CN1304914A - Transform process for cis (or trans)-isomer of alkyl cyclohexyl benzene derivative - Google Patents
Transform process for cis (or trans)-isomer of alkyl cyclohexyl benzene derivative Download PDFInfo
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- CN1304914A CN1304914A CN 00123925 CN00123925A CN1304914A CN 1304914 A CN1304914 A CN 1304914A CN 00123925 CN00123925 CN 00123925 CN 00123925 A CN00123925 A CN 00123925A CN 1304914 A CN1304914 A CN 1304914A
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Abstract
A process for transforming cis (or trans)-isomer of alkylcyclohexyl benzene derivative is disclosed, in which halohydrocarbon or aliphatic hydrocarbon is used as solvent and passivated lewis acid as catalyst. Its advantages are low temp (0-5 deg.C), short period (at least 4 hr), high yield up to 90% or more and very low cost.
Description
The present invention relates to a kind of method for transformation of organic compound cis-trans-isomer, the cis-trans-isomer method for transformation of especially a kind of alkyl-cyclohexyl benzene derivative.
At present, when industrial system liquid crystal and liquid crystal intermediates, owing to have cis-trans-isomer along anti-cyclohexanes liquid crystal, and the cis-structure body must remove, and causes the cyclohexanes liquid crystal cis-structure body abandoned of widely applying, and causes waste, improved cost.For addressing this problem, Te Kaiping 58-189124 discloses a kind of method of carrying out the cis-trans-isomer conversion with potassium tert.-butoxide, principle is that the hydrogen on the carbon atom that is connected on the phenyl ring has slightly acidic, make it to form carbanion with highly basic, generate a copline intermediate with phenyl ring, eliminate the cis-structure body, be rearranged into stable transconfiguration body then, this method is only applicable to the stable liquid crystal of alkalescence, and exists potential safety hazard.Te Kaiping 5-201881 discloses a kind of method of carrying out the cis-trans-isomer conversion with Lewis acid, principle is that Lewis acid will be connected on the carbon atom on the phenyl ring and carry out isomerization, but this method is owing to used strong acid catalysis, isomerization generates carbonium ion easily and produces alkyl migration or disengaging, make the most of decomposition of target compound, thereby the reduction yield, and only limit to 4-[4 '-alkyl cyclohexane] conversion of 1-alkoxy benzene derivatives.
The objective of the invention is to overcome the deficiency of above-mentioned prior art and provide a kind of alkyl-cyclohexyl benzene derivative cis-trans-isomer that can make to transform smoothly, and make the target product rate of decomposition less than 1%, the transconfiguration body rate of recovery reaches the method more than 90%.
Purpose of the present invention can reach by following measure: the cis-trans-isomer method for transformation of alkyl-cyclohexyl benzene derivative, alkyl-cyclohexyl benzene derivative structural formula is
N=0 or 2 wherein, m=0 or 1, A=hexanaphthene or benzene (n=0), the alkyl of X=carbon atom 1～10 or alkoxyl group, cyano group, halogen F, CI, Br or hydrogen atom, Y, Z=F or hydrogen atom, isomer conversion solvent are halohydrocarbon or aliphatic hydrocarbon, and its characteristics are that temperature is-15 ℃～5 ℃, time was at least 4 hours, and catalyzer is the Lewis acid of passivation.
Purpose of the present invention can also reach by following measure: the Lewis acid consumption of the catalyst deactivation of the conversion usefulness of alkyl-cyclohexyl benzene derivative cis-trans-isomer is 0.5～1 times of alkyl-cyclohexyl benzene derivative cis-trans isomerism mixture mole number, the Lewis acid of passivation is the complex compound of Lewis acid and ethers, the mass ratio of Lewis acid and ethers is 1: 2, and Lewis acid is an aluminum trichloride (anhydrous).
Compared with the prior art the present invention has following positively effect: 1, because the used catalyzer of the present invention is the Lewis acid of passivation, its structure is
, AICI
3Formed complex compound with ethers, thereby reduced the activity of lewis acid catalyst, in reaction process, hexanaphthene and phenyl ring form the intermediate of two dimensional structure, eliminate cis-trans-isomer, reset then, generate stable trans-isomer(ide), hexanaphthene and phenyl ring do not disconnect; 2, taked above-mentioned temperature of reaction, solvent, catalyzer and consumption thereof, reaction times to make the conversion good stability of alkyl-cyclohexyl benzene derivative cis-trans-isomer; 3, owing to take present method to make that the transformation efficiency of alkyl-cyclohexyl benzene derivative cis-trans-isomer is very high, the rate of decomposition of target product is less than 1%, and the trans-isomer(ide) yield of alkyl-cyclohexyl benzene derivative reaches more than 90%; 4, owing to take present method to make cost reduce greatly.
Describe the present invention below in detail and provide several embodiment: the cis-trans-isomer method for transformation of alkyl-cyclohexyl benzene derivative, be applicable to: 4-[4 '-(trans-4 " alkyl cyclohexane) cyclohexyl]-the 1-alkylbenzene; wherein carbonatoms is 1～10; 4-[4 '-(trans-4 " alkyl cyclohexane) cyclohexyl]-the 1-alkoxy benzene, wherein carbonatoms is 1～10,4-[4 '-(trans-4 " alkyl cyclohexane) cyclohexyl]-the 1-fluorobenzene; wherein carbonatoms is 1～10; 4-[4 '-(trans-4 " alkyl cyclohexane) cyclohexyl]-the 1-alkylbenzene, alkoxy benzene, fluorobenzene, 1-[4 '-trans alkyl cyclohexane]-2-[4 " cyclohexyl] alkylbenzene; alkoxy benzene-ethane; wherein carbonatoms is 1～10; the 4[alkyl cyclohexane]-4 '-biphenyl derivatives; wherein, carbonatoms is 1～10.Solvent for use halohydrocarbon or aliphatic hydrocarbon, halohydrocarbon can be ethylene dichloride, chloroform, tetracol phenixin etc.Aliphatic hydrocarbon can be normal hexane, hexanaphthene, sherwood oil etc.The mol ratio of solvent and alkyl-cyclohexyl benzene derivative cis-trans-isomer is 10: 1, promptly in 10 parts of solvents, add a alkyl-cyclohexyl benzene derivative cis-trans-isomer, invert point is-15 ℃～5 ℃, time was at least 4 hours, catalyzer is the Lewis acid of passivation, Lewis acid is aluminum trichloride (anhydrous), anhydrous alchlor, Anhydrous Ferric Chloride, boron tribromide etc., but the aluminum trichloride (anhydrous) effect is best.Used ether is aromatic oxide, crown ether, aliphatic ether etc., is best with aromatic oxide especially.When isomerization reaction finishes, the gained reaction solution can carry out refinement treatment according to a conventional method.This reaction solution is washed with dilute hydrochloric acid, Lewis acid is decomposed, follow with halohydrocarbon or aliphatic hydrocarbon organic solvent extraction, the extraction after washing is to neutral, and the distillation that reduces pressure is again removed and desolvated, and gets target product.
Embodiment 1:
In the 2L reaction flask, add ethylene dichloride 800ml, lower the temperature 5 ℃, in 5 ℃, add AICI then
366.8g (0.5mol), add crown ether 120g then rapidly, temperature is controlled in 5 ℃, is added dropwise to 272g (1mol) under this temperature
, (cis: 43.3%, trans: as 53.9%), in 5 ℃, to be incubated 7 hours again, pour hydrolysis in the frozen water into, water extracts once with the 200ml ethylene dichloride again, merges oil phase, wash with dilute hydrochloric acid, wash with water again, the pressure reducing and steaming ethylene dichloride to neutrality, decompression is collected 140～150 ℃ under 20Pa again, obtains the 232g product, and G.C analyzes (cis: 3.38%, trans: 95.77%), yield 85% is used normal butane and ethyl alcohol recrystallization again, obtain product 189g, yield 69.5%, G.C analyzes 100%.mp:34.4-35.3。
Embodiment 2: get
F33g, (cis: 45.9%, trans: 44.8%), join in the reaction flask, 0 ℃ adds aromatic oxide 10g down, adds AICI
34.0g, stirred 8 hours, pour hydrolysis in the frozen water into, water is got once with ethylene dichloride 50ml again, merges, and pickling is washed to neutrality, concentrates to do, the G.C analysis (cis: 5.64%, trans: 83.2%)
In the embodiment 3:200ml chloroform, add AICI
313.3g, aliphatic ether 28g ,-15 ℃ were reacted 0.5 hour down, then will
30.6g (0.1mol) (cis: 41.3g, trans: as 42.1g) to add, insulation is 5 hours in-15 ℃, pours hydrolysis in the frozen water into, and water extracts once with the 100ml chloroform again, merge oil phase, be washed to neutrality, concentrate and do, obtain product 29.4g, the G.C analysis (cis: 2.24%, trans: 98.4%).
Embodiment 4: get
(12.7g cis 47.2%, trans 46.6%), sherwood oil joins in the reaction flask for 200 milliliters, and 0 ℃ adds ALCL down
34.2g, add crown ether 8.5g again, be stirred to 0 ℃, 0 ℃～5 ℃ following insulation reaction 5 hours, pour hydrolysis in the frozen water into, water extracts once with 200 milliliters sherwood oil again, merges, and is washed to neutrality, G.C check and analysis, cis 6.7%, trans 84.2%.
The comparative example of Comparative Examples 5:(embodiment 2 uses the not Lewis acid of passivation, and transformation efficiency is very low, and part is decomposed).Get
F33g, (cis: 45.9%, trans: 44.8%), join in the reaction flask, 0 ℃ adds ethylene dichloride 100ml, AICI down
33.77g 0 ℃ was reacted 2 hours, sampling, and hydrolysis, the G.C analysis (cis: 24.4%, trans: 22.9%)
Claims (5)
1, the cis-trans-isomer method for transformation of alkyl-cyclohexyl benzene derivative, alkyl-cyclohexyl benzene derivative structural formula is
N=0 or 2 wherein, m=0 or 1, A=hexanaphthene or benzene (n=0), the alkyl of X=carbon atom 1～10 or alkoxyl group, cyano group, halogen F, CI, Br or hydrogen atom, Y, Z=F or hydrogen atom, the isomer conversion solvent is halohydrocarbon or aliphatic hydrocarbon, it is characterized in that temperature is-15 ℃～5 ℃, time was at least 4 hours, and catalyzer is the Lewis acid of passivation.
2, according to the cis-trans-isomer method for transformation of the described alkyl-cyclohexyl benzene derivative of claim 1, the Lewis acid consumption that it is characterized in that passivation is 0.5～1 times of alkyl-cyclohexyl benzene derivative cis-trans isomerism mixture mole number.
3, according to the cis-trans-isomer method for transformation of the described alkyl-cyclohexyl benzene derivative of claim 1, the Lewis acid that it is characterized in that passivation is the complex compound of Lewis acid and ethers.
4, according to the cis-trans-isomer method for transformation of the described alkyl-cyclohexyl benzene derivative of claim 3, the mass ratio that it is characterized in that Lewis acid and ethers is 1: 2.
5,, it is characterized in that Lewis acid is an aluminum trichloride (anhydrous) according to the cis-trans-isomer method for transformation of claim 1,3 or 4 described alkyl-cyclohexyl benzene derivatives.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101820A (en) * | 2009-12-17 | 2011-06-22 | 默克专利股份有限公司 | Isomerization method |
| CN102408284A (en) * | 2010-09-21 | 2012-04-11 | 江苏广域化学有限公司 | Method for converting cis-substituted cyclohexyl in organic molecules into trans-substituted cyclohexyl |
| CN102659509A (en) * | 2012-04-01 | 2012-09-12 | 烟台海川化学制品有限公司 | Preparation method of biphenyl liquid crystal compound |
| CN103172528A (en) * | 2011-12-23 | 2013-06-26 | 烟台万润精细化工股份有限公司 | Tranexamic acid preparation method |
| CN110964538A (en) * | 2019-12-18 | 2020-04-07 | 江苏创拓新材料有限公司 | Transposition method of 1-cyclohexyl-2, 3-difluorobenzene |
| CN111233605A (en) * | 2020-01-19 | 2020-06-05 | 西安瑞联新材料股份有限公司 | Synthesis method of (trans ) -4-alkyl-4 '-alkyl-1, 1' -bicyclohexane |
-
2000
- 2000-10-02 CN CN 00123925 patent/CN1284751C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101820A (en) * | 2009-12-17 | 2011-06-22 | 默克专利股份有限公司 | Isomerization method |
| CN102101820B (en) * | 2009-12-17 | 2015-01-14 | 默克专利股份有限公司 | Isomerization method |
| CN102408284A (en) * | 2010-09-21 | 2012-04-11 | 江苏广域化学有限公司 | Method for converting cis-substituted cyclohexyl in organic molecules into trans-substituted cyclohexyl |
| CN102408284B (en) * | 2010-09-21 | 2013-12-25 | 江苏广域化学有限公司 | Method for converting cis-substituted cyclohexyl in organic molecules into trans-substituted cyclohexyl |
| CN103172528A (en) * | 2011-12-23 | 2013-06-26 | 烟台万润精细化工股份有限公司 | Tranexamic acid preparation method |
| CN103172528B (en) * | 2011-12-23 | 2014-10-08 | 烟台万润精细化工股份有限公司 | Tranexamic acid preparation method |
| CN102659509A (en) * | 2012-04-01 | 2012-09-12 | 烟台海川化学制品有限公司 | Preparation method of biphenyl liquid crystal compound |
| CN102659509B (en) * | 2012-04-01 | 2015-04-22 | 烟台海川化学制品有限公司 | Preparation method of biphenyl liquid crystal compound |
| CN110964538A (en) * | 2019-12-18 | 2020-04-07 | 江苏创拓新材料有限公司 | Transposition method of 1-cyclohexyl-2, 3-difluorobenzene |
| CN110964538B (en) * | 2019-12-18 | 2022-01-04 | 江苏创拓新材料有限公司 | Transposition method of 1-cyclohexyl-2, 3-difluorobenzene |
| CN111233605A (en) * | 2020-01-19 | 2020-06-05 | 西安瑞联新材料股份有限公司 | Synthesis method of (trans ) -4-alkyl-4 '-alkyl-1, 1' -bicyclohexane |
| CN111233605B (en) * | 2020-01-19 | 2023-02-10 | 西安瑞联新材料股份有限公司 | Synthesis method of (trans ) -4-alkyl-4 '-alkyl-1, 1' -bicyclohexane |
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