CN1263927A - Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process - Google Patents

Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process Download PDF

Info

Publication number
CN1263927A
CN1263927A CN 00111985 CN00111985A CN1263927A CN 1263927 A CN1263927 A CN 1263927A CN 00111985 CN00111985 CN 00111985 CN 00111985 A CN00111985 A CN 00111985A CN 1263927 A CN1263927 A CN 1263927A
Authority
CN
China
Prior art keywords
side chain
oxygen
cdcl
ppm
liquid crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 00111985
Other languages
Chinese (zh)
Other versions
CN1101444C (en
Inventor
闻建勋
刘克刚
李衡峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Organic Chemistry of CAS
Original Assignee
Shanghai Institute of Organic Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Organic Chemistry of CAS filed Critical Shanghai Institute of Organic Chemistry of CAS
Priority to CN 00111985 priority Critical patent/CN1101444C/en
Publication of CN1263927A publication Critical patent/CN1263927A/en
Application granted granted Critical
Publication of CN1101444C publication Critical patent/CN1101444C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

A fluoric diphenylacetylene liquid crystal compound containing the side chain of olifinic oxygen is prepared by Heck reaction. Its advantages include low melting point, High brightness, wide range of liquid crstal, high double refractivity, chemical stability and liposolubility, and low viscosity.

Description

A kind of fluorine-containing tolane liquid crystalline cpd that contains side chain of olefinic oxygen and preparation method thereof
The present invention relates to a kind of fluorine-containing tolane liquid crystalline cpd that contains side chain of olefinic oxygen.
Liquid crystal material needs low melting point, high clearing point, mesomorphic phase wide ranges, chemical stability is good, degree of birefringence is high, fat-soluble good.People such as Wen Jianxun have reported the liquid crystalline cpd (CN9210 84444.7) of fluorine-containing phenyl ring, between ring and ring, introduce acetylene bond, can improve degree of birefringence, use lower, a wider range, fat-soluble good of transformation temperature, and intermediate that contains the perfluoro-benzene-ring liquid crystalline cpd and preparation method thereof is provided.People such as Wen Jianxun have also reported and have utilized the synthetic a kind of liquid crystalline cpd (CN 97106778.3) that closes cyclohexyl and perfluoro-benzene-ring of Heck reaction.Once reported in the liquid crystalline cpd and to introduce ethylene linkage and will help to reduce viscosity (Schaclt Metal 1990, Liq.Cryst.7,519), 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 liquid crystalline cpd and preparation method.Introduce fluorine-containing two phenyl ring acetylene in this liquid crystalline cpd simultaneously, be connected with alkene oxygen key, make this liquid crystalline cpd reach that viscosity is low, fusing point is low, clearing point is high, liquid crystal range is wide, phase is simple in fluorine-containing phenyl ring-side.
A kind of fluorobenzene diine liquid crystalline cpd that contains that contains side chain of olefinic oxygen of the present invention has following molecular formula:
Figure A0011198500031
R=C wherein 3-C 12Thiazolinyl, this thiazolinyl comprises the thiazolinyl of two keys of terminal olefinic link or different positions and the two keys of cis-trans, R 1, R 2Or R 3=H, F, C 1-3Perfluoroalkyl or C 1-3Perfluoro alkoxy.
The liquid crystalline cpd that contains the fluorine-containing tolane of side chain of olefinic oxygen of the present invention, can by
Figure A0011198500041
With
Figure A0011198500042
Make through the Heck reaction, reaction adopts two (trihydrocarbyl phosphine) dihalide palladium, two (trihydrocarbyl phosphine) palladium or two (trihydrocarbyl phosphine) Palladous nitrates and CuX to make catalyzer, and reaction formula is as follows: Wherein R, R 1, R 2And R 3As previously mentioned, B=I or Br, X=halogen.
Preparation method of the present invention, basic identical with the described method of CN97106778.3, The mol ratio of palladium compound and CuX is 1: 1-10: 0.01-0.2: 0.02-0.40.Reacted 0.5-100 hour to reflux temperature in room temperature.This reaction can be carried out in organic solvent.The existence of nitrogenous organic ligand will help the carrying out that react.Described 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, primary amine, pyridine, the bipyridine compounds that replace. With nitrogenous organic ligand mol ratio be 1: 0-100, recommending mol ratio is 1: 1-10.
Intermediate Can be by halo perfluor benzene and HC ≡ CSiMe 3Make through the Heck reaction
Figure A0011198500047
, in the presence of alkali, make with the enol reaction again.
Liquid crystalline cpd of the present invention is simple synthetic method not only, owing to introduce side chain of olefinic oxygen, fluorine-containing tolane, make this compound have the various sets of advantages of available liquid crystal compound in one, have the An height, advantage such as viscosity is low, response speed is fast, liquid crystal phase transition wide ranges, phase transformation are single, be a kind of liquid crystal material rare in the TFT-LCD technology, have very application prospects.To help to understand the present invention by following experiment, but not limit content of the present invention.
Embodiment 1
Figure A0011198500051
Preparation (1)
In the 100ml reaction flask, add 1.54g 2.52g two cyclohexyl nitrogen diimines (DCC), 25mg4-Dimethylamino pyridine (DMAP) and 30ml methylene dichloride at room temperature stir 24h, and TLC follows the tracks of, reaction use column chromatography after finishing product 3.13g, productive rate 83.2%.
Preparation (2)
Pd (pph is being housed 3) 2Cl 2Or Pd[p (C 8H 17) 3] 2(NO 3) 2250mg in the reaction flask of CuI or CuBr75-100mg, adds Et 3N and five fluorine iodobenzene 5.0g, trimethylsilyl acetylene 2.25g.Logical N 2After 5 minutes,, track to reaction with the fluorine spectrum and finish 25-30 ℃ of reaction down.Add the 20ml ether in reaction mixture, filter, organic phase washes with water to neutrality, and decompression obtains product 3.6g, productive rate 82.0%.
Figure A0011198500054
Preparation (3)
In reaction flask, add compound (2) 2.0g, 1.40g, K 2CO 32.0g reach toluene 20ml, stir under the room temperature, the fluorine spectrum tracks to reaction and finishes, and adds organic solvent and water extraction, organic phase Na 2SO 4Drying, steaming desolventizes, and column chromatography for separation gets compound (3) 1.48g, productive rate 81.3%.
19F?NMR(CDCl 3/TFA)，δ：63.0(m，2F)，80.9(m，2F)ppm.
HNMR(CDCl 3/TMS)，δ：6.01(M，1H)，5.40(dd，1H)，5.25(M，1H)，
4.55 (t, 2H), 3.72 (S, 1H), 2.77 (q, 2H) ppm.
Figure A0011198500061
Preparation (4)
With compound (3) 200mg, compound (1) 233mg, Pd (pph 3) 2Cl 2Or Pd[P (C 8H 17) 3] 2Br20-30mg, CuX 8-10mg places the 25ml round-bottomed bottle, adds 10ml Et 3N or bipyridine, at 50-60 ℃ by induction stirring 15-24h.Product concentrates and obtains compound (4) 323mg, productive rate 86.2% through column chromatography for separation.
MS(M/Z，％)：458(M +，11.16％)
Ultimate analysis: calculated value F 20.72 H3.30 C65.51
Measured value F 20.98 H3.47 C65.46
1H?NMR(CDCl 3/TMS)，δ：8.30(m，2H)，7.73(m，2H)，7.32(m，4H)，
5.87(m，1H)，5.32(dd，1H)，5.19(M，H)，4.41(t，2H)，2.65(q，
2H)ppm.
19F?NMR(CDCl 3/TFA)，δ：27.2(M，1F)，61.3(M，2F)，80.8(M，2F)ppm.
Embodiment 2
Will
Figure A0011198500062
1-5mmol, two (tri octyl phosphine) palladium or two (triphenylphosphine) Palladous chloride 20-50mg, CuX5-20mg places reaction flask.Add trioctylamine or pyridine 10-20ml, at room temperature to 80 ℃ reaction 10-30h, product concentrates and obtains through column chromatography for separation
Figure A0011198500063
, the results are shown in the following table: compound sequence number R R 1R 2R 3Productive rate 5 F F H 82.7%6
Figure A0011198500072
H OCF 3H 87.6%7
Figure A0011198500073
H F H 80.0%8 H CF 3H 78.9%9
Figure A0011198500075
H CF 3H 88.2%10
Figure A0011198500076
H OCF 3H 83.4%11 H F H 87.8%12 H CF 3H 82.6%13 H OCF 3H 83.90%14 F F H 81.2%15
Figure A00111985000711
F F F 79.8%
The product analysis result is as follows: compound (5)
MS(M/Z)：504(M +?0.86％)
Ultimate analysis: calculated value F22.60 H3.60 C64.29
Measured value F22.10 H3.42 C64.18
HNMR(CDCl 3/TMS)，7.24-7.97(m，7H)，5.32(m，2H)，4.26(t，2H)，
2.53(m，2H)，2.05(m，2H)，0.96(t，3H)ppm.
19FNMR(CDCl 3/TFA)：80.2(m，2F)，60.8(m，2F)，58.4(d，1F)，51.2(d，
1F) ppm. compound (6) MS (M/Z): 580 (M +) ultimate analysis: calculated value F 22.91 H3.99 C62.07
Measured value F 22.88 H3.87 C62.10 1HNMR (CDCl 3/ TMS): 8.37 (m, 2H), 7.80 (m, 2H), 7.34 (m, 4H), 5.81 (m,
1H)，5.05(dd，1H)，4.90(m，1H)，3.60(t，2H)，2.02(m，2H)，1.20-
1.42 (m, 8H) ppm. 19FNMR (CDCl 3/ TFA): 80.8 (m, 2F), 61.4 (m, 2F) ,-19.5 (s, 3F) ppm. compound (7) MS (M/Z): 542 (M +) ultimate analysis: calculated value F17.51 H5.02 C68.63
Measured value F17.48 H5.10 C68.70 1HN (CDCl 3/ TMS): 8.32 (m, 2H), 7.72 (m, 2H), 7.33 (m, 4H),
5.40(m，1H)，5.35(m，1H)，3.65(t，2H)，2.00(m，4H)，
1.15 (m, 2H), 1.10-1.48 (m, 6H), 0.91 (t, 3H) ppm. 19FNMR (CDCl 3/ TFA): 27.3 (m, F), 61.3 (m, 2F), 80.7 (m, 2F) ppm. compound (8) MS (M/Z): 606 (M +) ultimate analysis: calculated value F21.92 H4.82 C65.34
Measured value F21.88 H4.73 C65.29 1HNMR (CDCl 3/ TMS): 8.29 (m, 2H), 7.73 (m, 2H), 7.20 (m, 4H),
5.81(m，1H)，5.09(dd，1H)，4.85(m，1H)，3.69(m，2H)，
2.02 (m, 2H), 1.19-1.44 (m, 14H) ppm 19FNMR (CDCl 3/ TFA): 80.8 (m, 2F), 61.4 (m, 2F) ,-15.5 (s, 3F) ppm. compound (14) MS (M/Z, %): 476 (M +, 40.24%) and ultimate analysis: calculated value F23.93 H2.96 C63.03
Measured value F23.63 H2.75 C63.05 1HNMR (CDCl 3/ TMS): 7.27-8.18 (m, 7H), 5.73 (m, 1H), 5.26 (dd, 1H),
5.05(m，1H)，4.25(t，2H)，2.58(q，2H)ppm 19FNMR(CDCl 3/TFA)：50.0(d，1F)，58.5(d，1F)，60.6(m，2F)，79.9(m，
2F) ppm. compound (9) MS (M/Z, %): 508 (M +, 24.91%) and ultimate analysis: calculated value F26.16 H2.97 C61.43
Measured value F25.98 H2.95 C61.38 1HNMR (CDCl 3/ TMS): 8.20 (m, 2H), 7.47-7.73 (m, 4H), 7.13 (m, 2H),
5.64(m，1H)，5.18(dd，1H)，4.98(m，1H)，4.27(t，2H)，2.42(q，
2H) ppm. 19FNMR (CDCl 3/ TFA) :-14.5 (s, 3F), 60.6 (m, 2F), 80.0 (m, 2F) ppm. compound (10) MS (M/Z, %): 524 (M +, 16.81%) and ultimate analysis: calculated value F25.36 H2.88 C59.55
Measured value F25.31 H2.79 C59.48 1HNMR (CDCl 3/ TMS): 8.22 (m, 2H), 7.29-7.59 (m, 6H), 5.79 (m, 1H),
5.24 (dd, 1H), 5.01 (m, 1H), 4.33 (t, 2H), 2.58 (q, 2H) ppm. 19FNMR (CDCl 3/ TFA) :-19.5 (s, 3F), 60.7 (m, 2F), 80.2 (m, 2F) ppm. compound (11) MS (M/Z, %): 486 (M +, 0.31%) and ultimate analysis: calculated value F19.53 H3.94 C66.67
Measured value F19.83 H3.99 C66.45 1HNMR (CDCl 3/ TMS): 8.23 (m, 2H), 7.64 (m, 2H), 7.25 (m, 4H),
5.49(m，2H)，4.28(t，2H)，2.55(m，2H)，2.10(m，2H)，1.02(t，
3H) ppm 19FNMR (CDCl 3/ TFA): 26.66 (m, 1F), 60.9 (m, 2F), 80.3 (m, 2F) ppm compound (13) MS (M/Z, %): 552 (M +, 0.45%) and ultimate analysis: calculated value F24.07 H3.47 C60.88
Measured value F24.37 H3.24 C60.93
1HNMR(CDCl 3/TMS)：7.22-8.09(m，8H)，5.41(m，2H)，4.24(t，2H)，
2.52(m，2H)，2.06(m，2H)，0.96(t，3H)ppm.
19FNMR(CDCl 3/TFA)：-19.8(s，3F)，+60.9(m，2F)，+80.2(m，2F)ppm
Compound (12)
MS(M/Z，％)：536(M +，1.54％)
Ultimate analysis: calculated value F24.79 H3.57 C62.69
Measured value F25.02 H3.31 C62.55
1HNMR(CDCl 3/TMS)：8.22(m，2H)，7.51-7.74(m，4H)，7.13(m，2H)，
5.42(m，2H)，4.21(t，2H)，2.51(m，2H)，2.02(m，2H)，0.96(t，
3H)ppm.
19FNMR(CDCl 3/TFA)：-14.1(s，3F)，60.5(m，2F)，80.0(m，2F)ppm.
Compound (15)
MS(M/Z，％)：494(M +，10.1％)
Ultimate analysis: calculated value F26.90 H2.65 C60.74
Measured value F27.08 H2.37 C60.58
1HNMR(CDCl 3/TMS)：8.24(m，4H)，7.73(s，2H)，5.75(m，1H)，
5.15(dd，1H)，5.09(m，1H)，3.75(t，2H)，2.34(q，2H)ppm.
19FNMR(CDCl 3/TFA)：86.0(m，1F)，80.8(m，2F)，60.7(m，2F)，55.0(m，
2F)ppm.
Embodiment 3
Adopt orthogonal polarizing microscope that the part of compounds of embodiment 1 and 2 is carried out transformation behavior research, the phase transition property that in the lifting temperature course, occurs, during their thermal behavior is listed in the table below, wherein C represents crystal, SmA represents smectic A phase, N represents nematic phase, and I represents isotropic liquid, can find out that the temperature range of this compounds mesomorphic phase is very big from table.

Claims (3)

1. fluorine-containing tolane liquid crystalline cpd that contains side chain of olefinic oxygen has following molecular formula:
Figure A0011198500021
, R=C wherein 3-12Thiazolinyl, R 1, R 2Or R 3=H, F, C 1-3Perfluoroalkyl or C 1-3Perfluoro alkoxy.
2. preparation method who contains the fluorine-containing tolane liquid crystalline cpd of side chain of olefinic oxygen as claimed in claim 1, it is characterized in that by Palladium compound, CuX, nitrogenous organic ligand react 0.5-100h in room temperature to reflux temperature, the above-claimed cpd mol ratio is followed successively by 1: 1-10: 0.01-0.2: 0.02-0.40: 0-100, R wherein, R 1, R 2Each R 3With claim 1, 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, the bipyridine of alkyl.
3. the fluorine-containing tolane liquid crystals preparation method that contains side chain of olefinic oxygen as claimed in claim 2 is characterized in that described
Figure A0011198500023
With the mol ratio of nitrogenous organic ligand be 1: 1-10.
CN 00111985 2000-03-10 2000-03-10 Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process Expired - Fee Related CN1101444C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 00111985 CN1101444C (en) 2000-03-10 2000-03-10 Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 00111985 CN1101444C (en) 2000-03-10 2000-03-10 Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process

Publications (2)

Publication Number Publication Date
CN1263927A true CN1263927A (en) 2000-08-23
CN1101444C CN1101444C (en) 2003-02-12

Family

ID=4581881

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 00111985 Expired - Fee Related CN1101444C (en) 2000-03-10 2000-03-10 Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process

Country Status (1)

Country Link
CN (1) CN1101444C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325456C (en) * 2002-12-24 2007-07-11 株式会社艾迪科 Perfluoroallyloxy compound and liquid-crystal composition containing the compound
CN103333697A (en) * 2013-07-16 2013-10-02 上海天问化学有限公司 Nematic negative liquid crystal containing 2,3,5,6-tetrafluorotolane, synthetic method and application
TWI454559B (en) * 2011-10-24 2014-10-01 Ind Tech Res Inst Liquid crystal compound and liquid crystal display

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325456C (en) * 2002-12-24 2007-07-11 株式会社艾迪科 Perfluoroallyloxy compound and liquid-crystal composition containing the compound
TWI454559B (en) * 2011-10-24 2014-10-01 Ind Tech Res Inst Liquid crystal compound and liquid crystal display
CN103333697A (en) * 2013-07-16 2013-10-02 上海天问化学有限公司 Nematic negative liquid crystal containing 2,3,5,6-tetrafluorotolane, synthetic method and application
CN103333697B (en) * 2013-07-16 2015-06-03 福建省邵武市永晶化工有限公司 Nematic negative liquid crystal containing 2,3,5,6-tetrafluorotolane, synthetic method and application

Also Published As

Publication number Publication date
CN1101444C (en) 2003-02-12

Similar Documents

Publication Publication Date Title
JP4876420B2 (en) Difluorobenzene derivative
JP5131222B2 (en) Alkenyl compound having negative value of Δε, liquid crystal composition, and liquid crystal display device
JPH04501270A (en) Phenylcyclohexane compound and liquid crystal phase
JP2007314546A (en) Sulfur pentafluoride compound, and its manufacturing method and utilization
JPH0867641A (en) Diene compound and liquid crystal medium
JP3430548B2 (en) Fluorine-containing indane ring derivative compound and liquid crystal composition containing the same
CN1101444C (en) Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process
JP4465879B2 (en) Liquid crystalline compound having a piperidine ring, liquid crystal composition and liquid crystal display device
JP3991398B2 (en) Liquid crystal compound having negative dielectric anisotropy value, liquid crystal composition containing the liquid crystal compound, and liquid crystal display device using the liquid crystal composition
JP4258038B2 (en) Fluorine-substituted-2-phenylnaphthalene derivative
JP3797389B2 (en) Fluorine-substituted alkenyl liquid crystalline compound, liquid crystal composition, and liquid crystal display device
JP5043678B2 (en) Liquid crystal composition containing novel silicon-containing compound and liquid crystal display device using the same
US7297379B2 (en) Polyfluorinated fused aromatics and their use in liquid-crystal mixtures
EP1369406A1 (en) Fluorinated naphthalene derivatives, liquid crystal compositions and liquid crystal displays containing them
US6682785B2 (en) Fluorinated anthracenes, and their use in liquid-crystal mixtures
US20050258397A1 (en) Fluorinated fused aromatics and their use in liquid-crystal mixtures
EP0410756B1 (en) Cyclohexenylethane compounds
JP3105245B2 (en) Liquid crystal cyanoalkanes and cyanoalkenes
US7399505B2 (en) Fluorinated phenanthrenes and their use in liquid-crystal mixtures
JP3417969B2 (en) Fluorine-containing indene ring derivative compound and liquid crystal composition containing the same
CN1127465C (en) Fluoric bis(diphenyl)acetylene compounds and preparing process and usage thereof
CN110698332A (en) Tetraphenyl ethylene alkyne phenyl alkoxy bridging alkoxy benzophenanthrene binary compound and preparation method thereof
CN112457865A (en) Liquid crystal compound and composition and application thereof
EP0688752A1 (en) Trifluoro-2-(trans-4-substituted cyclohexyl) ethylenes and process for their production
JP5093828B2 (en) Phenyldecahydronaphthalene derivative

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee
REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1059952

Country of ref document: HK