CN110804444A - Environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal - Google Patents
Environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal Download PDFInfo
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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- C09K2019/301—Cy-Cy-Ph
Abstract
The invention discloses a green and environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal, belonging to the technical field of liquid crystal material synthesis methods and comprising the following steps: preparing a ylide reagent system by a wittig reaction by taking a water-insoluble solvent as a reaction solvent and taking bromoalkyl triphenylphosphine salt and alkali as raw materials; adding a compound shown in the formula (I) into the ylide reagent system, and reacting to obtain a crude product solution of a compound shown in the formula (II); carrying out aftertreatment on the crude product solution of the compound shown in the formula (II) to prepare the compound shown in the formula (II); the reaction solvent can be completely recycled, high-concentration tetrahydrofuran wastewater with biotoxicity is not generated, and industrial mass production is facilitated.
Description
Technical Field
The invention belongs to the technical field of liquid crystal material synthesis methods, and particularly relates to a green and environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal.
Background
The trans-4-substituted cyclohexyl olefin single crystal is liquid crystal containing a cyclohexane skeleton, has the properties of low viscosity, good intersolubility, good optical stability and the like, is mainly applied to reducing the concentration of liquid crystal in a mixed liquid crystal formula and improving the miscibility of mixed crystals so as to realize the quick response of the mixed liquid crystal. The liquid crystal monomer becomes the main component of liquid crystal materials such as high-grade TN-LCD, STN-LCD, TFT-LCD and the like. The liquid crystal is synthesized by wittig reaction of trans-4-substituted cyclohexyl formaldehyde, the reaction selectivity is good, but the process has the main problem of generating a large amount of high COD (chemical oxygen demand) and high-salt wastewater. In the Wittig reaction, tetrahydrofuran is used as a solvent at present, potassium tert-butoxide is used as an alkali, and the post-treatment step of the reaction is to add a non-polar solvent and wash the solvent to generate a large amount of high-COD wastewater, wherein the wastewater mainly contains tetrahydrofuran, tert-butanol, triphenyl phosphine oxide and inorganic salts. Tetrahydrofuran is very poorly biodegradable and is almost impossible to remove by biodegradation. Tetrahydrofuran and the by-product tert-butyl alcohol have close boiling points, and the tert-butyl alcohol in tetrahydrofuran is difficult to completely remove. At present, various methods for recovering tetrahydrofuran are that waste liquid containing tetrahydrofuran is distilled and concentrated for many times, the content of tetrahydrofuran is gradually increased, and then reagent is used for dehydration, filtration and rectification. Large equipment investment and large energy consumption. Today, the environmental protection situation is becoming more severe, and the standard discharge of sewage in industrial enterprises has become a hard index for the survival of the enterprises. The difficulty of sewage treatment is high, the cost is high, the sewage is not easy to be qualified and reach the standard, and the survival and the development of enterprises are gradually restricted. Therefore, the organic synthesis process must cut off the pollution source from the source, improve the synthesis process, lead the solvent which can generate pollution, recycle the auxiliary materials in the process, and achieve zero emission or little emission.
Disclosure of Invention
In order to solve the problem of high-concentration wastewater, the invention provides a green and environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal.
The invention aims to provide a green and environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal, which comprises the following steps:
preparing a ylide reagent system by a wittig reaction by taking a water-insoluble solvent as a reaction solvent and taking bromoalkyl triphenylphosphine salt and alkali as raw materials; adding a compound shown in the formula (I) into the ylide reagent system, and reacting to obtain a crude product solution of a compound shown in the formula (II); carrying out aftertreatment on the crude product solution of the compound shown in the formula (II) to prepare the compound shown in the formula (II);
the synthesis reaction equation is as follows:
wherein n is any integer between 0 and 8;
a is R,
R is a straight-chain alkyl group with 1-8 carbon atoms; r1And R2Is a hydrogen atom or a fluorine atom.
Preferably, the crude solution of the compound of formula (ii) is prepared by the following steps:
dissolving bromoalkyl triphenylphosphine salt and alkali in a water-insoluble solvent I, reacting for 1-3 h at 0-108 ℃, adding a compound of formula (I)/water-insoluble solvent II solution at-10-30 ℃, and reacting for 2h at-10-5 ℃ to prepare a crude compound solution of formula (II);
the compounds of formula (I): bromoalkyltriphenylphosphine salts: the molar ratio of the alkali is 1: 1.1-1.5: 1.05-1.45; bromoalkyltriphenylphosphine salts: the dosage ratio of the water-insoluble solvent I is 1g: 2-10 mL; water-insoluble solvent i: the volume ratio of the water-insoluble solvent II is 0.6-15: 1.
Preferably, the alkyl in the bromoalkyl triphenylphosphine salt refers to a straight-chain alkyl group with 1-5 carbon atoms.
Preferably, the base is sodium methoxide, potassium isopropoxide, sodium tert-butoxide or potassium tert-butoxide.
Preferably, the water-insoluble solvent I and the water-insoluble solvent II are the same and are n-heptane, n-hexane, methylcyclohexane or toluene.
Preferably, when the water-insoluble solvent I is n-heptane, n-hexane or methylcyclohexane, the crude solution of the compound of formula (II) is prepared by the following steps:
washing the crude compound solution of the formula (II), filtering, separating the organic phase from the filtrate, washing the organic phase with water, drying, passing through a silica gel column, concentrating the column passing solution, and recovering the solvent to obtain the concentrate, namely the compound of the formula (II).
Preferably, when the water-insoluble solvent I is toluene, the crude solution of the compound of formula (II) is prepared by the following steps:
washing the crude solution of the compound shown in the formula (II) with water, concentrating and recovering toluene, adding an extracting agent into the concentrate, filtering, drying the filtrate, passing through a silica gel column, and concentrating the column passing liquid to obtain the compound shown in the formula (II).
Preferably, the extractant is n-heptane, n-hexane or methylcyclohexane.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a non-water-soluble solvent is used as a wittig reaction solvent, and the solvent can be reused after drying and dewatering, so that the raw material cost is reduced and zero emission of the solvent is realized; the byproduct triphenylphosphine oxide is removed by filtration, so that the phenomenon that the product and the byproduct brought by tetrahydrofuran are put into water can be avoided, the recovered solvent only contains a small amount of alcohols, the solvent can be reused by treatment, no high-concentration tetrahydrofuran wastewater is generated, and the industrial mass production is facilitated.
Drawings
FIG. 1 is a mass spectrum of trans-4- (4-propylcyclohexyl) cyclohexylethylene prepared in example 1;
FIG. 2 is a mass spectrum of trans-4- (4-pentylcyclohexyl) cyclohexyl ethylene prepared in example 2;
FIG. 3 is a mass spectrum of trans-4- [4- (4-methylphenyl) cyclohexyl) ] cyclohexylbutene prepared in example 3;
FIG. 4 is a mass spectrum of trans-4- (2, 3-difluoro-4-ethoxy) phenyl-cyclohexylethylene prepared in example 4.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
Example 1
A green and environment-friendly synthesis method of trans-4- (4-propylcyclohexyl) cyclohexylethylene comprises the following steps:
under the protection of nitrogen, 3030ml of n-heptane, 303.0g of bromomethane triphenylphosphine salt and 87.2g of potassium isopropoxide are sequentially added into a 5L three-neck flask, the mixture is stirred and reacts for 3 hours at the temperature of 20 ℃, then the temperature is reduced to minus 10 ℃, a mixed solution prepared by 200ml of n-heptane and 200.0g of trans-4- (4-propylcyclohexyl) cyclohexyl formaldehyde is dripped, the temperature of a process control system is controlled to be minus 10 ℃, 2 hours after the dripping is finished, water is added after the reaction is finished, insoluble substances are removed by stirring and filtering, an organic phase is separated, the organic phase is washed and dried, then the organic phase passes through a silica gel column, the column passing liquid is decompressed, concentrated and the n-heptane is recovered to obtain 182.4g of white solid with the GC content of 99.8%, the yield is 92%, and the recovered n-heptane.
The mass spectrum of the compound shown in figure 1 can be obtained by GC-MS, wherein M is 234 and M is 205.
Example 2
A green and environment-friendly synthesis method of trans-4- (4-pentylcyclohexyl) cyclohexylethylene comprises the following steps:
under the protection of nitrogen, 2030ml of methylcyclohexane, 406.4g of bromomethane triphenylphosphine salt and 123.0g of potassium tert-butoxide are sequentially added into a 5L three-neck flask, the mixture is stirred and reacted at 0 ℃ for 3h, then the temperature is reduced to-5 ℃, a mixed solution prepared by 400ml of methylcyclohexane and 200.0g of trans-4- (4-pentylcyclohexyl) cyclohexylformaldehyde is dripped, the temperature of a process control system is controlled at 0 ℃, the mixed solution is dripped for 2h after the dripping is finished, water is added after the reaction is finished, insoluble substances are removed by stirring and filtering, an organic phase is separated, the organic phase is washed and dried, then the organic phase is passed through a silica gel column, the column liquid is decompressed and concentrated to recover the methylcyclohexane, 184.4g of white solid with the GC content of. The recovered methylcyclohexane can be used for the Wittig reaction of the next batch.
As shown in the mass spectrum of fig. 2, the GC-MS shows that M is 262; m- (═ 233.
Example 3
An environment-friendly synthesis method of trans-4- [4- (4-methylphenyl) cyclohexyl) ] cyclohexyl butene comprises the following steps:
under the protection of nitrogen, 596ml of toluene and 298.0g of bromomethane triphenylphosphine salt are sequentially added into a 3L three-neck flask, 43.2g of sodium methoxide is added, the temperature is raised to 108 ℃ for reaction for 1 hour, the temperature is reduced to 30 ℃, a mixed solution of 1000ml of toluene and 200.0g of trans-4- [4- (4-methylphenyl) cyclohexyl) ] cyclohexyl propionaldehyde is dropwise added, the temperature of a process control system is 5 ℃, and the reaction is carried out for 2 hours after the dropwise addition is finished; washing the reaction solution with water, and concentrating under reduced pressure to recover toluene; adding 6000ml of n-heptane into the concentrate, heating to 50 ℃, stirring for 30min, cooling to room temperature, filtering insoluble substances, drying the filtrate, passing through a silica gel column, concentrating the column-passing liquid to obtain 184.5g of white solid with the GC content of 99.8%, wherein the yield is 93%; the toluene is recovered to remove water and can be applied to the Wittig reaction of the next batch; and recovering n-heptane for use in the next extraction process.
As shown in the mass spectrum of fig. 3, the GC-MS is that M is 310;
example 4
An environment-friendly synthesis method of trans-4- (2, 3-difluoro-4-ethoxy) phenyl-cyclohexyl ethylene comprises the following steps:
under the protection of nitrogen, 1400ml of methylcyclohexane, 347.1g of bromomethane triphenylphosphine salt and 104.5g of potassium tert-butoxide are sequentially added into a 5L three-neck flask, the mixture is stirred and reacts for 3 hours at 50 ℃, then the temperature is reduced to minus 5 ℃, 2000ml of mixed solution prepared by methylcyclohexane and 200.0g of trans-4- (2, 3-difluoro-4-ethoxy) phenylcyclohexyl formaldehyde is dripped, the temperature of a process control system is controlled to minus 5 ℃, and 2 hours are carried out after the dripping is finished; after the reaction is finished, adding water, stirring, and filtering to remove insoluble substances; the organic phase was separated, washed with water and dried, passed through a silica gel column, and the column-passed liquid was concentrated under reduced pressure to recover methylcyclohexane, to give 178.6g of a white solid with a GC content of 99.8%, with a yield of 90%. The recovered methylcyclohexane can be used for the Wittig reaction of the next batch.
As shown in the mass spectrum of fig. 4, GC-MS, M266; m- (═ 237.
The trans-4-substituted cyclohexyl olefin liquid crystal is successfully prepared by adopting the method, and the water-insoluble solvent is adopted as the wittig reaction solvent, and can be reused after drying and dewatering, so that the raw material cost is reduced, and the zero emission of the solvent is realized; the byproduct triphenylphosphine oxide is removed by filtration, so that the phenomenon that the product and the byproduct brought by tetrahydrofuran are put into water can be avoided, the recovered solvent only contains a small amount of alcohols, the solvent can be reused by treatment, no high-concentration tetrahydrofuran wastewater is generated, and the industrial mass production is facilitated.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (8)
1. A green and environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal is characterized by comprising the following steps:
preparing a ylide reagent system by a wittig reaction by taking a water-insoluble solvent as a reaction solvent and taking bromoalkyl triphenylphosphine salt and alkali as raw materials; adding a compound shown in the formula (I) into the ylide reagent system, and reacting to obtain a crude product solution of a compound shown in the formula (II); carrying out aftertreatment on the crude product solution of the compound shown in the formula (II) to prepare the compound shown in the formula (II);
the synthesis reaction equation is as follows:
wherein n is any integer between 0 and 8;
a is R,
R is a straight-chain alkyl group with 1-8 carbon atoms; r1And R2Is a hydrogen atom or a fluorine atom.
2. The environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal as claimed in claim 1, characterized in that the crude compound solution of formula (II) is prepared by the following steps:
dissolving bromoalkyl triphenylphosphine salt and alkali in a water-insoluble solvent I, reacting for 1-3 h at 0-108 ℃, adding a compound of formula (I)/water-insoluble solvent II solution at-10-30 ℃, and reacting for 2h at-10-5 ℃ to prepare a crude compound solution of formula (II);
the compounds of formula (I): bromoalkyltriphenylphosphine salts: the molar ratio of the alkali is 1: 1.1-1.5: 1.05-1.45; bromoalkyltriphenylphosphine salts: the dosage ratio of the water-insoluble solvent I is 1g: 2-10 mL; water-insoluble solvent i: the volume ratio of the water-insoluble solvent II is 0.6-15: 1.
3. The green and environment-friendly synthesis method of the trans-4-substituted cyclohexyl olefin liquid crystal according to claim 2, characterized in that the alkyl group in the bromoalkyltriphenylphosphine salt refers to a straight-chain alkyl group with 1-5 carbon atoms.
4. The environmentally friendly method of synthesizing trans-4-substituted cyclohexyl olefin liquid crystal according to claim 2, wherein the base is sodium methoxide, potassium isopropoxide, sodium tert-butoxide or potassium tert-butoxide.
5. The method for synthesizing trans-4-substituted cyclohexyl olefin liquid crystal in green environment according to claim 2, wherein the water-insoluble solvent I and the water-insoluble solvent II are the same and are n-heptane, n-hexane, methylcyclohexane or toluene.
6. The method for green and environment-friendly synthesis of trans-4-substituted cyclohexyl olefin liquid crystal according to claim 5, wherein when the water-insoluble solvent I is n-heptane, n-hexane or methylcyclohexane, the crude solution of the compound of formula (II) is prepared by the following steps:
washing the crude compound solution of the formula (II), filtering, separating the organic phase from the filtrate, washing the organic phase with water, drying, passing through a silica gel column, concentrating the column passing solution, and recovering the solvent to obtain the concentrate, namely the compound of the formula (II).
7. The method for environmentally friendly synthesizing trans-4-substituted cyclohexyl olefin liquid crystal according to claim 5, wherein when the water insoluble solvent I is toluene, the crude solution of the compound of formula (II) is prepared by the following steps:
washing the crude solution of the compound shown in the formula (II) with water, concentrating and recovering toluene, adding an extracting agent into the concentrate, filtering, drying the filtrate, passing through a silica gel column, and concentrating the column passing liquid to obtain the compound shown in the formula (II).
8. The green and environment-friendly synthesis method of trans-4-substituted cyclohexyl olefin liquid crystal according to claim 7, characterized in that the extractant is n-heptane, n-hexane or methylcyclohexane.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0977692A (en) * | 1995-09-13 | 1997-03-25 | Dainippon Ink & Chem Inc | Bicyclohexane derivative |
| CN101244977A (en) * | 2008-03-11 | 2008-08-20 | 浙江永太科技股份有限公司 | Method for producing cyclohexyl group olefin hydrocarbon liquid crystal material |
| CN102010287A (en) * | 2010-10-20 | 2011-04-13 | 石家庄诚志永华显示材料有限公司 | Method for synthesizing (trans)-4-alkyl-3-alkene biphenyl derivative monomer liquid crystals |
| CN102167654A (en) * | 2011-03-10 | 2011-08-31 | 浙江永太科技股份有限公司 | Preparation method of trans-4-substituted cyclohexyl olefin compound |
| CN104017585A (en) * | 2014-05-29 | 2014-09-03 | 京东方科技集团股份有限公司 | Liquid crystal compound, liquid crystal composition, preparation methods thereof and liquid crystal display panel |
| JP2014162751A (en) * | 2013-02-25 | 2014-09-08 | Dic Corp | Compound, liquid crystal composition, and display device |
| JP2014162752A (en) * | 2013-02-25 | 2014-09-08 | Dic Corp | Compound, liquid crystal composition, and display device |
| CN104829409A (en) * | 2015-03-20 | 2015-08-12 | 中节能万润股份有限公司 | Preparation method of trans-4-substituted cyclohexyl ethylene |
| CN107963958A (en) * | 2017-08-10 | 2018-04-27 | 西安瑞联新材料股份有限公司 | The synthetic method of trans- 4- (trans- 4 '-alkyl-cyclohexyl) cyclohexyl. vinyl liquid crystal monomer |
-
2019
- 2019-11-13 CN CN201911108887.5A patent/CN110804444A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0977692A (en) * | 1995-09-13 | 1997-03-25 | Dainippon Ink & Chem Inc | Bicyclohexane derivative |
| CN101244977A (en) * | 2008-03-11 | 2008-08-20 | 浙江永太科技股份有限公司 | Method for producing cyclohexyl group olefin hydrocarbon liquid crystal material |
| CN102010287A (en) * | 2010-10-20 | 2011-04-13 | 石家庄诚志永华显示材料有限公司 | Method for synthesizing (trans)-4-alkyl-3-alkene biphenyl derivative monomer liquid crystals |
| CN102167654A (en) * | 2011-03-10 | 2011-08-31 | 浙江永太科技股份有限公司 | Preparation method of trans-4-substituted cyclohexyl olefin compound |
| JP2014162751A (en) * | 2013-02-25 | 2014-09-08 | Dic Corp | Compound, liquid crystal composition, and display device |
| JP2014162752A (en) * | 2013-02-25 | 2014-09-08 | Dic Corp | Compound, liquid crystal composition, and display device |
| CN104017585A (en) * | 2014-05-29 | 2014-09-03 | 京东方科技集团股份有限公司 | Liquid crystal compound, liquid crystal composition, preparation methods thereof and liquid crystal display panel |
| CN104829409A (en) * | 2015-03-20 | 2015-08-12 | 中节能万润股份有限公司 | Preparation method of trans-4-substituted cyclohexyl ethylene |
| CN107963958A (en) * | 2017-08-10 | 2018-04-27 | 西安瑞联新材料股份有限公司 | The synthetic method of trans- 4- (trans- 4 '-alkyl-cyclohexyl) cyclohexyl. vinyl liquid crystal monomer |
Non-Patent Citations (1)
| Title |
|---|
| （日）立本英机 等: "《活性炭的应用技术：其维持管理及存在问题》", 30 July 2002, 东南大学出版社 * |
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