CN1059459C - Liquid crystal compound contg. cyclohexyl and perfluoro benzene ring and preparing process thereof - Google Patents

Liquid crystal compound contg. cyclohexyl and perfluoro benzene ring and preparing process thereof Download PDF

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CN1059459C
CN1059459C CN97106778A CN97106778A CN1059459C CN 1059459 C CN1059459 C CN 1059459C CN 97106778 A CN97106778 A CN 97106778A CN 97106778 A CN97106778 A CN 97106778A CN 1059459 C CN1059459 C CN 1059459C
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liquid crystal
cyclohexyl
perfluoro
benzene ring
ring
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CN1183403A (en
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闻建勋
陈锡敏
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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 liquid crystal compound containing cyclohexyl and perfluoro benzene rings, which has the molecular formula as shown in the figure, wherein Z or Y is equal to R or RO; R or R' is equal to C1-14 straight chains, branch chains or chirality alkyl radicals; A or A' n = a benzene ring, a benzene ring with six carbon atoms, or a benzene ring with six carbon atoms and a fluorine atom; n is equal to 0 or 1. The liquid crystal compound is prepared by a Heck reaction and has the advantages of low melting point, high cleaning point, wide liquid crystal range, high birefringence rate, good chemical stability, good fat solubility and small viscosity, and furthermore, the liquid crystal material has wide application prospects.

Description

A kind of liquid crystalline cpd and preparation method who contains cyclohexyl and perfluoro-benzene-ring
The present invention relates to a kind of liquid crystalline cpd that contains cyclohexyl and perfluoro-benzene-ring, also can contain phenyl ring in this compound, ring with encircle between be connected by singly-bound or bridged bond.
Liquid crystal material needs low melting point, high clearing point, has wide mesomorphic phase scope, and phase wants simple.Introduce cyclohexyl or perfluoro-benzene-ring in the liquid crystal molecule respectively, can reduce liquid crystalline cpd viscosity, improve response speed, increase stability and improve clearing point temperature.Once report contained cyclohexyl and phenyl ring, or contained perfluoro-benzene-ring and phenyl ring liquid crystalline cpd (Lig, Cryst., 13 (5) 701-710,1993 as rigid nuclear; The same, 21 (2) 217-233,1996; J.Neter.Chem., 5 (3) 423-430,1995), but their weak point is that degree of birefringence is descended.People such as Wen Jianxun have reported the liquid crystalline cpd (CN92108444.7) that contains perfluoro-benzene-ring, between ring and ring, introduce acetylene bond, can improve degree of birefringence, make transformation temperature lower, a wider range, fat-soluble good, this patent also provides numerous intermediate that contains the perfluoro-benzene-ring liquid crystalline cpd and preparation method thereof.Because the huge applications potentiality of liquid crystal material, people are still constantly exploring the liquid crystal material of excellent property.
The purpose of this invention is to provide a kind of new liquid crystalline cpd and preparation method.Introduce cyclohexyl, perfluoro-benzene-ring and phenyl ring in this liquid crystalline cpd simultaneously, ring with encircle between with the center bridged bond or only singly-bound be connected, it is low to make this liquid crystalline cpd reach fusing point, the clearing point height, liquid crystal range is wide, phase is simple.
A kind of liquid crystalline cpd that contains cyclohexyl and perfluoro-benzene-ring of the present invention has following molecular formula:
Figure C9710677800031
Wherein Z or Y=R or R ' O, R or R '=C 1-14Straight chain, side chain or chirality alkyl, A or A '=
Figure C9710677800032
Or
Figure C9710677800033
N=0 or 1.The liquid crystalline cpd that contains cyclohexyl and perfluoro-benzene-ring of the present invention, can by Make through the Heck reaction, reaction employing=(trihydrocarbyl phosphine) dihalide palladium, two (trihydrocarbyl phosphine) palladium or two (trihydrocarbyl phosphine) Palladous nitrates and CuX make catalyzer, and reaction formula is as follows:
Figure C9710677800041
Wherein Z, Y, A and n as previously mentioned, B=I or Br, R "=C 1-14Alkyl or phenyl, X=halogen, X '=Br or I.
Figure C9710677800042
The mol ratio of palladium compound and CuX is 1: 1-10: 0.01-0.2: 0.02-0.40.
Adopt preparation method of the present invention, temperature of reaction be room temperature to reflux temperature, improve temperature of reaction and will help reaction and carry out.Reaction times is generally 0.5-100 hour.This reaction can be carried out in organic solvent.
When adopting preparation method of the present invention, the existence of nitrogenous organic ligand will help the carrying out that react.Nitrogenous organic ligand is the organic ligand that contains a nitrogen-atoms at least, is to have C 1-12The alkyl tertiary amine, secondary amine, the primary amine that replace, pyridine, the bipyridine compounds is as Trimethylamine 99, triethylamine, diethylamine, own butylamine, trioctylphosphine amine, pyridine, Tetramethyl Ethylene Diamine, tetraethylethylenediamine etc.
Figure C9710677800043
With nitrogenous organic ligand mol ratio be 1: 0-100, recommending mol ratio is 1: 1-10.
Intermediate
Figure C9710677800044
Substituted alkyl can be made by esterification.As by right-alkyl-cyclohexyl formic acid with to hydroxyl iodine or bromobenzene, at N, N-dicyclohexyl carbimide, following to pyrryl pyridine or the existence of 4-lutidine, mol ratio is followed successively by 1: 1-20: 1-3: 0.01-0.20, room temperature to reflux temperature, reaction times 1-100 hour.This alcoholization reaction carries out in polar solvent more favourable.
Liquid crystalline cpd of the present invention is simple synthetic method not only, owing to introduce cyclohexyl, perfluoro-benzene-ring and acetylene bond simultaneously, not only fusing point is low, viscosity is little, clearing point is high, liquid range is wide to make this compound, can reach 150 ℃, the degree of birefringence height, chemical stability is good, and phase is simple, removes minority and has S concurrently AWith N mutually outside, majority has only the N phase.It is a kind of liquid crystal material with wide application prospect.
To help to understand the present invention by following embodiment, but not limit content of the present invention.Embodiment 1
Will
Figure C9710677800051
6mmol,
Figure C9710677800052
6.6mmol, N, N-dicyclohexyl carbimide 6-10mmol and to pyrryl pyridine 10mg, stirring at room is about 5 hours in the ethylene dichloride solvent, chromatogram tracking to reaction finishes.Filter, after filtrate removing desolvated.Use column chromatography purification, use sherwood oil: the mixed solution of ethyl acetate=20: 1 is made eluent, concentrate white solid 2.282 grams.Productive rate 95.08%.Product 1HNMR (CCl 4/ TMS): 0.95 (t, 3H, CH 3), 1.1-2.8 (m, 16H, 6.85 (d, and 2H)/7.70 (d, 2H).Embodiment 2
With 152mg embodiment product,
Figure C9710677800053
0.4-0.5mmol, Pd (PPh 3) 2Cl 20.02-0.03mmol, CuI 0.05-0.08mmol and Et 3N 30ml, stirring at room 0.5h, back flow reaction 0.5-10h, chromatogram tracking finishes to reacting, and filters, and uses column chromatography after filtrate removing desolvated, and concentrates, and gets white crystal 183mg, with methyl alcohol-acetone recrystallization, obtains white Needle crystal, the product analysis result is as follows:
R '=C 8H 17, productive rate 70%.
1HNMR(CCl 4/TMS)：0.90(t，6H，2CH 3)，1.1-2.6(m，30H)；
4.20(t，2H，OCH 2)，7.0(d，2H)/7.50(d，2H)； 19FNMR(CCl 4/TFA)：60.0(m，2F)，79.5(m，2F)。IR(KBr，cm -1)： 2924，2853，2230，1754，1647，1599，1514，1493，1390，1243，
1211,1163,1128,983,848,725,570,533 MS (M/Z, %): 574 (M +, 167) and ultimate analysis: calculated value C 71.08, H 7.32, and F 13.24
Measured value C 71.18, H 7.23, F 12.87 R '=C 2H 5, productive rate 82% 1HNMR (Ccl 4/ TMS): 0.90 (t, 3H, CH 3), 0.95 (t, 3H, CH 3),
1.1-2.57(m，18H)，4.25(t，2H，OCH 2)，
7.0(d，2H)/7.50(d，2H)。 19FNMR(Ccl 4/TFA)：60.0(m. 27)，29.5(m，2F)IR(Kbr，cm -1)： 2924，2852，2233，1755，1648，1600，1513，1495，1290，1240，
1211，1162，1130，980，850，725，570，535。MS (M/Z, %): 490 (M +, 1.80) and ultimate analysis: calculated value C 68.57, H 6.12, and F 15.51
Measured value C 68.60, H 6.15, F 15.50R '=C 14H 29, productive rate 75%. 1HNMR(Ccl 4/TMS)：0.90(t，6H，2CH 3)，1.0-2.8(m，42H)，
4.30(t，2H，OCH 2)，7.05(d，2H/1.55(d，2H) 19F NMR(CCl 4/TFA)：59.5(m，2F)，79.0(m，2F)IR(KBr，cm -1)： 2926，2854，2235，1756，1649，1598，1510，1495，1390，1245，1210，
1165，1130，980，852，725，570。MS (M/Z, %): 658 (M +, 1.70) and ultimate analysis: calculated value C 72.95, H 8.21, and F 11.55
Measured value C 72.92, H 8.20, F 11.52 embodiment 3:
Will
Figure C9710677800061
0.1mmol,
Figure C9710677800062
0.1-0.5mmol and Pd (pph 3) 2X 2, 0.2mmol, CuX, 0.4mmol adds 30ml Et 3Among the N, 40 ℃ were reacted 1 hour, and product obtains with column chromatography and solvent recrystallization
Figure C9710677800063
Productive rate: 75-82%.The result is as follows: 1HNMR:0.95 (t; 6H, 2CH 3), 1.1-2.7 (m, 24H) (CCl 4/ TMS) 4.20 (t, 2H, OCH 2), 72.0 (m, 4H, Harom)
7.55/8.00(dd，4H，Harom)。
19FNMR(CCl 4/TFA)：60.5(m，2F)，80.5(m，2F)
MS(M/Z，％)：608(M +，4.16)
IR(KBr/cm -1)：2960，2918，2228，1733，1610，1516，1492，1393，1200
1060,983,882,700,537 ultimate analyses: theoretical value: C:73.03 H:6.58 F:12.50
Actual measurement: C:73.25 H:6.50 F:12.80
Figure C9710677800071
1HNMR(CCl 4/TMS)：0.95(t，6H，2CH 3)，1.1-27(m，26H)
4.25(t，2H，OCH 2)，7.30(m，4H，Harom)
7.60/8.10(dd，4H，Harom)
19FNMR(CCl 4/TFA)：60.0(m，2F)，80.0(m，2F)
MS(M/Z，％)：623(M ++1，3.75)
IR(KBr，cm -1)：2957，2922，2228，2734，1610，1516，1492，1390
1201,1064,983,880,700,538 ultimate analyses: theoretical (%): C 73.31 H 6.75 F 12.22
Actual measurement (%): C 73.52 H 6.81 F 12.30
1HNMR(CCl 4/TMS)：0.90(t，6H，2CH 3)1.0-2.60(m，28H)
4.25(t，2H，OCH 2)，7.25(m，4H，Harom)，
7.60/8.05(dd，4H，Harom)。
19FNMR(CCl 4/TFA)：60.0(m，2F)，80.0(m，2F)
MS(M/Z，％)：637(M ++1，2.99)
IR(KBr/cm -1)：2957，2922，2227，1734，1609，1491，1389，1203，
1063,983,845,699,539 ultimate analyses: theoretical (%): C 73.58 H 6.92 F 11.92
Actual measurement (%): C 73.60 H 6.72 F 11.93
1HNMR(CCl 4/TMS)：0.95(t，6H，2CH 3)，1.0-2.50(m，3OH)，
4.25(t，2H，OCH 2)，7.25(m，4H，Harom)
7.55/8.05(dd，4H，Harom)
19FNMR(CCl 4/TFA)：60.0(m，2F)，80.0(m，2F)
MS(M/Z，％)：651(M ++1，1.66)
IR(KBr/cm -1)：2954，2920，2221，1731，1619，1492，1389，1201，
1065,983,700,535 yuan of rope analyses: theoretical (%): C 73.85 H 7.08 F 11.69
Actual measurement (%): C 73.80 H 7.10 F 11.72 embodiment 4
Adopt the DSC collection of illustrative plates right
Figure C9710677800082
Compound is observed the variation of transformation temperature and heat content [℃ (J/g)], and the listed transformation temperature of its table 2 conforms to the polarizer observations substantially.Table 2.DSC method is measured
Figure C9710677800083
Temperature of degree mutually and heat content
Compound R 1 Phase C → N N → I I → N N → C
C 5H11 ℃ J/g C 6H 13 ℃ J/g C 7H 15 ℃ J/g C 8H 17 ℃ J/g C 9H 19 ℃ J/g C 12H 25 ℃ J/g 60.9 194.7 193.0 42.3 -55.55 -1.43 1.32 54.60 54.3 191.0 189.2 37.3 -102.31 -2.46 2.64 97.45 58.9 183.7 182.0 39.1 -2.21 -1.22 1.37 46.72 54.6 179.6 177.7 41.2 -71.95 -1.49 1.65 55.96 56.0 173.2 166.8 40.0 -58.93 -0.87 0.64 35.14 63.7 160.2 158.1 45.8 -104.18 -1.29 1.40 105.78
Embodiment 5
The employing orthogonal polarizing microscope is right Carry out transformation behavior research, the phase transition property that in heating and cooling process, occurs, their thermal behavior is listed in the table below, and wherein C represents crystal, and SA represented brilliant A phase, and N represents nematic phase, I represents isotropic liquid.From table, can find out that the temperature range of this compounds mesomorphic phase is very big, work as R 1〉=C 8H 17The time, nematic phase only appears.
Table 1
Figure C9710677800092
Phase transition property
Compound, R ' Phase transition property
C 5H 11 C 6H 13 C 7H 15 C 8H 17 C 9H 19 C 12H 25 60.5℃ 81.0℃ 192.8℃ 192.1℃ 74.2℃ 34.7℃ C———→S A———→N———→I———→N———→S A———→C 53.8℃ 63.2℃ 188.3℃ 186.7℃ 63.2℃ 30.8℃ C———→S A———→N———→I———→N———→S A———→C 57.3℃ 69.1℃ 181.6℃ 181.1℃ 67.6℃ 31.3℃ C———→S A———→N———→I———→N———→S A———→C 52.9℃ 177.9℃ 177.6℃ 40.4℃ C———→N———→I———→N———→C 51.6℃ 171.9℃ 177.6℃ 40.4℃ C———→N———→I———→N———→C 51.6℃ 171.4 169.9℃ 38.3℃ C———→N———→I———→N———→C

Claims (4)

1, a kind of liquid crystalline cpd that contains cyclohexyl and perfluoro-benzene-ring is characterized in that having following molecular formula: Wherein Z or Y=R or R ' O, R or R '=C 1-14Straight chain, side chain or chirality alkyl, A or A '=
Figure C9710677800022
Or
Figure C9710677800023
N=0 or 1.
2, liquid crystalline cpd as claimed in claim 1 is characterized in that having following molecular formula:
Figure C9710677800024
Z or Y=R or R ' O, R or R '=C 1-14Straight chain, side chain or chirality alkyl.
3, a kind of preparation method who contains the liquid crystalline cpd of cyclohexyl and perfluoro-benzene-ring as claimed in claim 1, it is characterized in that by
Figure C9710677800025
Palladium compound, CuX, nitrogenous organic ligand is in room temperature reaction 0.5-100 hour to the reflux temperature, and the above-claimed cpd mol ratio is followed successively by 1: 1-10: 0.01-0.2: 0.02-0.40: 0-100, wherein Z or Y=R or R ' O, R or R '=C 1-14Straight chain, side chain or chirality alkyl, A or A '=
Figure C9710677800026
Or
Figure C9710677800027
N=1 or 0, B=I or Br, X=halogen, described palladium compound are two (trihydrocarbyl phosphine) dihalide palladium, two (trihydrocarbyl phosphine) palladium or two (trihydrocarbyl phosphine) Palladous nitrate, and described nitrogenous organic ligand is to have C 1-12Tertiary amine, secondary amine, primary amine, pyridine, bipyridine, Tetramethyl Ethylene Diamine, the tetraethylethylenediamine of alkyl.
4, preparation method as claimed in claim 3 is characterized in that described
Figure C9710677800028
With the mol ratio of nitrogenous organic ligand be 1: 1-10.
CN97106778A 1997-12-15 1997-12-15 Liquid crystal compound contg. cyclohexyl and perfluoro benzene ring and preparing process thereof Expired - Fee Related CN1059459C (en)

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CN1307284C (en) * 2004-08-03 2007-03-28 江苏傲伦达科技实业股份有限公司 Alkyl cyclohexyl alkynes liquid crystal compound and its preparation method
CN102031120B (en) * 2010-11-17 2013-07-10 上海天问化学有限公司 Fluorine-containing liquid crystal of 4-(2,3,5,6-tetrafluo-R substituent phenethyl) benzoic acid-4'-fluo-4-biphenyl ester
CN102020553B (en) * 2010-11-17 2013-10-30 上海天问化学有限公司 P-alkyl group substituted-4-fluorophenylacetic acid, synthesis method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4111998A1 (en) * 1990-04-13 1991-10-17 Merck Patent Gmbh Liq. crystal mixt. with wide nematic phase range etc. - contg. one or more substd. alkyl 1,4-cyclohexylene phenylene fluoride(s)
CN1066458A (en) * 1992-06-04 1992-11-25 中国科学院上海有机化学研究所 Contain liquid crystalline cpd of perfluoro-benzene-ring and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4111998A1 (en) * 1990-04-13 1991-10-17 Merck Patent Gmbh Liq. crystal mixt. with wide nematic phase range etc. - contg. one or more substd. alkyl 1,4-cyclohexylene phenylene fluoride(s)
CN1066458A (en) * 1992-06-04 1992-11-25 中国科学院上海有机化学研究所 Contain liquid crystalline cpd of perfluoro-benzene-ring and preparation method thereof

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