CN100497285C - Method for synthesizing inverse-4-(inverse-4'-alkyl cyclohexyl) cyclohexyl methyl aldehyde - Google Patents
Method for synthesizing inverse-4-(inverse-4'-alkyl cyclohexyl) cyclohexyl methyl aldehyde Download PDFInfo
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- CN100497285C CN100497285C CNB2007100177849A CN200710017784A CN100497285C CN 100497285 C CN100497285 C CN 100497285C CN B2007100177849 A CNB2007100177849 A CN B2007100177849A CN 200710017784 A CN200710017784 A CN 200710017784A CN 100497285 C CN100497285 C CN 100497285C
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Abstract
The invention discloses a synthesizing method of inverse -4- (inverse-4'-alkyl group cyclohexyl) cyclohexyl oxymethylene, which comprises the following steps: choosing 1-methoxyl methine-4- (inverse-4'-alkyl group cyclohexyl) as raw material; proceeding hydrolytic reaction under accelerant function of silica gel solid carrier sulfonic acid; heating continually; proceeding isomerization reaction; getting the product. This invention possesses simple operation and easy to separate, which is fit for industrial production.
Description
Technical field
The present invention relates to a kind of important liquid crystal intermediates anti--synthetic method of 4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzaldehyde, its structural formula is shown in (I):
R is that carbonatoms is 1～7 straight chained alkyl in the formula.
Background technology
The cyclohexanes liquid crystal is the liquid crystal that contains the hexanaphthene skeleton, because of having the stability of height, and the nematic phase warm area of broad and be subjected to people's favor.Behind the hexanaphthene substituted benzene ring, the πDian Zi system reduces, and charge distribution density reduces, and polarization weakens, thereby fusing point is lower, but its clearing point has increase trend.Another advantage of using hexanaphthene replacement phenyl ring is the reduction of viscosity, overcome and at present still widely usedly contain that phenyl ring skeleton liquid crystal viscosity is big, the slower shortcoming of response speed, the cyclohexanes liquid crystal material becomes the indispensable active principle of medium-to-high grade mixed liquid crystal material day by day.Instead-4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzaldehyde is the synthetic very important intermediate of this class liquid crystal material, so it synthetic has significant application value.Introduce among the Chinese patent CN02103898.8 with instead-4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzoic acid is a raw material, be reduced to instead-4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzyl alcohol through lithium aluminium hydride, generate anti--4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzaldehyde through the oxidation of chromium trioxide pyridine hydrochloride again, the used prices of raw and semifnished materials of this method are higher, and generation contains the chromium refuse, easily pollutes environment.
Summary of the invention
The invention provides a kind of " one kettle way " preparation anti--method of 4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzaldehyde (I), its building-up reactions formula is as follows:
The present invention is a raw material with 1-methoxyl group methyne-4-(anti--4 '-alkyl-cyclohexyl) hexanaphthene (II); reaction solvent is normal heptane-tetrahydrofuran (THF)-water mixed solvent; add the supported on silica-gel sulfonic acid catalyst; reaction system charges into the helium protection, heat temperature raising to 40 under stirring～50 ℃, and the reaction times is 10～15 hours; reaction is hydrolyzed; system temperature is risen to 60～70 ℃ then, carry out isomerization reaction, reaction continues 5～10 hours.Reduce to room temperature after reaction finishes, remove by filter catalyzer, filtrate obtains the faint yellow solid crude product after concentrating, and with this crude product of normal heptane recrystallization, the freezing product that makes is separated out, filter and dry after obtain product anti--4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzaldehyde.
The present invention is a raw material with 1-methoxyl group methyne-4-(anti--4 '-alkyl-cyclohexyl) hexanaphthene (II), behind the hydrolysis reaction, generate hexahydrobenzaldehyde (III) along anti-blended 4-(anti--4 '-alkyl-cyclohexyl), product need not separate, directly carry out isomerization reaction in this system, obtain product (I), this two-step reaction carries out in same reactor continuously, easy and simple to handle, save the refining purifying in the process.The structural formula of the immobilized sulfonic acid catalyst of used silica gel is as shown below:
The sulfonic acid group that wherein has catalytic activity is connected with silica gel by phenyl ring, and post catalyst reaction can pass through the filter type Separation and Recovery, and pollution-free waste is discharged, and does not cause environmental pollution, is suitable for suitability for industrialized production.
Embodiment
Embodiment 1
In the 2L three-necked bottle that agitator is housed, add 1-methoxyl group methyne-4-(anti--4 '-n-propyl cyclohexyl) hexanaphthene 250g (1mol), normal heptane 500g, tetrahydrofuran (THF) 750g, water 25g and supported on silica-gel sulfonic acid catalyst 50g; reaction system charges into the helium protection; stir down heat temperature raising to 40 ℃; after hydrolysis reaction carries out 15 hours; system temperature is risen to 60 ℃; carry out isomerization reaction, reaction continues 10 hours.Reaction is reduced to room temperature after finishing, remove by filter catalyzer, filtrate concentrating obtains the faint yellow solid crude product after doing, with this crude product of 250g normal heptane recrystallization, the freezing product that makes is separated out, filter and dry after obtain anti--4-(anti--4 '-n-propyl cyclohexyl) hexahydrobenzaldehyde 146.7g, productive rate 62.2%, by infrared and mass spectroscopy, determined the structure of the said products, its analytical data is as follows:
IR(KBr)v/cm
-1：2918，2850，2704，1727，1449，956，923GC-MS(EI)：236(M
+)，218，205。
Embodiment 2
In the 2L three-necked bottle that agitator is housed, add 1-methoxyl group methyne-4-(anti--4 '-normal-butyl cyclohexyl) hexanaphthene 264g (1mol), other condition is with embodiment 1, obtain anti--4-(anti--4 '-normal-butyl cyclohexyl) hexahydrobenzaldehyde 161.5g, productive rate 64.6%, by infrared and mass spectroscopy, determined the structure of the said products, its analytical data is as follows:
IR(KBr)v/cm
-1：2918，2850，2711，1726，1447，946，923GC-MS(EI)：250(M
+)，232，219。
Embodiment 3
In the 2L three-necked bottle that agitator is housed, add 1-methoxyl group methyne-4-(anti--4 '-n-pentyl cyclohexyl) hexanaphthene 278g (1mol), other condition is with embodiment 1, obtain anti--4-(anti--4 '-n-pentyl cyclohexyl) cyclohexyl formaldehyde 158.7g, productive rate 60.1%, by infrared and mass spectroscopy, determined the structure of the said products, its analytical data is as follows:
IR(KBr)v/cm
-1：2917，2849，2708，1721，1447，952，923GC-MS(EI)：264(M
+)，246，233。
Embodiment 4
In the 2L three-necked bottle that agitator is housed, add 1-methoxyl group methyne-4-(anti--4 '-n-propyl cyclohexyl) hexanaphthene 250g (1mol), normal heptane 500g, tetrahydrofuran (THF) 750g, water 25g and supported on silica-gel sulfonic acid catalyst 50g; reaction system charges into the helium protection; stir down heat temperature raising to 50 ℃; after hydrolysis reaction carries out 10 hours; system temperature is risen to 70 ℃; carry out isomerization reaction, reaction continues 5 hours.Other condition is with embodiment 1, obtains anti--4-(anti--4 '-n-propyl cyclohexyl) hexahydrobenzaldehyde 139.2g, productive rate 59.0%.
Claims (1)
1, the synthetic method of anti--4-(anti--4 '-alkyl-cyclohexyl) hexahydrobenzaldehyde, its molecular structural formula is shown in (I):
R is that carbonatoms is 1～7 straight chained alkyl in the formula, it is characterized in that: with 1-methoxyl group methyne-4-(anti--4 '-alkyl-cyclohexyl) hexanaphthene (II) is raw material, reaction solvent is normal heptane-tetrahydrofuran (THF)-water mixed solvent, add the supported on silica-gel sulfonic acid catalyst, the structural formula of the immobilized sulfonic acid catalyst of used silica gel is as shown below:
The sulfonic acid group that wherein has catalytic activity is connected with silica gel by phenyl ring; reaction system charges into the helium protection; heat temperature raising to 40 under stirring～50 ℃; reaction times is 10～15 hours; reaction is hydrolyzed; system temperature is risen to 60～70 ℃ then; carry out isomerization reaction; reaction continues 5～10 hours; reaction is reduced to room temperature after finishing; remove by filter catalyzer, obtain the faint yellow solid crude product after filtrate concentrates, with the normal heptane recrystallization obtain product anti--4-(instead-4 '-alkyl-cyclohexyl) hexahydrobenzaldehyde (I).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100177849A CN100497285C (en) | 2007-04-30 | 2007-04-30 | Method for synthesizing inverse-4-(inverse-4'-alkyl cyclohexyl) cyclohexyl methyl aldehyde |
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| CNB2007100177849A CN100497285C (en) | 2007-04-30 | 2007-04-30 | Method for synthesizing inverse-4-(inverse-4'-alkyl cyclohexyl) cyclohexyl methyl aldehyde |
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| CN100497285C true CN100497285C (en) | 2009-06-10 |
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| WO2015037665A1 (en) * | 2013-09-12 | 2015-03-19 | 信越化学工業株式会社 | METHOD FOR PRODUCING β-CYCLOLAVANDULAL AND DERIVATIVE OF SAME |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2102000A (en) * | 1981-07-17 | 1983-01-26 | Hoffmann La Roche | 2-(Cyclohexyl)ethyl-cyclo- hexylnitriles and their use in liquid crystal compositions |
| US4797228A (en) * | 1985-06-10 | 1989-01-10 | Chisso Corporation | Cyclohexane derivative and liquid crystal composition containing same |
| EP0688754A1 (en) * | 1993-03-10 | 1995-12-27 | Chisso Corporation | Dicyclohexylethylene derivative |
| CN1436761A (en) * | 2002-02-06 | 2003-08-20 | 清华大学 | Alkyl cyclohexyl alkyne type liquid crystal and its production process |
-
2007
- 2007-04-30 CN CNB2007100177849A patent/CN100497285C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2102000A (en) * | 1981-07-17 | 1983-01-26 | Hoffmann La Roche | 2-(Cyclohexyl)ethyl-cyclo- hexylnitriles and their use in liquid crystal compositions |
| US4797228A (en) * | 1985-06-10 | 1989-01-10 | Chisso Corporation | Cyclohexane derivative and liquid crystal composition containing same |
| EP0688754A1 (en) * | 1993-03-10 | 1995-12-27 | Chisso Corporation | Dicyclohexylethylene derivative |
| CN1436761A (en) * | 2002-02-06 | 2003-08-20 | 清华大学 | Alkyl cyclohexyl alkyne type liquid crystal and its production process |
Non-Patent Citations (9)
| Title |
|---|
| 1-(反式-4-烷基环己基)苯基-2-含氟苯基取代乙炔类液晶的合成与性能. 陈新兵等.精细化工，第22卷第11期. 2005 |
| 1-(反式-4-烷基环己基)苯基-2-含氟苯基取代乙炔类液晶的合成与性能. 陈新兵等.精细化工，第22卷第11期. 2005 * |
| 1,2-双取代的乙烷类液晶. 郑远洋等.液晶与显示，第12卷第4期. 1997 |
| 1,2-双取代的乙烷类液晶. 郑远洋等.液晶与显示，第12卷第4期. 1997 * |
| 4-[2'-(反式-4''-戊基环己基)乙基]环己酮的合成. 张晓军等.精细化工，第19卷第7期. 2002 |
| 4-[2'-(反式-4''-戊基环己基)乙基]环己酮的合成. 张晓军等.精细化工，第19卷第7期. 2002 * |
| C2桥键类液晶的合成进展. 陈新兵等.合成化学，第11卷第1期. 2003 |
| C2桥键类液晶的合成进展. 陈新兵等.合成化学，第11卷第1期. 2003 * |
| 利用Witting反应制备乙烷类液晶. 夏永涛等.合成化学，第13卷第6期. 2005 |
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Application publication date: 20071031 Assignee: WEINAN HIGH-NEW DISTRICT HAIQIN NEW ELECTRONIC MATERIAL Co.,Ltd. Assignor: Xi'an Ruilian Modern Electronic Chemicals Co.,Ltd. Contract record no.: 2010610000006 Denomination of invention: Synthesis method of reverse -4- (trans -4 '- alkyl cyclohexyl) cyclohexyl formaldehyde Granted publication date: 20090610 License type: Exclusive License Record date: 20100406 |
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