CN1124273C - Fluoric diphenylacetylene compounds and preparing process and application thereof - Google Patents

Fluoric diphenylacetylene compounds and preparing process and application thereof Download PDF

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CN1124273C
CN1124273C CN00115133A CN00115133A CN1124273C CN 1124273 C CN1124273 C CN 1124273C CN 00115133 A CN00115133 A CN 00115133A CN 00115133 A CN00115133 A CN 00115133A CN 1124273 C CN1124273 C CN 1124273C
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fluorine
cdcl
nmr
diphenyl
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CN1271712A (en
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闻建勋
李衡峰
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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

The present invention relates to a diphenylacetylene compound containing fluorine, which has the molecular formula as the following figure, wherein R or R'=C<1 to 12> alkyl radicals; X=H or F; a is like the right lower figure. The present invention is prepared by a Heck reaction or a condensation reaction. The compound has the characteristics of wide liquid crystal phase range, low viscosity and good fat solubility, and furthermore, the compound of the present invention is new liquid crystal material.

Description

Fluorine-containing (diphenyl) acetylene compounds, Preparation method and use.
The present invention relates to a kind of fluorine-containing (diphenyl) acetylene compounds.This compound one side connects alkoxyl group, and opposite side connects oxygen, sulphur, heterogeneous ring compounds such as boron.This compound can make respectively by Heck reaction or condensation reaction, is a kind of novel liquid crystal material.
Liquid crystal material needs low melting point, high clearing point, and the mesomorphic phase wide ranges, chemical stability is good, the degree of birefringence height, viscosity is low, and is fat-soluble good.Haruyoshi Takatsu, people such as Kodaira have reported a kind of tolane nematic liquid crystalline cpd (U.S.P.4705870,1987).People such as Wen Jianxun have reported the liquid crystalline cpd (CN 9,210 84444.7) of fluorine-containing phenyl ring, introduce acetylene bond between ring and ring, can improve degree of birefringence, use transformation temperature lower, and a wider range is fat-soluble good.People such as Wen Jianxun have also reported and have utilized the synthetic fluorine-containing tolane liquid crystalline cpd (CN 00111985.0) that contains the liquid crystalline cpd (CN 97106778.3) of cyclohexyl and perfluoro-benzene-ring and contain side chain of olefinic oxygen of Heck reaction.Because the increasingly extensive application of liquid crystal material, people still expect constantly to explore the liquid crystal material of excellent property.
The purpose of this invention is to provide a kind of new fluorine-containing (diphenyl) acetylene compounds.Connect alkoxyl group and heterocycle respectively in the compound both sides.
Purpose of the present invention also provides the method for preparing above-claimed cpd.
Another object of the present invention provides the purposes that above-claimed cpd is used for liquid crystal material.
Fluorine-containing (diphenyl) acetylene compounds of the present invention has following molecular formula:
Figure C0011513300041
R or R '=C wherein 1-12Alkyl, X=H or F, As following compound:
Figure C0011513300044
Figure C0011513300051
Deng.
The preparation of fluorine-containing (diphenyl) acetylene compounds of the present invention can be made respectively by Heck reaction or condensation reaction, further describes as follows:
The oxygen that contains of the present invention, sulphur, the fluorine-containing (diphenyl) acetylene compounds of heterocyclic such as boron can be by molecular formula: The palkoxy benzene acetylene compound and molecular formula be I or Halogenide makes through the Heck reaction, and reaction formula is:
Figure C0011513300055
Or
Figure C0011513300056
R wherein, R ', X and A are all ditto described.
Specifically, above-mentioned fluorine-containing (diphenyl) acetylene compounds, halogenide is at palladium compound, CuX and nitrogenous organic ligand exist down, to reflux temperature, react 0.5-100h in room temperature, the above-claimed cpd mol ratio is followed successively by 1: 1-10: 0.01-0.2: 0.02-0.40: 0-100.Described palladium compound is two (trihydrocarbyl phosphine) dihalide palladium, two (trihydrocarbyl phosphine) palladium, and two (trihydrocarbyl phosphine) Palladous nitrate, common described alkyl is C 1-12Alkyl, described nitrogenous organic ligand is to have C 1-12The tertiary amine of alkyl, secondary amine, primary amine, pyridine, bipyridine etc.The having of nitrogenous organic ligand helps the carrying out that react, and the above-mentioned halogenide and the mol ratio of nitrogenous organic ligand are recommended as 1: 1-10, recommend to use triethylamine.
The oxygen that contains of the present invention, sulphur, the fluorine-containing (diphenyl) acetylene compounds of heterocyclic such as boron also can be made by condensation reaction, and reaction formula is as follows: Or
Figure C0011513300062
Figure C0011513300063
R wherein, R ', X are all ditto described, Y or Z=O or S.Described condensation reaction is in organic solvent, and under the reflux conditions, molecular formula is Benzaldehyde compound, or molecular formula is
Figure C0011513300065
Aryl boric acid, tosic acid and molecular formula are
Figure C0011513300066
Heteroatoms alkylol cpd, mol ratio are 1: 0.01-0.2: 1-10, the reaction times is 0.5-24h.Recommend mol ratio to be followed successively by 1: 0.01: 1.1.
Because the existence of sulphur atom in the thia ring, palladium compound is poisoned and the reduction reaction yield, so adopt alcohol condensation under Catalyzed by p-Toluenesulfonic Acid of aldehyde cpd and sulfur-bearing, can obtain the fluorine-containing (diphenyl) acetylene compounds of higher yields, have more practical value.
Fluorine-containing (diphenyl) acetylene compounds of the present invention is simple synthetic method not only, and is a kind of novel good TN, STN and TFT liquid crystal display material.Have low melting point, high clearing point, the mesomorphic phase wide ranges, chemical stability is good, the degree of birefringence height, viscosity is low, and fat-soluble characteristics such as good are suitable for suitability for industrialized production and application.
The present invention will be helped to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1 Preparation:
With I or
Figure C0011513300071
200mg, 100-150mg, two (triphenylphosphine) Palladous chlorides or Palladous nitrate 5-15mg, CuI 10-20mg, triethylamine 5-20ml is at room temperature to 60 ℃ stirring 10-24h, high pressure liquid chromatography or fluorine spectrum track to reaction and finish, filter, add organic solvent extraction, the organic phase dried over sodium sulfate, boil off solvent, column chromatography for separation.The result is as shown in the table:
Sequence number R Productive rate %
1 2 3 4 5 6 C 4H 9 C 5H 11 C 6H 13 C 7H 15 C 8H 17 C 12H 25 51 57 53 54 54 49
Compound 1: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.78 (m, 18H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.5Hz); 3.95-4.01 (m, 2H); 4.22-4.27 (m, 2H); 5.41 (s, 1H); 6.84-6.90 (m, 2H); 7.44-7.53 (m, 6H) .MS m/z (%): 406 (M +, 100.0), 222 (43.35) ultimate analyses: calculated value .C, 79.77; H, 8.43%.
Analytical value .C, 79.91; H, 8.53%. compound 2: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.78 (m, 20H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.5Hz); 3.95-4.01 (m, 2H); 4.22-4.27 (m, 2H); 5.41 (s, 1H); 6.84-6.90 (m, 2H); 7.44-7.53 (m, 6H) .MS m/z (%): 420 (M +, 100.0), 222 (27.96) ultimate analyses: calculated value .C, 79.96; H, 8.63%.
Analytical value .C, 80.23; H, 8.78%. compound 3: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.78 (m, 22H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.5Hz); 3.95-4.01 (m, 2H); 4.22-4.27 (m, 2H); 5.41 (s, 1H); 6.84-6.90 (m, 2H); 7.44-7.53 (m, 6H) .MS m/z (%): 434 (M +, 100.0), 222 (30.26) ultimate analyses: calculated value .C, 80.14; H, 8.81%.
Analytical value .C, 80.21; H, 8.91%. compound 4: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.78 (m, 24H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.5Hz); 3.95-4.01 (m, 2H); 4.22-4.27 (m, 2H); 5.41 (s, 1H); 6.84-6.90 (m, 2H); 7.44-7.53 (m, 6H) .MS m/z (%): 448 (M +, 100.0), 222 (54.99) ultimate analyses: calculated value .C, 80.32; H, 8.99%.
Analytical value .C, 80.39; H, 9.08%. compound 5: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.78 (m, 26H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.5Hz); 3.95-4.01 (m, 2H); 4.22-4.27 (m, 2H); 5.41 (s, 1H); 6.84-6.90 (m, 2H); 7.44-7.53 (m, 6H) .MSm/z (%): 462 (M +, 100.0), 222 (63.67) ultimate analyses: calculated value .C, 80.48; H, 9.15%.
Analytical value .C, 80.64; H, 9.24%. compound 6: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.78 (m, 34H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.5Hz); 3.95-4.01 (m, 2H); 4.22-4.27 (m, 2H); 5.41 (s, 1H); 6.84-6.90 (m, 2H); 7.44-7.53 (m, 6H) .MSm/z (%): 518 (M +, 100.0), 222 (58.21) ultimate analyses: calculated value .C, 81.03; H, 9.71%.
Analytical value .C, 80.89; H, 9.85%.
Embodiment 2
Figure C0011513300081
Preparation:
With I or
Figure C0011513300082
0.1mmol,
Figure C0011513300083
0.1-0.15mmol, two (triphenylphosphine) Palladous chlorides or two (tri octyl phosphine) Palladous nitrate 5-15mg, CuI10-20mg adds triethylamine or pyridine 10ml, and at room temperature to 60 ℃ stirring 24h, product concentrates through column chromatography for separation.The result is as follows:
Sequence number R Productive rate %
7 8 C 4H 9 C 5H 11 48 48
10 11 12 C 7H 15 C 8H 17 CH 3 46 48 52
Compound 7: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.80 (m, 18H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.4Hz); 4.22-4.29 (m, 4H); 5.42 (s, 1H); 7.48-7.59 (m, 4H). 19FNMR δ F(60MHz; CDCl 3TFA): 60.0 (m, 2F); 79.6 (m, 2F) MS m/z (%): 478 (M +, 72.32), 294 (100.0) ultimate analyses: calculated value .C, 67.77; H, 6.32; F, 15.88%.
Analytical value .C, 67.58; H, 6.17; F, 16.29%. compound 8: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.80 (m, 20H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.4Hz); 4.22-4.29 (m, 4H); 5.42 (s, 1H); 7.48-7.59 (m, 4H). 19F NMR δ F(60MHz; CDCl 3TFA): 60.0 (m, 2F); 79.6 (m, 2F) MS m/z (%): 492 (M +, 84.02), 294 (100.0) ultimate analyses: calculated value .C, 68.28; H, 6.55; F, 15.43%.
Analytical value .C, 68.29; H, 6.49; F, 15.49%. compound 9: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.80 (m, 22H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.4Hz); 4.22-4.29 (m, 4H); 5.42 (s, 1H); 7.48-7.59 (m, 4H). 19F NMR δ F(60MHz; CDCl 3TFA): 60.0 (m, 2F); 79.6 (m, 2F) MS m/z (%): 506 (M +, 61.51), 294 (100.0) ultimate analyses: calculated value .C, 68.76; H, 6.76; F, 15.00%.
Analytical value .C, 68.82; H, 6.72; F, 15.26%. compound 10: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.80 (m, 24H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.4Hz); 4.22-4.29 (m, 4H); 5.42 (s, 1H); 7.48-7.59 (m, 4H). 19F NMR δ F(60MHz; CDCl 3TFA): 60.0 (m, 2F); 79.6 (m, 2F) MSm/z (%): 520 (M +, 100.0), 294 (94.52) ultimate analyses: calculated value .C, 69.21; H, 6.97; F, 14.60%.
Analytical value .C, 69.12; H, 6.91; F, 14.88%. compound 11: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.80 (m, 26H); 2.15 (m, 1H); 3.54 (t, 2H, J=11.4Hz); 4.22-4.29 (m, 4H); 5.42 (s, 1H); 7.48-7.59 (m, 4H). 19F NMR δ F(60MHz; CDCl 3TFA): 60.0 (m, 2F); 79.6 (m, 2F) MS m/z (%): 534 (M +, 99.82), 294 (89.57) ultimate analyses: calculated value .C, 69.64; H, 7.16; F, 14.21%.
Analytical value .C, 69.72; H, 7.11; F, 14.54%. compound 12: 1H NMR δ H(300MHz; CDCl 3TMS): 0.88-1.80 (m, 11H); 2.15 (m, 1H); 3.54 (m, 3H); 4.22-4.29 (m, 4H); 5.42 (s, 1H); 7.48-7.59 (m, 4H). 19F NMR δ F(60MHz; CDCl 3TFA): 60.0 (m, 2F); 79.6 (m, 2F) MS m/z (%): 436 (M +, 100.0), 294 (95.34) ultimate analyses: calculated value .C, 66.05; H, 5.54; F, 17.41%.
Analytical value .C, 66.31; H, 5.51; F, 17.32%.
Embodiment 3
Figure C0011513300101
Preparation: adopt
Figure C0011513300102
With Be raw material, operation is with embodiment 1, and the result is as follows:
Sequence number R Productive rate %
13 14 15 16 17 C 4H 9 C 5H 11 C 6H 13 C 7H 15 C 8H 17 53 57 51 58 58
Compound 13: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.82 (m, 18H); 2.09 (m, 1H); 3.51 (t, 2H, J=11.4Hz); 3.96-4.00 (m, 2H); 4.21-4.26 (m, 2H); 5.35 (s, 1H); 6.86-7.52 (m, 6H). 19FNMR δ F(60MHz; CDCl 3TFA): 30.0 (s, 2F) MS m/z (%): 442 (M+, 100.0), 258 (29.62) ultimate analyses: calculated value .C, 67.77; H, 6.32; F, 8.59%.
Analytical value .C, 67.58; H, 6.17; F, 8.40%. compound 14: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.82 (m, 20H); 2.09 (m, 1H); 3.51 (t, 2H, J=11.4Hz); 3.96-4.00 (m, 2H); 4.21-4.26 (m, 2H); 5.35 (s, 1H); 6.86-7.52 (m, 6H). 19F NMR δ F(60MHz; CDCl 3TFA): 30.0 (s, 2F) MS m/z (%): 456 (M +, 100.0), 258 (79.59) ultimate analyses: calculated value .C, 67.77; H, 6.32; F, 8.32%.
Analytical value .C, 67.58; H, 6.17; F, 8.42%. compound 15: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.82 (m, 22H); 2.09 (m .1H); 3.51 (t, 2H, J=11.4Hz); 3.96-4.00 (m, 2H); 4.21-4.26 (m, 2H); 5.35 (s, 1H); 6.86-7.52 (m, 6H). 19FNMR δ F(60MHz; CDCl 3TFA): 30.0 (s, 2F) MSm/z (%): 470 (M +, 100.0), 258 (73.76) ultimate analyses: calculated value .C, 67.77; H, 6.32; F, 8.07%.
Analytical value .C, 67.58; H, 6.17; F, 8.04%. compound 16: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.82 (m, 24H); 2.09 (m, 1H); 3.51 (t, 2H, J=11.4Hz); 3.96-4.00 (m, 2H); 4.21-4.26 (m, 2H); 5.35 (s, 1H); 6.86-7.52 (m, 6H). 19F NMR δ F(60MHz; CDCl 3TFA): 30.0 (s, 2F) MS m/z (%): 484 (M +, 100.0), 258 (75.15) ultimate analyses: calculated value .C, 67.77; H, 6.32; F, 7.84%..
Analytical value .C, 67.58; H, 6.17; F, 7.92%. compound 17: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.82 (m, 26H); 2.09 (m, 1H); 3.51 (t, 2H, J=11.4Hz); 3.96-4.00 (m, 2H); 4.21-4.26 (m, 2H); 5.35 (s, 1H); 6.86-7.52 (m, 6H). 19F NMR δ F(60MHz; CDCl 3TFA): 30.0 (s, 2F) MS m/z (%): 498 (M +, 100.0), 258 (75.30) ultimate analyses: calculated value .C, 67.77; H, 6.32; F, 7.62%.
Analytical value .C, 67.58; H, 6.17; F, 7.46%.
Embodiment 4
Figure C0011513300111
Preparation: adopt
Figure C0011513300112
With Be raw material, operation is with embodiment 2, and the result is as follows:
Sequence number R Productive rate %
18 19 20 21 22 C 4H 9 C 5H 11 C 6H 13 C 7H 15 C 8H 17 45 43 43 46 42
Compound 18: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.81 (m, 18H); 2.11 (m, 1H); 3.52 (t, 2H, J=11.4Hz); 4.21-4.31 (m, 4H); 5.34 (s, 1H); 7.08-7.12 (m, 2H). 19F NMR δ F(60MHz; CDCl 3TFA): 28.6 (s, 2F); 59.8 (m, 2F); 79.9 (m, 2F) MS m/z (%): 514 (M +, 31.38), 330 (100.0.) ultimate analysis: calculated value .C, 63.03; H, 5.49; F, 22.16%.
Analytical value .C, 62.95; H, 5.41; F, 22.45%. compound 19: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.81 (m, 20H); 2.12 (m, 1H); 3.51 (t, 2H, J=11.5Hz); 4.21-4.30 (m, 4H); 5.36 (s, 1H); 7.09-7.12 (m, 2H). 19F NMR δ F(60MHz; CDCl 3TFA): 28.6 (s, 2F); 59.8 (m, 2F); 79.9 (m, 2F) MS m/z (%): 528 (M +, 25.55), 330 (100.0.) ultimate analysis: calculated value .C, 63.63; H, 5.72; F, 21.57%.
Analytical value .C, 63.48; H, 5.64; F, 21.45%. compound 20: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.83 (m, 22H); 2.13 (m, 1H); 3.52 (t, 2H, J=11.5Hz); 4.21-4.30 (m, 4H); 5.37 (s, 1H); 7.10-7.12 (m, 2H). 19F NMR δ F(60MHz; CDCl 3TFA): 28.6 (s, 2F); 59.8 (m, 2F); 79.9 (m, 2F) MS m/z (%): 542 (M +, 23.12), 330 (100.0.) ultimate analysis: calculated value .C, 64.20; H, 5.94; F, 21.01%.
Analytical value .C, 63.90; H, 5.85; F, 21.08%. compound 21: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.88 (m, 24H); 2.12 (m, 1H); 3.52 (t, 2H, J=11.5Hz); 4.21-4.30 (m, 4H); 5.36 (s, 1H); 7.10-7.12 (m, 2H). 19F NMR δ F(60MHz; CDCl 3TFA): 28.6 (s, 2F); 59.8 (m, 2F); 79.9 (m, 2F) MS m/z (%): 556 (M +, 26.11), 330 (100.0.) ultimate analysis: calculated value .C, 64.74; H, 6.16; F, 20.48%.
Analytical value .C, 64.60; H, 6.13; F, 20.84%.J=11.5Hz); 4.21-4.30 (m, 4H); 5.36 (s, 1H); 7.10-7.12 (m, 2H). 19F NMR δ F(60MHz; CDCl 3TFA): 28.6 (s, 2F); 59.8 (m, 2F); 79.9 (m, 2F) MS m/z (%): 556 (M +, 26.11), 330 (100.0.) ultimate analysis: calculated value .C, 64.74; H, 6.16; F, 20.48%.
Analytical value .C, 64.60; H, 6.13; F, 20.84%. compound 22: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.81 (m, 26H); 2.12 (m, 1H); 3.52 (t, 2H, J=11.4Hz); 4.21-4.30 (m, 4H); 5.37 (s, 1H); 7.10-7.12 (m, 2H). 19F NMR δ F(60MHz; CDCl 3TFA): 28.6 (s, 2F); 59.8 (m, 2F); 79.9 (m, 2F) MS m/z (%): 570 (M +, 18.37), 330 (100.0.) ultimate analysis: calculated value .C, 65.25; H, 6.36; F, 19.98%.
Analytical value .C, 65.37; H, 6.42; F, 19.87%.
Embodiment 5 The preparation of compound 23: will 250mg, C 6H 13CH (CH 2OH) 2170mg, tosic acid 5-20mg, acetone 20ml places reaction flask, reflux 2 hours, removal of solvent under reduced pressure, column chromatography for separation, the productive rate with 82% gets compound 23.Compound 23: 1H NMR δ H(300MHz; CDCl 3TMS): 0.87-1.82 (22H); 2.16 (m, 1H); 3.78-3.85 (t, 2H, J=10.2Hz); 3.95-3.99 (t, 2H, J=6.6Hz); 4.17-4.22 (m, 2H); 6.85-6.98 (m, 4H); 7.43-7.45 (m, 2H) ppm. 19F NMR δ F(60MHz; CDCl 3TFA): 25.2 (s, 2F) ppm.MS m/z (%): 468 (M +, 100.0), 398 (57.19). ultimate analysis: calculated value .C, 71.80; H, 7.53%.
Analytical value .C, 71.79; H, 7.42%.
Embodiment 6
Figure C0011513300133
The preparation of compound 24: 2H, J=6.55Hz); 5.12 (s, 1H); 6.85-7.51 (m, ArH, 6H) ppm.MS m/z (%): 452 (M +, 100.0). ultimate analysis: calculated value .C, 74.29; H, 8.02%.
Analytical value .C, 74.47; H, 7.81%.
Embodiment 7
Figure C0011513300141
The preparation of compound 25: adopt
Figure C0011513300142
Be raw material, operation is with embodiment 6, and the result is as follows: compound 25: 1H NMR δ H(300MHz; CDCl 3TMS): 0.89-1.91 (20H); 2.74-3.18 (m, 4H); 3.97 (t, 2H, J=6.55Hz); 5.72 (s, 1H); 6.85-7.51 (m, ArH, 6H) ppm.MS m/z (rel.int.): 436 (M +, 100.0). ultimate analysis: calculated value .C, 77.02; H, 8.31%.
Analytical value .C, 77.22; H, 8.29%.
Embodiment 8
Adopt orthogonal polarizing microscope the part of compounds of embodiment 1 to 7 to be carried out phase research, the phase transition property that in heating and cooling process, occurs.During their transformation behavior was listed in the table below, wherein C represented crystal, and N represents nematic phase, and I represents isotropic liquid, and Recr represents recrystallization.From table, can find out that the mesomorphic phase scope of this compounds is very wide.
The compound sequence number Phase transition property
1 Cr104.4N216.3I201.9N92.7Recr
2 Cr100.2N205.5I200.1N89.2Recr
3 Cr94.9N201.1I197.9N92.0Recr
4 Cr98.4N192.9I188.8N95.6Recr
5 Cr100.9N188.8I186.4N97.5Recr
7 Cr77.3N176.9I175.0N66.4Recr
8 Cr65.2N167.8I166.0N51.2Recr
9 Cr58.7N163.0I160.9N44.7Recr
10 Cr58.7N155.3I153.5N46.1Recr
11 Cr59.2N153.3I152.0N42.5Recr
13 Cr94.3N188.5I180.3N88.7Recr
14 Cr86.3N177.9I176.3N73.9Recr
15 Cr94.4N157.5I156.8N75.4Recr
16 Cr97.2N158.5I156.8N73.8Recr
17 Cr85.0N165.0I163.6N78.4Recr
18 Cr87.2N167.1I165.1N61.8Recr
19 Cr74.2N155.7I154.0N56.4Recr
20 Cr66.2N153.0I151.0N43.3Recr
21 Cr60.3N145.2I143.7N49.7Recr
22 Cr63.4N143.6I142.0N60.5Recr
23 Cr68.3N118.1I116.5N55.7Recr
24 Cr119.6N195.2I192.9N91.4Recr
25 Cr109.6N172.7I170.9N79.3Recr

Claims (7)

1. fluorine-containing tolane compound is characterized in that having following molecular formula: R or R '=C wherein 1-12Alkyl, X=H or F, A
2. fluorine-containing (diphenyl) acetylene compounds as claimed in claim 1 is characterized in that molecular formula is:
Figure C0011513300023
R wherein, R ' and X are described with claim 1.
3. fluorine-containing (diphenyl) acetylene compounds as claimed in claim 1 is characterized in that molecular formula is:
Figure C0011513300024
R wherein, R ' and X are described with claim 1.
4. fluorine-containing (diphenyl) acetylene compounds as claimed in claim 1 is characterized in that molecular formula is:
Figure C0011513300025
R wherein, R ' and X are described with claim 1.
5. fluorine-containing (diphenyl) acetylene compounds as claimed in claim 1 is characterized in that molecular formula is: R wherein, R ' and X are described with claim 1.
6. the preparation method of a fluorine-containing (diphenyl) acetylene compounds as claimed in claim 1 is characterized in that making respectively with following method:
(1). by The substitutedphenylethynyl compounds, Br or Halogenide at palladium compound, CuI exists down, makes through the Heck reaction;
(2). in organic solvent and room temperature to reflux temperature, by Aldehyde cpd, or Boronic acid compounds, tosic acid and molecular formula are The condensation reaction of heteroatoms alkylol cpd make, mol ratio is 1: 0.01-0.2: 1-10, reacted 0.5-24 hour;
R wherein, R ' and X are described with claim 1, Y=O or S, Z=O or S.
7. the purposes of a fluorine-containing (diphenyl) acetylene compounds as claimed in claim 1 is characterized in that being used for liquid crystal material.
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US4705870A (en) * 1984-01-23 1987-11-10 Dainippon Ink And Chemicals, Inc. Tolan-type nematic liquid crystalline compounds

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US4705870A (en) * 1984-01-23 1987-11-10 Dainippon Ink And Chemicals, Inc. Tolan-type nematic liquid crystalline compounds

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