CN1199737A - Sterol polyfluoro aromatic ester and its synthesis and use - Google Patents

Sterol polyfluoro aromatic ester and its synthesis and use Download PDF

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CN1199737A
CN1199737A CN 98110842 CN98110842A CN1199737A CN 1199737 A CN1199737 A CN 1199737A CN 98110842 CN98110842 CN 98110842 CN 98110842 A CN98110842 A CN 98110842A CN 1199737 A CN1199737 A CN 1199737A
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sterol
polyfluoro
polyfluoro aromatic
aromatic ester
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CN1064369C (en
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闻建勋
沈悦海
冯遵杰
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

Sterol polyfluoro aromatic ester is produced either through esterification of corresponding polyfluoro aromatic acid and sterol in dewatering agent and solvent, or through the reaction of corresponding polyfluoro aromatic acid and cryl halogenating agent to produce polyfluoro aromatic cryl halide and the reaction of polyfluoro aromatic cryl halide with sterol. The present invention has the advantages of simple synthesis process, easy available material, high yield and being suitable for industrial production, and the product is cholesteric phase product and is one high-performance LC material with wide application range.

Description

Sterol polyfluoro aromatic ester, preparation method and use
The present invention relates to a kind of sterol polyfluoro aromatic ester, preparation method and use.
Since finding liquid crystal in 1888,, in information display technology, chemical industry, obtained to use widely because liquid crystal has the character of many uniquenesses.With fluorine atom replace one or two hydrogen in the liquid crystal nuclear can effectively reduce liquid crystal viscosity, improve chemistry and light stability, replace atom (JP02,11570 (90,11570) on the flexible side-chains that is connected liquid crystal nuclear two ends with fluorine atom; JP01,283258 (89,283 258)), also obtained ideal results.People such as Wen Jianxun once reported the liquid crystalline cpd that contains perfluoro-benzene-ring, and (CN 9210844.7, CN97106778.3), having that transformation temperature is low, clearing point is high, viscosity is low, liquid crystal phase temperature range is wide, degree of birefringence is high, chemical stability is good and fat-soluble characteristic such as good, is a kind of liquid crystal material with wide application prospect.
The sterol ester liquid crystal is the liquid crystal material of cholesteric phase of excellent performance, is actually used in the dispensing liquid crystal.And in this class liquid crystalline cpd molecule, introduce the phenyl ring contain a fluorine, can improve its performance, once reported the cholesterol neighbour, to and a position single fluorine substituted benzoyl acid esters (Acta Phys.Chem., 1979,25 (3-4), 173-8; JP59.161,399 (1984)).Because the huge applications potentiality of liquid crystal material, people are still at the liquid crystal material of constantly exploring excellent property.
The purpose of this invention is to provide a kind of sterol polyfluoro aromatic ester, specifically at the fluorine atom that has on the aromatic ring more than two or two.
Another object of the present invention provides the method for synthetic this sterol polyfluoro aromatic ester.
Purpose of the present invention also provides the purposes of this sterol polyfluoro aromatic ester.
Sterol polyfluoro aromatic ester of the present invention has following molecular formula:
Figure A9811084200041
N=2 or 3 wherein, A=singly-bound or HC=CH, B=5, the two keys or 5 of 6-, 6-dihydro.As cholesterol or Dihydrocholesterol-3,5-difluoro-benzoic acid ester, cholesterol or Dihydrocholesterol-3,4,5-trifluoromethyl benzonitrile acid esters, cholesterol or Dihydrocholesterol-3,5-cinnamic acid difluoride ester, cholesterol or Dihydrocholesterol-3,4,5-trifluoro laurate, cholesterol or Dihydrocholesterol-3,4-difluoro-benzoic acid ester and cholesterol or Dihydrocholesterol-3,4-cinnamic acid difluoride ester etc.
Sterol polyfluoro aromatic ester of the present invention can also can be made with the sterol reaction by polyfluoro aromatic elder generation carboxylic acid halides generation polyfluoro virtue carboxylic acid halides by cholesterol and polyfluoro aromatic direct esterification (dehydrating condensation) again, and described sterol is cholesterol or Dihydrocholesterol.Above-mentioned two kinds of methods can be expressed from the next respectively.
Figure A9811084200042
N=2 or 3 wherein, A=singly-bound or CH=CH.
One of synthetic method of the present invention by molecular formula is Polyfluoro aromatic and sterol in the presence of solvent and dewatering agent, reaction is 5-48 hour in the time of-10-50 ℃, n=2 or 3 wherein.Described dewatering agent is N, N-dicyclohexyl phosphinylidyne diimine (DCC).Described solvent is non-aprotic solvent, as ether, trichloroethane, ethylene dichloride, tetracol phenixin, tetrahydrofuran (THF), benzene, toluene, acetonitrile etc.
When adopting this synthetic method, will help reaction to carry out if there is catalyzer to exist, described catalyzer is N, N-dimethyl amine pyridine (DMAP).The mol ratio of described polyfluoro aromatic, sterol, dewatering agent and catalyzer is followed successively by 1: 0.8-5: 0.5-5: 0-0.10, recommending mol ratio is 1: 0.8-1.5: 0.8-1.5: 0.01-0.10.
Another synthetic method of the present invention is that described polyfluoro aromatic was reacted 0.5-5 hour with the acyl halogenating agent in solvent, makes polyfluoro virtue carboxylic acid halides, and temperature of reaction is 30-150 ℃, and the mol ratio of polyfluoro aromatic and acyl halogenating agent is 1: 0.5-5.Recommending mol ratio is 1: 1-2, temperature of reaction is a reflux temperature.Described acyl halogenating agent is thionyl chloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, phosphorus tribromide etc.
Polyfluoro virtue carboxylic acid halides in solvent and sterol-10-50 ℃ reaction 2-70 hour, make sterol polyfluoro aromatic ester.Can reduce pressure simultaneously during this reaction and extract hydrogenchloride, perhaps add organic bases in reactant, the mol ratio of polyfluoro virtue carboxylic acid halides, sterol and organic bases is 1: 0.8-2: 0.8-5, recommend mol ratio to be followed successively by 1: 0.8-1.5: 0.8-1.5, temperature of reaction is a room temperature, and the reaction times is 1-24 hour.Described organic bases is the organic amine compound that has lone-pair electron on the nitrogen-atoms, as triethylamine, trioctylamine, bipyridine, pyridine, picoline, Tetramethyl Ethylene Diamine etc.
Sterol polyfluoro aromatic ester of the present invention is compared with similar not fluorine-containing liquid crystalline cpd, and fusing point is constant substantially, and clearing point improves, and liquid crystal phase temperature range is expanded greatly, and all only is cholesteryl phase, and performance also significantly improves, and is the liquid crystalline cpd of excellent performance.
Liquid crystalline cpd of the present invention is simple synthetic method not only, and raw material all is industrialization products, and synthetic yield is a kind of liquid crystal material that is suitable for industrial production and application all greater than 87%.
To help to understand the present invention by following embodiment, but not place restrictions on content of the present invention.
Embodiment 1 cholesterol-3,4, the synthetic and liquid crystal liquid crystal property of 5-trifluoro laurate (a3)
Method 1
With 0.96g (4.73mmol) 3,4,5-three fluoro cinnamic acids, 1.85g (4.78mmol) cholesterol, 4.75mmol N, N '-dicyclohexyl imide, 20mg N, N dimethylamine yl pyridines (DMAP) stirred 5-48 hour under the room temperature in 10-30ml anhydrous tetrahydro furan, ethylene dichloride or diethyl ether solution, filter, filtrate steaming removal solvent D post chromatography purification gets product 2.53g, productive rate 93.7%.
Method 2
With 4.73mmol 3,4,5-three fluoro cinnamic acids and 10-50ml benzene, sherwood oil or tetracol phenixin splash into 3-5ml thionyl chloride or phosphorus trichloride under stirring, and reflux 0.5-1 hour, decompression desolventized.Add 4-10mmol cholesterol and 10-50ml pyridine or triethylamine, stirring at room 1-24 hour.Add 50-100ml ether or ethyl acetate in the reaction solution, add water washing, anhydrous Na 2SO 4Drying desolventizes the D post chromatography purification, productive rate 94.5%.
The product analysis result:
1H?NMR(CDCl 3)，δppm：7.0-7.6(2H，Ar-H)，6.2-6.5(2H，CH＝CH)，5.4(1H，6-H)，4.5-4.9(1H，3α-H)。
19F?NMR(CCl 4)，δppm：56.5(2F，m-F)，80.5(1F，p-F).
MS?m/e：570(M +)
IR(KBr，cm -1)：1713(-CO 2)。
Ultimate analysis: calculated value: C 75.75, H 8.65, and F 9.99
Measured value: C 75.81, H 8.60, and F 9.90
Cr?75?2(℃)Ch?149.6(℃)I?147.6(℃)Ch?465.(℃)Cr(DSC)。
Embodiment 2 cholesterol-3, the synthetic and liquid crystal liquid crystal property of 5-difluoro-benzoic acid ester (b2)
Method 1:
With 5.0g (31.6mmol) 3,5-difluoro-benzoic acid, 45mmol cholesterol, 31.6-5.0mmolDCC, 50-200mgDMAP stirred 24-48 hour under the room temperature in 20-100ml benzene, filtered, and desolventized, and pureization of post layer gets product.Productive rate 94.7%.
Method 2:
4-8ml thionyl chloride or oxalyl chloride are splashed into above-mentioned 3, in 5-difluoro-benzoic acid and 30-50ml toluene or the ether, back flow reaction 1-2 hour, desolventize.Add the 20-30ml acetonitrile, 12.3g (31.6mmol) cholesterol and 31-40 mmol bipyridine or Tetramethyl Ethylene Diamine, stirring at room 5-20 hour, add 50-100ml ether, ethyl acetate or methylene dichloride in the reaction solution, wash anhydrous MgSO with water 4Drying is filtered, and desolventizes, and pureization of post layer gets product 16.04g, productive rate 96.3%.
The product analysis result:
1H?NMR(CDCl 3)，δppm：6.8-7.7(3H，Ar-H)，5.5(1H，6-H)，4.6-5.2(1H，3α-H)。
19F?NMR(CCl 4)，δ(TFA，ppm)：31.0(m-F)。
MS?m/e：526(M +).
IR(KBr，cm -1)：1724(CO 2)。
Ultimate analysis C 34H 48F 2O 2:
Calculated value: C 77.52, H 9.19, and F 7.21
Measured value: C 77.49, H 9.23, F 7.19 embodiment 3 cholesterol polyfluoro aromatic esters synthetic
With 10mmol Polyfluoro aromatic, 5-8mmol cholesterol, 5-40mmolN, N '-dicyclohexyl carbimide and 0.05-1mmol N, the N dimethylamine yl pyridines, in the 10-50ml tetrahydrofuran solution and-10-40 ℃ reaction 30 hours, filter, steam except that behind the solvent in the filtrate,, the results are shown in table 1 with purification by silica gel column chromatography.
Table 1. Analytical results is as follows:
Figure A9811084200071
1H?NMR(CDCl 3)，δppm：7.4-7.9(3H，Ar-H)，6.1-6.5(2H，CH＝CH)，5.4(1H，6-H)，4.5-5.1(1H，3α-H)
19F?NMR(CCl 4)，δ(TFA，ppm)：56.5(1F，p-F)，58.3(1F，m-F)
MS?m/e：552(M +).
IR(KBr，cm -1)：1713(CO 2)。
Ultimate analysis C 36H 50F 2O 2:
Calculated value: C 78.22, H 9.12, and F 6.87
Measured value: C 78.30, H 9.14, and F 6.78
1H?NMR(CDCl 3)，δppm：6.7-7.5(3H，Ar-H)，6.2-6.5(2H，CH＝CH)，5.5(1H，6-H)，4.6-5.2(1H，3α-H)
19F?NMR(CCl 4)，δ(TFA，ppm)：31.0(m-F)。
MS?m/e：552(M +).
IR(KBr，cm -1)：1715(CO 2)。
Ultimate analysis C 36H 50F 2O 2:
Calculated value: C 78.22, H 9.12, and F 6.87
Measured value: C 78.20, H 9.16, and F 6.83
1H?NMR(CDCl 3)，δppm：7.5-8.2(3H，Ar-H)，5.4(1H，6-H)，4.5-5.1(1H，3α-H).
19F?NMR(CCl 4)，δ(TFA，ppm)：53.0(1F，m-F)，59.3(1F，p-F)。
MS?m/e：526(M +).
IR(KBr，cm -1)：1723(CO 2)。
Ultimate analysis C 36H 48F 2O 2:
Calculated value: C 77.52, H 9.19, and F 7.21
Measured value: C 77.55, H 9.20, and F 7.15
Figure A9811084200081
1H?NMR(CDCl 3)，δppm：7.0-7.6(2H，Ar-H)，5.4(1H，6-H)，4.5-5.1(1H，3α-H).
19F?NMR(CCl 4)，δ(TFA，ppm)：50.0(2F，m-F)，75.5(1F，p-F)。
MS?m/e：544(M +).
IR(KBr，cm -1)：1725(CO 2)。
Ultimate analysis C 36H 47F 3O 2:
Calculated value: C 74.96, H 8.70, and F 10.46
Measured value: C 75.03, H 8.69, and F 10.41
Embodiment 4 Dihydrocholesterols 3, the synthetic method 1. of 4-difluoro-benzoic acid ester (dl)
With 3.0g (19.0mmol) 3, the 4-difluoro-benzoic acid, 7.75g (19.9mmol) Dihydrocholesterol, 5.5g (26.6mmol) DCC and 100mgDMAP are dissolved in the 30ml trichloromethane, stirred 48 hours under the room temperature, filter filtrate steaming removal solvent D post chromatography purification (silica gel 200-500 order, eluent sherwood oil (60-90 ℃)-ethyl acetate).Get product 9.85g, productive rate 98.2%.Method 2.
With 3.0g (19.0mmol) 3, the 4-difluoro-benzoic acid is dissolved in the 30ml benzene, stirs to add 3.95g (19.0mmol) phosphorus pentachloride down, and reflux 1 hour removes the phosphorus oxychloride of solvent and generation under reduced pressure.Add 7.75g (19.9mmol) cholesterol, 2.9ml (19.91mmol) triethylamine and 30ml trichloromethane, stirring at room 24 hours.Reaction solution is with water washing, anhydrous Na 2SO 4Drying, steaming desolventizes the D post chromatography purification, gets product 9.71g, productive rate 96.8%.
Figure A9811084200082
1H?NMR(CDCl 3)，δppm：7.5-8.2(3H，Ar-H)
19F?NMR(CCl 4)，δ(TFA，ppm)：54.1(1F，m-F)，60.5(1F，p-F)。
MS?m/e：528(M +).
IR(KBr，cm -1)：1724(CO 2)。
Ultimate analysis C 34H 50F 2O 2:
Calculated value: C 77.23, H 9.53, and F 7.19
Measured value: C 77.31, H 9.50, and F 7.20
Synthesizing of embodiment 5 Dihydrocholesterol polyfluoro aromatic esters
With embodiment 4 methods 2, change polyfluoro aromatic, result such as table 2.
Table 2.
Figure A9811084200091
The above-claimed cpd analytical results is as follows:
Figure A9811084200092
1H NMR (CDCl 3), δ ppm:7.4-7.9 (3H, Ar-H), 6.1-6.5 (2H, CH=CH), 19F NMR (CCl 4), δ (TFA, ppm): 56.5 (1F, m-F), 61.0 (1F, p-F).MS?m/e：554(M +).IR(KBr，cm -1)：1712(CO 2)。Ultimate analysis C 36H 52F 2O 2:
Calculated value: C 77.93, H 9.45, and F 6.85
Measured value: C 77.99, H 9.45, and F 6.74
Figure A9811084200093
1H NMR (CDCl 3), δ ppm:6.7-7.5 (3H, Ar-H), 6.1-6.5 (2H, CH=CH), 19F NMR (CCl 4), δ (TFA, ppm): 31.0 (m-F).MS?m/e：554(M +).IR(KBr，cm -1)：1714(CO 2)。Ultimate analysis C 36H 52F 2O 2:
Calculated value: C 77.93, H 9.45, and F 6.85
Measured value: C 77.94, H 9.47, and F 6.79
Figure A9811084200101
1H NMR (CDCl 3), δ ppm:7.0-7.6 (2H, Ar-H), 6.2-6.5 (2H, CH=CH), 19F NMR (CCl 4), δ (TFA, ppm): 55.7 (2F, m-F), 80.0 (1F, p-F).MS?m/e：572(M +).IR(KBr，cm -1)：1713(CO 2)。Ultimate analysis C 36H 51F 3O 2:
Calculated value: C 75.49, H 8.98, and F 9.95
Measured value: C 75.40, H 8.97, and F 9.86
Figure A9811084200102
1H NMR (CDCl 3), δ ppm:7.0-7.7 (3H, Ar-H) 19F NMR (CCl 4), δ (TFA, ppm): 31.0 (m-F).MS?m/e：528(M +)IR(KBr，cm -1)：1722(CO 2)。Ultimate analysis C 34H 50F 2O 2:
Calculated value: C 77.23, H 9.53, and F 7.19
Measured value: C 77.25, H 9.54, and F 7.10
Figure A9811084200103
1H NMR (CDCl 3), δ ppm:7.0-7.6 (2H, Ar-H) 19F NMR (CCl 4), δ (TFA, ppm): 50.0 (2F, m-F), 75.5 (1F, p-F).MS?m/e：546(M +).IR(KBr，cm -1)：1724(CO 2)。Ultimate analysis C 34H 49F 3O 2:
Calculated value: C 74.69, H 9.03, and F 10.43
Measured value: C 74.65, H 9.12, and F 10.33
1H?NMR(CDCl 3)，δppm：7.4-7.9(3H，Ar-H)，6.1-6.5(2H，CH＝CH)，
19F?NMR(CCl 4)，δ(TFA，ppm)：56.5(1F，m-F)，61.0(1F，p-F)。
MS?m/e：554(M +).
IR(KBr，cm -1)：1?712(CO 2)。
Ultimate analysis C 36H 52F 2O 2:
Calculated value: C 77.93, H 9.45, and F 6.85
Measured value: C 77.99, H 9.45, and F 6.74
The transformation temperature of embodiment 6 sterol polyfluoro aromatic esters
The transformation temperature of embodiment 1-5 institute synthetic compound and phase are measured with the polarized light microscopy method, and confirm that with dsc (DSC) result is as shown in table 3:
The transformation temperature numbering compound phase of table 3. sterol polyfluoro aromatic ester *And transformation temperature (℃)
Figure A9811084200112
Figure A9811084200114
Figure A9811084200115
Figure A9811084200116
Figure A9811084200119
Figure A98110842001110
Figure A98110842001113
*Cr-crystal wherein, Ch-cholesteryl phase, I-isotropic liquid.

Claims (12)

1. sterol polyfluoro aromatic ester is characterized in that having following molecular formula: N=2 or 3 wherein, A=singly-bound or HC=CH, B=5, the two keys or 5 of 6-, 6-dihydro.
2. sterol polyfluoro aromatic ester as claimed in claim 1 is characterized in that having following molecular formula:
Figure A9811084200022
, B=5, the two keys or 5 of 6-, 6-dihydro.
3. sterol polyfluoro aromatic ester as claimed in claim 1 is characterized in that having following molecular formula: B=5, the two keys or 5 of 6-, 6-dihydro.
4. sterol polyfluoro aromatic ester as claimed in claim 1 is characterized in that having following molecular formula:
Figure A9811084200024
, B=5, the two keys or 5 of 6-, 6-dihydro.
5. sterol polyfluoro aromatic ester as claimed in claim 1 is characterized in that having following molecular formula: , B=5, the two keys or 5 of 6-, 6-dihydro.
6. sterol polyfluoro aromatic ester as claimed in claim 1, its feature has following molecular formula: , B=5, the two keys or 5 of 6-, 6-dihydro.
7. sterol polyfluoro aromatic ester as claimed in claim 1, its feature has following molecular formula: , B=5, the two keys or 5 of 6-, 6-dihydro.
8. the synthetic method of sterol polyfluoro aromatic ester as claimed in claim 1 is characterized in that making respectively with following two kinds of methods: Polyfluoro aromatic and sterol, dewatering agent and catalyzer are in the presence of solvent,-10-50 ℃ was reacted 5-48 hour, n=2 or 3 wherein, A=singly-bound or HC=CH, the mol ratio of polyfluoro aromatic, sterol and dewatering agent is 1: 0.8-5: 0.5-5: 0-0.10, and described dewatering agent is N, N-dicyclohexyl phosphinylidyne diimine, catalyzer is N, N-dimethyl amine pyridine.
2) described polyfluoro aromatic is in solvent and 30-150 ℃ the time, with acyl halogenating agent reaction 0.5-5 hour, make polyfluoro virtue carboxylic acid halides, the mol ratio of polyfluoro aromatic and acyl halogenating agent is 1: 0.5-5 polyfluoro virtue carboxylic acid halides and sterol and organic bases were solvent neutralization-10-50 ℃ of reaction 0.5-24 hour, the mol ratio of polyfluoro virtue carboxylic acid halides and sterol, organic bases is 1: 0.8-2: 0.8-5, described organic bases is the organic amine compound that has lone-pair electron on the nitrogen-atoms, and sterol is cholesterol or Dihydrocholesterol.
9. the synthetic method of sterol polyfluoro aromatic ester as claimed in claim 6, the mol ratio that it is characterized in that above-mentioned polyfluoro aromatic, cholesterol, dewatering agent and catalyzer is 1: 0.8-1.5: 0.8-1.5: 0.01-0.10, temperature of reaction is a room temperature.
10. the synthetic method of sterol polyfluoro virtue carboxylic acid halides as claimed in claim 6, it is characterized in that the mol ratio of above-mentioned polyfluoro aromatic and acyl halogenating agent is 1: 2-1, temperature of reaction is a reflux temperature.
11. the synthetic method of sterol polyfluoro aromatic ester as claimed in claim 6, it is characterized in that the mol ratio of above-mentioned polyfluoro virtue carboxylic acid halides, sterol and organic bases is 1: 0.8-15: 0.8-1.5, temperature of reaction is a room temperature.
12. the purposes as claim 1,2,3,4 or 5 described sterol polyfluoro aromatic esters is characterized in that liquid crystal material.
CN98110842A 1998-05-15 1998-05-15 Sterol polyfluoro aromatic ester and its synthesis and use Expired - Fee Related CN1064369C (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN1111169C (en) * 1999-12-24 2003-06-11 中国科学院上海有机化学研究所 Sterol derivative, synthesis method and its application
CN1111167C (en) * 1999-10-22 2003-06-11 中国科学院上海有机化学研究所 3 beta-hydroxy-5-cholenic acid ester derivant, synthesis process and use thereof

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US491136A (en) * 1893-02-07 Blatt
FR2576025B1 (en) * 1985-01-14 1987-01-23 Roussel Uclaf NOVEL SUBSTITUTED STEROIDS IN POSITION 10, THEIR PROCESS AND THE PREPARATION INTERMEDIATES, THEIR APPLICATION AS MEDICAMENTS, THE PHARMACEUTICAL COMPOSITIONS CONTAINING THEM
HU201091B (en) * 1985-12-26 1990-09-28 Mitsubishi Chem Ind Process for producing gonatriene derivatives and pharmaceutical compositions comprising same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1111167C (en) * 1999-10-22 2003-06-11 中国科学院上海有机化学研究所 3 beta-hydroxy-5-cholenic acid ester derivant, synthesis process and use thereof
CN1111169C (en) * 1999-12-24 2003-06-11 中国科学院上海有机化学研究所 Sterol derivative, synthesis method and its application

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