bicarbonate and then with water, dried and concentrated to dryness by distillation under reduced pressure. Chromatograph the residue on silica gel, eluting with a mixture of petroleum ether (b.p., 35-70 sec.) And ethyl ether. Acetic acid (9-1), 5.08 g of crude product (m.p.) are obtained, the product is recrystallized 6 volumes of isopropanol and collect 4.2 g of the target product, so pl. . -11 ± 2 (, 6% in benzene). Molecular weight 401.51. Elemental analysis: Calculated,%: C 77.77; H 6.78; N 3.49. b (g Haydeno,%: C 77.8; H 6.8; Found, N -3.3., NMR spectrum (deuterochloroform): peaks at 1.13-1.20 ppm for hydrogens paired methyls replacing cyclopropyl; peaks at 1.42-1.51 parts per μplion, characteristic for hydrogens in position 1 and 3 cyclopropyl; peaks at 1.50-1.83 parts per million hydrogens in position 3 and 4 cyclopentyl ; peaks at 2.00-2.50 parts per million of hydrogens in position 2 and 5 of cyclopentyl; peaks at 4.955, 08 parts per million of ethylene hydrogen; peaks at 6.90-7.5 parts per million, characteristic for aromatic hydrogens.
Circular dichrose (dioxane); i -8 at 224 mmk (max); D. 8 +0.28 at 283 mmk (max); d +0,3 at 287 MMK (max).
Source (8) -cyano-3-phenoxybenzyl alcohol can be obtained as follows.
A. A mixture of PC, 55) -6,6-dime Il-4 (K) C (5) -cyano (3-phenoxyphenyl) methoxy-Zd3-oxabicyclo- (3,1,0) -hexan-2-one il (1R , 5S) -b, 6-dimethyl-4 (R) - C (R) -cyan (3-phenoxyphenyl) methoxy-3-oxabicyclo- (3,1,0) -hexan-2-one.
22.5 g of (K, 5) -o (.-Cyano-3-phenoxybenzyl alcohol) are mixed} 9.46 g of cis-2,2-dimethyl-35 (dioxymethyl) -cyclopropane-lR-carboxylic acid lactone and 0.150 g of monohydrate paratoluenesulfonic acid is heated to vacuum in Hg and the reaction mixture is kept under these conditions for 2 hours, the water thus formed is removed by distillation. The mixture is cooled and 30.70 g of (1R, 5S) -b, b-dimethyl-4 is obtained. (R) j (S) -cyano- (3-phenoxy phenyl) MeTOKCHj, 3-oxabicyclo- (3,1,0) -hexan-2-one and (1R, 5S) -b, b-dimethyl-4 ( R) -G (R) cyano- (3-phenoxyphenyl) methoxy-3 oxabicyclo- (3,1,0) -hexan-2-one, containing as Esses are mainly unreacted starting materials (mixture A).
B. (1R, 5S) .- b, b-dimethyl-4 (R) - (S) cyano- (3-phenoxyphenyl) methoxy-3-x-x-cyclo- (3,1,0) -hexan-2-one.
The resulting mixture A is chromatographed on silica gel, eluting with a mixture of benzene-ethyl acetate (95-5), and 10.9 g (1R, 5S) b, b-dimethyl-4 (R) -CZ) -cyano- (3 -phenoxyphenyl) methoxyZ-3-oxabicyclo (3,1,0) -hexan-2-gon (Compound B) of T.L2b ° C; 3L -71® (in benzene). .
UV spectrum (ethanol): inflection at 226 mmk ("319); kink at 267 mcc (E 52); kink at 271 MMK (EJ 56); maximum at 276 KIMK (ECH - 60) and a bend at 280 MMK (E :; 48).
. Circular dichroie (dioxane): De 4,2 at 225 mmk (max) and Ai +0.39 at 287 mmk (max).
B. (5) -in-cyano-metaphenoxybenzyl alcohol.
10 g of the obtained compound B are introduced into a mixture of 100 cm of dioxin and 50 cm of water, and then 1 g of monohydrite p-toluenesulfox sputum is heated, the reaction mixture is heated under reflux, maintained at boiling for 23 hours, concentrated by distillation under reduced pressure to to obtain half of the original volume, add ethyl acetate, stir the organic layer by decantation, wash it with water, dry it and concentrate to dryness by distillation under reduced pressure. The residue is chromatographed (9.5 g) on silica gel, eluting with a mixture of benzene-ethyl ester of acetic acid (9-1), to give 6.1 g of (5) -in cyanomephenoxybenzyl alcohol, -1b, 5 ± 1.5 (, 8 % in benzene).
NMR spectrum (deuterochloroform): peak at 3.25 ppm x, characteristic of hydrogen hydroxyl group; the peak at 5.42 ppm is characteristic of hydrogen on the same carbon as the nitrile group.
Example 5. (R, S) -e.-cyano-3phenoxybenzyl ester (lR, cis) 2, 2-dimethyl-3-cyclopentylidenemethylcyclopropane-1-carboxylic acid.
Act as in Example 1, but proceeding from 11 g of (R, S) -ct-cyano-3-phenoxybenzyl alcohol and 15.3 g of chloride (lR, cis) -2,2-dimethyl-3-cyclopentylidenemethylcyclopropane-1-carboxylic acid and after purification by chromatography on silica and elution with a mixture of cyclohexane-ethyl acetate (9-1) and then with benzene, 7.5 g of the expected product are obtained, o (% +32 i2U 0.5% in benzene). Mol mass is 401.507.
Elemental analysis:
Calculated,%: C 77.78; H 6.78; N, 3.49.
Found,%: C 78.1; H 6.8; N 3,5 ..
P, p and m b. (5) C.-Cyano-3-phenoxy-benzyl ester (lR, cis) -2,2-dimethyl-3-cyclopentylidene methylcyclopropane-1-carboxylic acid.
Act as in Example 5, but starting from 4.4 g of chloride (lR, cis) -2,2-dimethyl-3-cyclopentylidenemethylcyclopropane-1-carboxylic acid and 4.5 g of (8) - "6-cyano-3-phenoxybenzyl alcohol, and after purification by chromatography on silica and elution with a mixture of benzene-cyclrhexane (7-3), 1 g of the desired product with a molecular weight of 401.507, oLb +85, (, 4% in benzene) is obtained.
Elemental analysis:
Calculated,%: C 77.78; H 6.78; N 3.49.
", N0
Found %: C 78.0; H 6.8; N 3.4.
Example 7. (5) -o1-cyano-3phenoxybenzyl ester (1K, cis) -2,2 dimethyl-3-cyclobutylidene methylcyclopropane-1-carboxylic acid.
Act as in Example 1, but starting from 2.5 g of chloride (lR, cis) -2,2-dimethyl-3-cyclobutylated-methyl-cyclopropan-1-carboxylic acid and 3 g of 5) -o6-cyano-3-phenoxybenzyl alcohol, and after purification by chromatography on silica and elution with benzene, 1.9 g of a cel-product with a molecular weight of 387.479, +95 ± 3 (, 54% in benzene) are obtained; tpl ..
Elemental Anshiz:
Calculated,%: C 77.49; H 6.50; N 3.61.
(g
Found,%: C 77.2; H 6.3; N 3.5.
Example 8. (E, 5) -o6-cyano-3phenoxybenzyl ester {1K, cis) -2,2. Dimethyl-3-cyclobutylidenemethylcyclopr-1-carboxylic acid.
The procedure is as in Example 1, starting with 2.5 g of (1H, cis) -2,2-dimethyl-3-cyclobutylidenemethylcyclopropane-1-carboxylic chloride and 3 g of (R, S) -s.-cyano-3-pheno: ibenzyl alcohol, and after purification by chromatography on silica and elution with benzene, 2.5 target products with a molecular weight of 387.479 ° are obtained. 47 ± 0.5 (in benzene).
Elemental analysis: Calculated,%: C 77.49; H 6.50; NJ, 61.
Kaidano,%: C 77.3; H 6.3;
N 3.6.
Example 9. (5) -Oycyano-3phenoxybenzyl ester (1K, cis) -2,2 dimethyl-3-cyclobutylidenemethylcyclopropane-1-carboxylic acid.
2 g of (K, 5) -C.-cyano-3-phenoxy-benzyl ester (1E, cis) -2,2-dimethyl3-cyclobutylidenemethylcyclopropane-1carboxylic acid is added to 8 cm from propanol and 0.08 cm of triethylamine is added. . Seeding of several crystals of the target product obtained in the previous example is stirred for 16 hours at 20 ° C and obtained after separation of 1 g of the crystalline target product with a molecular weight of 387.479; .9.5 (, 9% in benzene); mp.76C.
Elemental analysis: Calculated,%: C 77.49; H 6.50;
N 3.61.
-is found,%: C 77.3; H 6.5; 5 N 3.7.
The NMR spectrum (CDCl-j) indicates the absence of ester of (R) -oi-cyano-3-phenoxybenzyl alcohol.
Example 10 (5) -c-diano-310 phenoxybenzyl ester (1R, trans) 2, 2-dimethyl-3-cyclobutylidenembethylcyclopropane-1-carboxylic acid.
The reaction is carried out analogously to example 1, but starting from 2.5 g of chloride 5 (1R, trans} -2,2-dimethyl-3-cyclobutylidenemethylcyclopropane-1-carboxylic acid 2.2 g of (5) -v / .- cyano- 3-phenoxybenzyl alcohol and, after purification by chromatography on silica, eluting with petroleum ether-ethyl ether (9-1), obtain 1.2 g of the desired product, molecular weight 387.479of 12 +1 (in benzene). 5 Elemental analysis:
Calculated: C 77.49; H 6.50; N 3.61.
Found,%: C77.3; H6.6;
0 3,5 ..
Example 11. (R, S) -ab-cyano-3-. (1R, trans) 2, 2-dimethyl-3-cyclopropylidenemethylcyclopropane-1-carboxylic acid phenoxybenzyl ester.
The reaction is carried out analogously to example 1, but starting from (1R, trans) -2,2-dimethyl-3-cyclopropylidenemethylcyclopropane-1-carboxylic chloride, prepared from 5.5 g of the corresponding acid and 7.5 g
0 (R, S) -oL-cyano-3-phenoxybenzyl alcohol, and after purification by chromatography on silica and eluting with benzene-petroleum ether (8-2), 4.2 g are obtained
5 target product; oL -40.5
(, 8% in chloroform); molecular weight 373,428.
Elemental English: Calculated,%: C 77.19; H 6.21; N 3.75.
| Found%: C 77.1; H 6.2;
N 3.5.
Example 12. (5) -o6-cyano-3phenoxybenzene ester (1R, trans) 2, 2-dimethyl-3-cyclopropylidenemethylcyclopropane-1-carboxylic acid.
The reaction is carried out analogously to example 1, but starting from chloride (1R,
trans) -2,2-dimethyl-3-cyclopropylidenemethylcyclopropane-1-carboxylic acid, prepared on the basis of 16 g of the corresponding acid and 27 g of (S) -c. 1-dano-3-phenoxybenzyl alcohol, and

权利要求:
Claims (2)
[1]
5 after purification by chromatography, cnoqo6oM on silica and eluent mixtures of benzene-petroleum ether (8-2), 16.7 g of the expected product are obtained, ot | ° -38.5 ° +, 5 (in chloroform ;; molecular weight 373.428. Elemental analysis: Calculated,%: C 77.19; H 6.21; N 3.75. Found,% C 77.0; H 6.1; N 3.5. (R, S) - "J - UHaHo3-phenoxybenzyl ester (1H, cis) 2, 2-dimethyl-3-cyclopropylidenemethyl cyclopropane-1-carboxylic acid. The reaction is carried out similarly with measure 1, but the outcome of their chloride (1K , c 2,2-dimethyl-3-cyclopropylidenemethyl diclopropane-1-carboxylic acid, obtained from 3.5 g corresponding acids and 4.8 g of (K, 5) -o1. Cyano-3-phenoxybenzyl alcohol, and after chromatography on silica, eluting with benzene-petroleum ether (8-2), 4 g target product with a molecular weight of 373.428; oL +48 +1.5 (, chloroform). Elemental analysis: Calculated,%: C 77.19; H 6.21; N 3.75 Found,%: C 76.7 ; H 6.2; 3.7. Example 14. (5) -c-cyano-3-feioxybenzyl ester (1K, cis) 2, 2-dimethyl-3-cyclopropylidenemethylcyclopropane-1-carboxylic acid. The reaction is carried out analogously to example 1, starting from C1H, cis) 2,2-dimethyl-3-cyclopropylidenemethylcyclopropane-1-carboxylic chloride and 15 g of (5) -o-cyano-3-phenoxybenzyl alcohol, and after purification by chromatography on dioxide silicon, eluting with a benzene-petroleum ether (8-2) mixture, afforded 8.6 g of a target product with a molecular weight of 373, .555 (k, chloroform). Elemental analysis: Calculated,%: C 77.19; H 6.21; N 3.75. Found,%: C 76.2; H 6.1; N 3.6. . For the determination of insecticidal activity, Epilachna Varivesteis larva was used as a test, with IT carrying out a topical application of 1 ml of an acetone solution of the test compound to the dorsal thorax of each larva at the last larval stage and after treatment the larvae are fed with seedlings of the beans. Efficiency control (percentage of mortality versus control) was carried out 24 hours after treatment and the lethal dose was determined for each individual. The data obtained in comparison with the known compound are presented in the table. 11 As can be seen from the table, the proposed compounds are more active than the known. The invention method for producing ester-substituted cis or trans-cyclopropane carboxylic acids and o4-cyano-3-oxybenzyl alcohol (S) - or (R, S) - configuration of total formula 1ede P: 1-3, O TL and h and y and i with the fact that 1 chloride cyclopropanecarboxylic acid with the general formula 2. 54 VN / CO Hv ,, -OH where p has the indicated values is reacted with "/ -cyano-3-phenoxybenzyl alcohol (S) - or (R, S) -configuration in the presence of a tertiary aromatic amine in an aromatic hydrocarbon at 20-25 ° C, The resulting product is isolated or, if necessary, the ether (R, S) -configuration is treated with an aliphatic amine in a medium of lower aliphatic alcohol at a temperature of from -5 to 5 ° C to translate into an (S) -configuration. Priority by featured. 06.06.78p 3. 05.06.79p 1.2. Sources, information Bo received attention during examination 1.Patent of France. 2354998, class C 07 C 121/70, published 13.01.78.
[2]
2. The patent of France 2240914, cl. C 07 C 69/74, published 1975.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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FR1505423A|1966-08-26|1967-12-15|Roussel Uclaf|New derivatives of cyclopropane and method of preparation|

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JPS515450B1|1971-06-29|1976-02-20|

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CH611593A5|1973-08-15|1979-06-15|Nat Res Dev|Process for the preparation of a cyclopropanecarboxylic acid ester|

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FR2341307B1|1976-02-19|1982-07-30|Roussel Uclaf|

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FR2375161B1|1976-04-23|1979-04-13|Roussel Uclaf|

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FR2384494B2|1977-03-25|1982-09-17|Roussel Uclaf|FR2471187B1|1979-12-10|1984-07-27|Roussel Uclaf|

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FR2522323B2|1981-04-16|1989-07-21|Roussel Uclaf|NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID, THEIR PREPARATION METHOD, THEIR APPLICATION TO THE CONTROL OF PESTS|

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FR2533556B1|1982-09-29|1985-03-22|Roussel Uclaf|

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EP0312124A3|1982-11-22|1989-09-13|E.I. Du Pont De Nemours And Company|Process for the preparation of optically-active cyanomethyl esters|

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FR2686602B1|1992-01-28|1994-03-11|Roussel Uclaf|NOVEL DERIVATIVES OF 2,2-DIMETHYL ACID 3 - [(2,2-DIFLUOROCYCLOPROPYLIDENE METHYL] CYCLOPROPANE CARBOXYLIC, PROCESS FOR THEIR PREPARATION AND THEIR USE AS PESTICIDES.|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR7816858A|FR2428029B1|1978-06-06|1978-06-06|

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