Process for producing cis- and trans-isomers of substituted dihalovinylcyclopropanecarboxylic acids

专利摘要:
1498931 Haloketones SUMITOMO CHEMICAL CO Ltd 2 Feb 1976 [12 Feb 1975 (4)] 04037/76 Heading C2C The invention comprises compounds of the formula where R 1 is H or alkyl, R 2 is C 1-6 alkyl, R 3 is H, C 1-6 alkyl, acyl or alkoxycarboxyl, X is Cl or Br and Y 1 , Y 2 and Y 3 are F, Cl or Br provided that when X is Cl each of Y 1 , Y 2 and Y 3 is F or Cl. The compounds may be prepared by reacting compounds of the formulµ The compounds may be treated with a base to yield compounds of the formulµ where R<SP>1</SP> 3 is H, C 1-6 alkyl, acyl, carboxy or alkoxycarbonyl, oxidation of which yields compounds of the formulµ Compounds of Formulµ III and V may be converted to compounds of Formulµ IV and VI, respectively, by treatment with a base.
公开号:SU940644A3
申请号:SU762322217
申请日:1976-02-11
公开日:1982-06-30
发明作者:Мацуо Такаси；Итая Нобусиге；Магара Осаму
申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
IPC主号:

专利说明:

39 -.-Alkyl or benzyl 3-phenoxybenzyl, oC-cyano-3 Phenoxybenzylgroup; X is a halogen, by dehalogenation of esters of halo-substituted carboxylic acids of the general formula product, or if R is C – C-alkyl by transesterification with alcohol, selected from the group that includes benzyl, 3-phenoxybenzyl or C — cy-3 phenoxybenzyl alcohol, from 0-200 0 2. However, the known method does not allow regulate the content of cisi trans isomer s get esters. The purpose of the invention is to provide the possibility of regulating the content of cis and trans isomers of substituted di-halovinylcyclopropane carboxylic acids or their esters. This goal is achieved by the fact that according to the method of producing derivative dihalovinylcyclopropanecarbonic acid of the formula
bnz
% x /
(J- - yook (I)
 Ji
R: hydrogen or C -C-alkyl; hydrogen, C-C-alkyl, or C-C4 alkoxycarbonyl; hydrogen or C - (- C4 alkyl;
Yt-dH-dH-d - ciQ-R B
-R SNZ
(iv):
C1H3

权利要求:
Claims (6)
[1]
where R, R, R, y, y, y3 have the indicated values by oxidation of the latter with sodium, calcium or potassium hypohalide, taken in 3 10-fold molar beat, at a temperature of from -20 to y and Y is fluorine, chlorine or bromine, using dehalogenation of halogen-substituted acids or esters in the presence of a strong base in a solvent medium, substituted alkylbutyl-3 or ketone of the general formula dHR C1H-C dH-ciOR (p) where R, R have the indicated values; R - C-Sc.-alkyl, is reacted with tetrahalomethane with the general formula. where Y is chlorine, fluorine, bromine; X is chlorine, bromine, moreover, if X is chlorine, then Y, U, U is chlorine or fluorine, at 30–200 ° C and a pressure of 1–50 atm in a neutral or amine type solvent in the presence of a radical initiator of divalent copper or iron or ot, C1-azobisbutyronitrile, or benzoyl peroxide followed by cyclization of the resulting compound of the general formula From 1 (YY, -d-CiHrC-CiH-CiOE (iB) where y, y, X, R, R, Rff have the indicated values; U1 or U, in the presence of an alkali metal hydroxide or calcium or an alkali metal alcoholate in an aqueous or organic solvent at a temperature pe from -20 to + 100 ° C, or a C-Cg-alkanol or water-alcohol solution at a temperature from -20 to + kQ ° C and atm pressure to form a compound of the general formula + 70 ° C and a pressure of 1-10 atm in water , alcohol or mixtures thereof to form a compound of the general formula d-ciH-ciH-b - cioop I, / B / e 1 dHj (where R, R2, R, y-y3 - have the above values, and its dehalation with a strong base with a molar ratio of 1: 2-20. The cyclization is carried out in the presence of caustic alkali at a temperature of from -20 to in methanol with a molar ratio of cyclized compound and alkali 1: 1-3. As starting materials, you can use k, -dimethylhexene-5-on-2 and carbon tetrachloride. Dehalidation is carried out by hydroxide alkali metal at the boiling point of the solvent. Carrying out the process of obtaining cis- and trans-isomers of substituted dihalovinylcyclopropanecarboxylic acids of the formula (|), thus, allows to obtain a compound with a given cis / trans ratio ranging from cis-enriched to trans-enriched under the choice of reaction conditions. Example 1, A. In 50 ml of tert, amyl alcohol is dissolved, 1 g (32.5 mmol), -dimethyl-5-hexene-2-one and 0.1 g (2% by weight of enon) copper (I) chloride, 0.1 g (2, k wt.% of enon) copper chloride dihydrate (I 1 g (2, wt. of enon) monoethanolamine and 15 g (97.5 mmol) of carbon tetrachloride. The mixture was heated under reflux for 12 hours. After removing the solvent under reduced pressure, 50 ml of water and 50 ml of benzene were added to the residue and the mixture was shaken. The benzene layer was washed with 20 ml of aqueous sodium chloride and dried over anhydrous sulfate After the removal of the ash under reduced pressure, the mixture is distilled under vacuum; 8 g (17.1 mmol) of 4, -dimethyl-5,7,7,7, -tetrahloroheptan-2-one is obtained in the form of an oil - yellow color. 6 T.KIP. PO-116 ° C / 1 MM PT.CT., refractive index, E70 (). NMR spectrum, cL (CCP4): 58 (IH, g, g, J 6, 5; 3.0 Hz; 3.25 (IH, g, g, J 16.0; 3.0 Hz); 2.91 (IH, g, g, J 16.0; 6.5 Hz); 2.80 (F, g, J = 17 Hz); 2.80 (IH, g, J 17 Hz); 2.10 (3H, s); 1.22 (ЗН, s); 1.06 (ZN, s). Exit 52.7. Found,%: C 37.9; H, 9; С 50.1 Calculated,%: С ЗВ, 6; H 5.0; CP 50.6 B. To a refluxed mixture of 52 g (366.7 mmol), dimethyl-5-hexene-2-one (89.0%), 127 g (925.5 mmol) of carbon tetrachloride , 500 mg (1 wt.% Of enone) copper (I) chloride, 20 mg (0, wt.% Of enone) copper (11) chloride (dihydrate) and 250 ml of tert-amyl alcohol are added dropwise over 2 hours into the solution obtained by dissolving 50, g (109 weightL from enon) monoethanolamine, 300 mg of chloride (0.6% by weight of enon) copper (I) and 10 mg (0.02 weightD from enon) copper chloride dihydrate ( Ii) in amyl alcohol, in an amount necessary to obtain a total volume of 100 ml. After completion of the reaction, the lower boiling point components are removed, the residue is diluted with water, extracted with ether, and after removal of the ether from the ether layer, the latter is distilled in vacuum; 88.5 g (289.5 mmol) 4, “- dimethyl-5,7,7,7-tetrachloroheptan-2-one are obtained; bp 90100 ° C / 0, nd mm Hg, purity 91.6%; yield 78.8%. The data of the IR spectrum, NMR and gas chromatography analysis of the product are consistent with the data for the product of Example 1A. Example
[2]
2. The process is carried out analogously to Example 1B, except that 27 g (825.5 mmol) of carbon tetrabromide are used instead of 127 g of carbon tetrachloride. 137.7 g (268.3 mmol), -dimethyl-5,7,7,7-tetrabromheptan-2-one are obtained. Bp , k mm Hg; purity 89.2% yield Found,%: C 2.3; H 3.3; Br 67.9 Calculated,%: C 23.6; H 3.1; Br 68.8 MK-cneKTp.Vwcmo cm clear 1726; 1370; 1260-1150. NMR spectrum, cL (CCE4): 4.63 (1H, g, g, J 7.2 Hz; J 3.2 Hz); 3.52, 2 (4H, m); 2.10 (ЗН, s); 1.22 (ЗН, s); 1.06 EF, s). Example
[3]
3. A mixture of 10.1 g (80.0 mmol), 4-dimethyl-5-hexene-2-one, 48 g (0 mmol) of trichlorobromomethane and 50 mg (0.5% weight from enone) d-, o1- Azobis-isobutyronitrile (ABIBN) is heated under reflux, added after 1 h and after 3 50 mg (0.5 ppm from the enone) ABIBN. After heating under the above conditions, the treatment is carried out for k hours as in Example 1B, and 3.1 g of the starting product and 3.7 g (37.6 mmol), -dimethyl-5-bromo-7, 7, are obtained. 7-trichloroheptan-2-one; bp 95-105 ° C / a, i) mm Hg, purity 89.0, yield, .0%. Found: C 25.3; H 3.6; halogen 65.1 Calculated: С 2b, 1; H 3 ;; halogen 66.8 IR spectrum, cm: clear 1727; 1368; 1271; 990. NMR spectrum, cL (SSB4):, 6 (1H, g, 9, J 7.1 Hz; J 3.0 Hz); 3.52, 2- (, m); 2.10 (ЗН, s); 1.22 (ЗН, s); 1.06 (ZN, s). Example
[4]
4. In 15 g (07.5 mmol carbon tetrachloride, 5.0 g (25.2 mmol) of 3-ethoxycarbonyl-4, 4-rimethyl-5 hexen-2-one is dissolved, and 0.3 g is added to the resulting solution. (6% by weight of enon) benzoyl peroxide. The mixture is heated for 3 hours in an autoclave at 120 ° C. The reaction mixture is washed with an aqueous solution of sodium sulfite, and then carbon tetrachloride is removed under reduced pressure. By distillation in vacuo, 8.4 is obtained (2, 7 mmol) 3-ethoxycarbonyl-, -dimethyl-5, 7,7, 7-tetrachloroheptan-2-one. T.KIP. 120-130 ° C / 0.7 mm Hg, refractive index 1.5018 (19, 5 Exit 9,
[5]
5. Example 5 5b g (183.2 mmol i, -dimethyl-5,7, 7,7-tetrachloroheptan-2-one (91,) is dissolved in 1 bO ml of methanol and the solution is cooled to 0 ° C. To this solution 80 ml of a methanol solution containing 9.6 g (mmol) of sodium hydroxide are added dropwise over 30 minutes at this temperature and stirred for 1 hour at a temperature from 0 to -5 ° C. Then the reaction mixture is diluted with water The mixture is neutralized with hydrochloric acid and extracted with ether, and distillation in vacuo gives C, 2 g (180.7 mmol) of 2,2-dimethyl-3-cis-trans (2, 2, 2-trichloroethyl) -cyclopropylmethyl ketone. 78-86 ° С / О, 6 mm r therefore, the cis / trans ratio is 91.5 / 8.5; purity is 99.6%. The yield is 98, according to NMR and gas chromatography analysis, the product is similar to the product of example 1. Example
[6]
6. To 60 ml of the methyl solution containing 2.9 g of sodium hydroxide, 10.0 g, 4-dimethyl-5, 7,7,7-tetrachlorohepgan-2-one is added at 25 ° C and the mixture is stirred for 2 hours at the same temperature The mixture is diluted with water and subjected to extraction with ether. After the ether layer was washed with water, the ether was distilled off. This leads to the formation of 8.0 g of 2,2-dimethyl-3- (2, 2,2-trichloroethyl) -cyclopropyl methyl ketone with a cis / trans ratio of 83/17, t. Bale. 75-82 with / / 1 mm Hg and yield 92. Example 7-The reaction is carried out analogously to example 6, except that the 4TQ mixture is stirred A h at 25 ° C, which results in 8.2 g of 2.2-dimethyl-3- (2.2.2 -trichloroethyl) -cyclopropyl methyl ketone with a cis / trans ratio of 78/22 and yield 94. Example 8. To 120 ml of a methanol solution containing 5.8 g of sodium hydroxide, 20.0 g of 4.4 are added dropwise in 10 minutes -dimethyl-5,7,7,7-tetrachloroheptan-2-one at 35 ° C and the mixture is stirred for 2 hours at. Next, the mixture is processed in the same way as described in Example 6 and 15.0 g of 2,2-dimethyl-3- (2,2,2-trichloroethyl) -cyclopropyl methyl ketone are obtained with a cis / trans ratio of 65/35 and a yield of 86. Example 9- 2.3 g (E, 4 mmol) (j) 2,2-dimethyl-3-cis, trans (2,2,2-trichloroethyl) -cyclopropyl methyl ketone (cis / trans 55 / ratio) was introduced into a 50-ml four-necked flask with a capacity of 50 ml. 45) and 15 g (20.1 mmol) of a 10% aqueous solution of sodium hypochlorite are added dropwise at a temperature. The mixture is stirred for 2 hours at the same temperature and then for 12 hours at 20-25 ° C. The reaction mixture is then extracted with 20 ml of benzene to remove unreacted product and acidified with 10% hydrochloric acid to pH t. The aqueous layer was extracted with 30 ml of benzene, the benzene layer was washed with 20 ml of water, and the benzene was removed by evaporation. By distillation in vacuum, 1.85 g (7.5 mmol) of the desired (t) 2,2-dimethyl-3-cis, trans- (2,2,2-trichloroethyl) cyclopropane-1-carboxylic acid (cis / trans) in the form of a clear, colorless oil. T. Kip. 120-130 ° C / 0, it mm Hg, the refractive index 1.5020 (2lc) yield 80.0%. H 46.1; C6 42, Found, 1; H 45.2; Calculated it, s IR spectrum, l) msz.c .; cm-3400-2 00; 1705; 1250; 805 NMR spectrum, сА (ССе4): 11.80 (1H, s 3.20-2.60 (2H, M); 2.00-1, + 0 (2H, m) 1, -fjO-1.20 (CH KB) .Example 10. In a four-necked flask with a capacity of 50 ml, add 3.5 g (11.1 mmol) of (+) 1-ethoxycarbonyl-2, 2-dimethyl-3-cis, trans- (2, 2 - trichloroethyl) cyclopropyl methyl ketone (cis / trans-55/5 ratio) and 20 g (26.9 mmol) of 10% aqueous sodium hypochlorite aqueous pacTBO ra are added dropwise at 0-5 ° C. The mixture is stirred for 2 hours at the indicated temperature and 15 hours at 20-25 0. Then the reaction mixture is extracted with 20 ml of benzene to remove unreacted product and the aqueous layer is acidified with 10% hydrochloric acid to pH 1. Aqueous The layer is extracted with 30 ml of benzene, the benzene layer is washed with 20 m of water and the benzene is removed under reduced pressure. 1.9 g (6.0 mmol) of (t) 1-ethoxycarbonyl-1-carboxylic acid are obtained by distillation in vacuum (ratio: cis / trans 55/45) as an oil of light yellow color, bp 140-145 ° C / 0.1 mm Hg 1.5163 (21C), the refractive index is 53.9%. Found,% : C 42.3; H 4.7; CE 33.8 Calculated, C 41.6; H 4.8; All 33.5 IR spectrum, clear , VMOIKC 3400-2400; 1740-1700; 1476; 1210; 800. 10 NMR spectrum, cL (CCP4): 11.90 (1H, s); , 10 (2H, q, J 8.0 Hz); 3.202, 60 (2H, m); 2.00-1.30 (1H, m); 1.30 (6H, s); 1.23 (ZN, t, J 8.0 Hz). Example 11. To 250 ml of a solution containing 3 g of g (0.9 mol) of sodium hydroxide and methanol, 26.8 g (0.11 mol) of 2,2-dimethyl-3 (2,2,2-trichloroethyl) were added. -cyclopropyl methyl ketone (purity 97.9%, with a cis / trans ratio of 91.5 (8.5) with ice cooling, absorb 100% of chlorine from the surface of the solution for 100 min. and mix for 30 minutes After that, 25.2 (0.1 mol) of sodium sulfate (seven times) and 200 ml of water are added, the mixture is stirred for 30 minutes to decompose the excess hypochlorite. The reaction mixture is acidified with concentrated hydrochloric acid, separated extracted with ether and the aqueous layer is mixed with the separated organic layer and washed with an aqueous solution of sodium bicarbonate and then with a saturated solution of sodium chloride. After the ether is distilled off, the distillation is carried out in a vacuum and 3.3 g (0.028 mol) of methyl ether are obtained 2,2-dimethyl-3- (2,2,2-trichloroethyl) -cyclopropanecarboxylic acid. Cyp. 77 ° C / 0.4 mm Hg, cis ratio / / trans 88/12. Found,%: C 42.7; H 5.2; Calculated,%: C 41.6; H 5.0; SS 41.0 IR spectrum, clear. cm 1700; 1290; 1290; 770; 715 NMR spectrum, o (CCe4): 3.55 (3N); 3.20-0.60 (2H, m); 1.70-1.30 (2H, m); 1.25 (6H, s). Purity 87.89%; yield 26.3%, and 15 g (0.05b mol) of 2,2-dimethyl-3 (2, 2, 2-trichloroethyl) cyclopropanecarboxylic acid. According to NMR and gas chromatographic analysis, in terms of methyl ether using diazomethane, the product is consistent with the product of example 1. So b.p. 104 120С / 0, 4 mm Hg, cis / trans ratio 82.8 / 17.2, purity 91.8%; yield 52.0%. After acidifying the aqueous solution of sodium bicarbonate, 1.4 g (0.006 mol) of 2,3-dimethyl-3 (2,2,2-trichloroethyl) cyclopropanecarboxylic acid are obtained. 11E Example 12. Into a flask with a capacity of 20 ml, 3.0 g (12.2 mmol) (1, 2, 2-dimethyl-3-cis, trans- (2, 2, 2-trichloroethyl) cyclopropane-1-carboxylic acid (cis / trans ratio) and 10 g added dropwise at room temperature (25 mmol of an aqueous aqueous solution of caustic per pa. After heating under reflux for 5 hours, the reaction mixture is acidified to pH 1 with hydrochloric acid and extracted with 50 ml of benzene. The benzene layer is washed with 20 ml of an aqueous solution of sodium chloride and dried over anhydrous magnesium sulphate. After removing benzene under reduced pressure In this way, distillation is carried out under vacuum and 2, k g (11.5 mmo target (t) -2,2-dimethyl-3 cis, trans - (2,2-dichlorovinyl) cyclopropane-1 carboxylic acid (cis / trans ratio) are obtained in the form of a clear, colorless oil. T. bale. lOO-IIO / o, l mm mm Hg, refractive index is not 1.5117 (); yield 9.0. According to NMR and gas chromatographic analysis, this product is consistent with the product of example. 9 (acid is considered as methyl ester obtained by interaction with diazomethane). Example 13. A gaseous solution of 0.92 g (40 mmol) of metallic sodium in methanol is added with g (26.3 mmol) of 2,2-dimethyl-3- (2, 2,2-trichloroethyl) cyclopropanecarboxylic acid methyl ester (purity 87.8%, cis / t. Trans ratio-88/12), and the resulting mixture was heated under reflux for 35 hours. After distilling off the methanol, the mixture was diluted with hydrochloric acid and extracted with ether. The ether layer is washed with an aqueous solution of sodium bicarbonate and with a saturated aqueous solution of sodium chloride, and then the ether is distilled off. When distilled under vacuum, 5. g (1.3 mmol) of 2,2-dimethyl-3- (2, 2, -dichlorovinyl) cyclopropanecarboxylic acid methyl ester are obtained, b.p. 64-72 ° C / 1.2 mm Hg The cis / trans ratio was 90.9 / 9, l, purity 87.8%, yield 79.8%. Upon acidification of the washing aqueous solution of sodium bicarbonate, 0.5 g of 2,2-dimethyl-3- (2, 2-dichlorovinyl) cyclopropanecarboxylic acid is additionally obtained. All data NMR and gas chromatograph analysis of these products are similar to the data of example 9 (the acid in gas chromatography is calculated as methyl ester). An example. To 120 ml of a solution of 4.8 g (120. mmol) of sodium hydroxide in methanol was added 11.1 g of C, 5 mmol) of 2,2-dimethyl-3- (2, 2.2 trichloroethyl) cyclopropanecarboxylic acid (purity 91, 8%, cis / trans-82.8 / 17.2) ratio, and the resulting mixture is heated with reflux. NIKOM 37 hours. The mixture is then diluted with water and the neutral part is removed by extraction with ether. The aqueous layer is acidified with concentrated hydrochloric acid and extracted with ether. The ether layer is concentrated and 8.15 g (Gt, 0 mmol) of 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid: lot1 (cis / trans ratio 79.8 / 20.2, purity 92 , 4%, yield 86.8%). Example 15-The process is carried out similarly to the previous example, except that 5 g (18, mmol) of 2.2 dimethyl-3 methyl ester are added to a mixture of k g (100 mmol) of sodium hydroxide, 20 ml of methanol and 30 ml of water. 2, 2.2-trichloroethyl) -cyclopropanecarboxylic acid (purity 95.8%, cis / trans ratio 92.7 / 7.3), and the resulting mixture heated under reflux for 10 hours. Get 3.31 g (15.3 mmol) 2,2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropanecarboxylic acid (cis / trans ratio 98.8 / 1.2, purity 9b,%, yield = 8%). Claim 1. Investigation method for cis- and then ns-isomers of substituted dihydvinylcyclopropanecarboxylic. acids or their esters of the general formula y, 1 s / cid-Cii l-C-doop hydrogen or C-C4 alkyl; hydrogen, C-C-alkyl, or C-C4-alkoxy-, carbonyl;

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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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JP50018295A|JPS5195043A|1975-02-12|1975-02-12| beeta jiharogenoetenirushikuropuropanjudotaino seizohoho|

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JP1829775A|JPS5721173B2|1975-02-12|1975-02-12|

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JP50018298A|JPS6059221B2|1975-02-12|1975-02-12|

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JP50018296A|JPS5195010A|1975-02-12|1975-02-12|Arukiru 35555 tetoraharogenopenchiruketonjudotainoseizohoho|

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