CN1450040A - Alkyl dicyclohexyl alkyne group liquid crystal and production method thereof - Google Patents
Alkyl dicyclohexyl alkyne group liquid crystal and production method thereof Download PDFInfo
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- CN1450040A CN1450040A CN 02103898 CN02103898A CN1450040A CN 1450040 A CN1450040 A CN 1450040A CN 02103898 CN02103898 CN 02103898 CN 02103898 A CN02103898 A CN 02103898A CN 1450040 A CN1450040 A CN 1450040A
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- Prior art keywords
- cyclohexyl
- instead
- benzene
- acetylene base
- ethynyl
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Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 title claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 20
- 125000002355 alkine group Chemical group 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 5
- -1 alkyl dicyclohexyl acetylenes Chemical class 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 324
- SSDZYLQUYMOSAK-UHFFFAOYSA-N ethynylcyclohexane Chemical group C#CC1CCCCC1 SSDZYLQUYMOSAK-UHFFFAOYSA-N 0.000 claims description 125
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 88
- 238000002360 preparation method Methods 0.000 claims description 52
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 47
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 47
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 47
- 229910052794 bromium Inorganic materials 0.000 claims description 47
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 33
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 29
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 24
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 16
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 16
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 claims description 8
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 7
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- XFPAOXIWRDDQGG-UHFFFAOYSA-N 4-ethynyl-1,2-difluorobenzene Chemical group FC1=CC=C(C#C)C=C1F XFPAOXIWRDDQGG-UHFFFAOYSA-N 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 150000004768 bromobenzenes Chemical class 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- DLXVEDWAIZIKJP-UHFFFAOYSA-N C#C.FC=1C(=C(C=CC1)F)F Chemical group C#C.FC=1C(=C(C=CC1)F)F DLXVEDWAIZIKJP-UHFFFAOYSA-N 0.000 claims description 3
- CRFJRGSTIQFTQW-UHFFFAOYSA-N acetylene fluorobenzene Chemical group C#C.FC1=CC=CC=C1 CRFJRGSTIQFTQW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000012044 organic layer Substances 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000013459 approach Methods 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 3
- GQYAWVVNZAWBEI-UHFFFAOYSA-N C#C.C(CCC)C1=CC=CC=C1 Chemical group C#C.C(CCC)C1=CC=CC=C1 GQYAWVVNZAWBEI-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- JKFPHRRMFFHRDM-UHFFFAOYSA-N acetylene ethylbenzene Chemical group C#C.C(C)C1=CC=CC=C1 JKFPHRRMFFHRDM-UHFFFAOYSA-N 0.000 description 1
- KULRJZAIWUUKLH-UHFFFAOYSA-N acetylene pentylbenzene Chemical group C#C.C(CCCC)C1=CC=CC=C1 KULRJZAIWUUKLH-UHFFFAOYSA-N 0.000 description 1
- UGLXZBZLTWYGTA-UHFFFAOYSA-N acetylene propylbenzene Chemical group C#C.C(CC)C1=CC=CC=C1 UGLXZBZLTWYGTA-UHFFFAOYSA-N 0.000 description 1
- BLJLOSJXZCESDI-UHFFFAOYSA-N acetylene toluene Chemical group C#C.CC1=CC=CC=C1 BLJLOSJXZCESDI-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- HERWQQFSESWGRK-UHFFFAOYSA-N chromium(6+) oxygen(2-) pyridin-1-ium chloride Chemical compound Cl.N1=CC=CC=C1.[O-2].[O-2].[O-2].[Cr+6] HERWQQFSESWGRK-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an alkyl dicyclohexyl acetylenes liquid crystal and its production process. Said invention is aimed at providing a liquid crystal compound whose molecular melting point is lower, liquid crystal phase range is wider, liposolubility is better and at the same time whose optical anisotropy is larger. Said invention also provides its technological process and steps for preparing said liquid crystal compound.
Description
Technical field
The present invention relates to a kind of liquid crystal material and production method thereof.
Background technology
Liquid crystal material has widespread use in field of information display, the application in optical communication also make progress (S.T.Wu, D.K.Yang.Reflective Liquid Crystal Displays.Wiley, 2001).Along with the further development of lcd technology and optical communication technology, people have proposed new requirement to the performance of liquid crystal material.Because any single component liquid crystal all can not satisfy whole requirements of liquid-crystal display, therefore need the different monomer liquid crystal of exploitation performance, then the plurality of liquid crystals compound is satisfied the different requirements that show by the mixed optimum matching in the hope of the various characteristics parameter of suitable proportion.
Optical anisotropy (Δ n) is the critical nature of liquid crystal, needs careful regulation and control in liquid-crystal display.In the last few years, big Δ n liquid crystal material received publicity, and some big Δ n liquid crystal materials are synthesized out, but these materials otherwise since in the molecule two carbon carbon triple bonds directly link to each other and make stable not ideal (R.A.Shenoy, M.E.Neubert etc, 2000, Liq.Cryst., 27,801.), because phenyl ring causes molecule fusing point too high (C.Sekine, K.Iwa kura etc, 2001 more in the molecule, Liq.Cryst., 28,1375.), or fat-soluble not too satisfactory.
Summary of the invention
It is lower to the purpose of this invention is to provide a kind of molecule fusing point, and mesomorphic phase a wider range is fat-soluble better, simultaneously the bigger liquid crystalline cpd of optical anisotropy.
The present invention is to provide the liquid crystalline cpd of following logical formula V:
Wherein, n=2-5; R=F or H; I=F or C
mH
2m+1, m=2-5; X=F or H.
Work as R=H; X=H; I=C
mH
2m+1The time, the compound of logical formula V is formula (I) compound:
Wherein, n=2-5; M=2-5.
Work as R=H; X=H; During I=F, the compound of logical formula V is formula (II) compound:
Wherein, n=2-5.
Work as X=H; R=F; During I=F, the compound of logical formula V is formula (III) compound:
Work as R=F; X=F; During I=F, the compound of logical formula V is formula (IV) compound:
Wherein, n=2-5.
Specifically, compound of the present invention can be a kind of among the following family member:
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene.
Second purpose of the present invention provides a kind of method of producing the liquid crystalline cpd of logical formula V.
A kind of method of producing the logical described compound of formula V may further comprise the steps:
1) preparation (instead)-4-[(is anti-respectively)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene and 4-alkyl-4 ' bromine tolane or 4-fluoro-4 ' bromine tolane or 3,4-two fluoro-4 ' bromine tolane or 3,4,5-three fluoro-4 ' bromine tolane; Described alkyl is methyl, ethyl, propyl group, butyl or amyl group;
2) (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene and 4-alkyl-4 ' bromine tolane or 4-fluoro-4 ' bromine tolane or 3,4 two fluoro-4 ' bromine tolane or 3,4, ' the bromine tolane is at four (triphenyl) phosphorus palladium chloride for 5-three fluoro-4,1-{ (instead)-4-[(is anti-for the following generation of the catalysis of cuprous iodide and triphenyl phosphorus)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[4-alkyl phenyl ethynyl] benzene, 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene, 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] or 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene; Described alkyl is methyl, ethyl, propyl group, butyl or amyl group.
Wherein, described preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene may further comprise the steps:
1) anti-with (instead)-4-[()-the 4-alkyl-cyclohexyl] hexahydrobenzoic acid is raw material, (instead)-4-[(is anti-in preparation)-4-ethyl cyclohexyl] hexahydrobenzyl alcohol;
2) preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] hexahydrobenzaldehyde;
3) preparation (instead) (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane;
4) preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene;
Described preparation 4-alkyl-4 ' the bromine tolane may further comprise the steps:
1) pure and mild with 2-methyl-3-alkane alkynes-2-is raw material to the alkyl bromobenzene, generates 2-methyl-4-(4-alkyl phenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;
2) preparation is to alkylbenzene acetylene;
3) preparation 4-alkyl-4 ' bromine tolane;
Described preparation 4-fluoro-4 ' the bromine tolane may further comprise the steps:
1) is raw material with 2-methyl-fluorine-based bromobenzene of the pure and mild 4-of 3-alkane alkynes-2-, under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus, generates 2-methyl-4-(4-fluorophenyl)-3-alkane alkynes-2-alcohol;
2) preparation 4-fluorobenzene acetylene;
3) preparation 4-fluoro-4 ' bromine tolane;
Described preparation 3,4-two fluoro-4 ' the bromine tolane may further comprise the steps:
1) pure and mild 3 with 2-methyl-3-alkane alkynes-2-, 4-two fluorine-based bromobenzenes are raw material, generate 2-methyl-4-(3, the 4-difluorophenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;
2) preparation 3,4-difluoro phenylacetylene;
3) preparation 3,4-two fluoro-4 ' bromine tolane;
Described preparation 3,4,5-three fluoro-4 ' the bromine tolane may further comprise the steps:
1) pure and mild 3,4 with 2-methyl-3-alkane alkynes-2-, 5-three fluorine-based bromobenzenes are raw material, generate 2-methyl-4-(3, the 4-difluorophenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;
2) preparation 3,4,5-trifluoro-benzene acetylene;
3) preparation 3,4,5-three fluoro-4 ' bromine tolane.
The route steps of synthetic The compounds of this invention can be represented with following formula:
In liquid crystal molecule, to compare with phenyl ring, cyclohexyl has the molecule of reduction fusing point, and broadening mesomorphic phase scope increases fat-soluble effect; The introducing of side direction fluorine atom can keep some good characteristics of liquid crystal, suppresses the generation of orderly smectic phase simultaneously, strengthens the dielectric anisotropy of liquid crystal.
The present invention will be further described below in conjunction with embodiment.
Embodiment
Embodiment 1, the preparation 1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base-4-[4-butyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-in preparation)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene may further comprise the steps:
1, preparation (instead)-4-[(is anti-)-4-propyl group cyclohexyl] hexahydrobenzyl alcohol
In the 250ml reaction flask, add 100ml tetrahydrofuran (THF) (THF), 7.6g lithium aluminium hydride, stir under the room temperature, slowly Dropwise 5 0ml contains that 23.5g (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the THF solution of hexahydrobenzoic acid, drip and finish, at room temperature continue to stir after 4 hours, in reaction flask, drip the potassium sodium tartrate solution of 40ml 40%, collected organic layer, revolve to steam to remove and desolvate, the faint yellow solid crude product, use the hexane recrystallization, must white solid (instead)-4-[(be anti-)-4-propyl group cyclohexyl] hexahydrobenzyl alcohol 19.8g, gas chromatographic analysis purity: 99.2%, productive rate: 88.4%.
Can make following compounds with similar approach by corresponding carboxylic acid:
(instead)-4-[(is anti-)-4-ethyl cyclohexyl] hexahydrobenzyl alcohol
(instead)-4-[(is anti-)-4-butyl cyclohexyl] hexahydrobenzyl alcohol
(instead)-4-[(is anti-)-4-amyl group cyclohexyl] hexahydrobenzyl alcohol
2, preparation (instead)-4-[(is anti-)-4-propyl group cyclohexyl] hexahydrobenzaldehyde
It is anti-to add (the instead)-4-[(that obtains in 100ml methylene dichloride, the 19.8g above-mentioned steps 1 in the 250ml reaction flask)-4-propyl group cyclohexyl] hexahydrobenzyl alcohol, 28.4g chromium trioxide pyridine hydrochloride (PCC), stir under the room temperature and add the 100ml anhydrous diethyl ether after 2 hours, continue to stir 1 hour, leave standstill, drain solution, revolve to steam to remove and desolvate, the underpressure distillation residuum, 150 ℃/5mmHg colourless liquid (instead)-4-[(is anti-in collection)-4-propyl group cyclohexyl] hexahydrobenzaldehyde 15.8g, gas chromatographic analysis purity: 98.1%, productive rate: 79.8%.
Can make following compounds with similar approach by correspondent alcohol:
(instead)-4-[(is anti-)-4-ethyl cyclohexyl] hexahydrobenzaldehyde
(instead)-4-[(is anti-)-4-butyl cyclohexyl] hexahydrobenzaldehyde
(instead)-4-[(is anti-)-4-amyl group cyclohexyl] hexahydrobenzaldehyde
3, the preparation (instead) (instead)-4-[(is anti-)-4-propyl group cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane
In the 500ml reaction flask, add the dichloromethane solution that 150ml contains the 68.9g triphenyl phosphorus, be cooled to subzero 20 ℃, under agitation drip 100ml and contain the dichloromethane solution of 48.6g carbon tetrabromide, keep temperature to be lower than subzero 10 ℃, continue dripping 20ml, to contain (instead)-4-[(that 15.8g above-mentioned steps 2 obtains anti-)-4-propyl group cyclohexyl] dichloromethane solution of hexahydrobenzaldehyde, reaction finishes, with reaction flask subzero 20 ℃ place 12 hours after, the upper strata brown-red solution is strained in the 1000ml hexane, left standstill 3 hours, drain supernatant liquor, revolve to steam to remove and desolvate the underpressure distillation residuum, 160 ℃/150Pa colourless liquid (instead) (instead)-4-[(is anti-in collection)-4-propyl group cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane 23.2g, gas chromatographic analysis purity: 98.6%, productive rate 86.3%.
Can make following compounds with similar approach by corresponding aldehyde:
(instead)-4-[(is anti-)-4-ethyl cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane
(instead)-4-[(is anti-)-4-butyl cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane
(instead)-4-[(is anti-)-4-amyl group cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane
4, preparation (instead)-4-[(is anti-)-4-propyl group cyclohexyl] cyclohexyl-acetylene
Add in the 100ml reaction flask that 50ml contains that 23.2g above-mentioned steps 3 obtains (instead) (instead)-4-[(is anti-)-4-propyl group cyclohexyl] cyclohexyl-β, the tetrahydrofuran solution of β '-sym-dibromoethane, the magnetic stirred solution, the sealed reaction bottle, at the subzero hexane solution that slowly injects 45.5ml 2.78M n-Butyl Lithium below 78 ℃, add n-Butyl Lithium, continue reaction after 1 hour, reaction solution is poured in the 400ml water, and water layer merges organic layer with 3 * 150ml hexane wash, with 2 * 150ml washing organic layer, with the washing of 150ml saturated common salt, collected organic layer revolves to steam to remove and desolvates again, the underpressure distillation residuum, 96 ℃/150Pa colourless liquid (instead)-4-[(is anti-in collection)-4-propyl group cyclohexyl] cyclohexyl-acetylene 9.2g, gas chromatographic analysis purity: 99.3%, productive rate 68.7%.
Can make following compounds with similar approach by corresponding raw material:
(instead)-4-[(is anti-)-4-ethyl cyclohexyl] cyclohexyl-acetylene
(instead)-4-[(is anti-)-4-butyl cyclohexyl] cyclohexyl-acetylene
(instead)-4-[(is anti-)-4-amyl group cyclohexyl] cyclohexyl-acetylene
5, preparation 2-methyl-4-(4-aminomethyl phenyl)-3-butyne-2-alcohol
In the 250ml reaction flask, add the 100ml triethylamine, 8.4g 2-methyl-3-butyne-2-alcohol, 17.1g to the methyl bromobenzene, four 0.4g (triphenyl) phosphorus palladium chloride, 0.4g cuprous iodide, 0.8g triphenyl phosphorus, stirring and refluxing 12 hours, be cooled to room temperature, add 50ml saturated ammonium chloride solution and 50ml methylene dichloride, stir several minutes, separatory, water layer is with 3 * 40ml washed with dichloromethane, merge organic layer, with 3 * 50ml washing organic layer, collected organic layer with one night of anhydrous sodium sulfate drying, revolves to steam to remove and desolvates, the underpressure distillation residuum, collect 95 ℃/150Pa cut, get colourless liquid 2-methyl-4-(4-aminomethyl phenyl)-3-butyne-2-alcohol 12.1g, gas chromatographic analysis purity: 97.5%, productive rate: 69.5%
Can make following compounds with similar approach by the respective reaction thing:
2-methyl-4-(4-ethylphenyl)-3-butyne-2-alcohol
2-methyl-4-(4-propyl group phenyl)-3-butyne-2-alcohol
2-methyl-4-(4-butyl phenyl)-3-butyne-2-alcohol
2-methyl-4-(4-amyl group phenyl)-3-butyne-2-alcohol
6, preparation is to butylbenzene acetylene
Adding 100ml toluene, 12.1g above-mentioned steps 5 obtain in the 250ml reaction flask 2-methyl-4-(4-aminomethyl phenyl)-3-butyne-2-alcohol, 4g NaOH, refluxed 4 hours, revolve to steam to remove and desolvate, the underpressure distillation residuum, collect the cut of 35 ℃/150Pa, get colourless liquid to butylbenzene acetylene 9.2g, gas chromatographic analysis purity: productive rate 98.8%: 80%
Can make following compounds with similar approach by the respective reaction thing:
To methylbenzene acetylene
To ethylbenzene acetylene
To propylbenzene acetylene
To amylbenzene acetylene
7, preparation 4-butyl-4 ' bromine tolane
In the 250ml reaction flask, add the 100ml triethylamine, 9.2g above-mentioned steps 6 obtain to butylbenzene acetylene, 22.6g to bromo-iodobenzene, four 0.3g (triphenyl) phosphorus palladium chloride, 0.3g cuprous iodide, 0.6g triphenyl phosphorus, stirring and refluxing 12 hours, be cooled to room temperature, add 50ml saturated ammonium chloride solution and 50ml methylene dichloride, stir several minutes, separatory, water layer is with 3 * 40ml washed with dichloromethane, merge organic layer, with 3 * 50ml washing organic layer, collected organic layer with one night of anhydrous sodium sulfate drying, revolves to steam to remove and desolvates, after residuum is used the normal hexane recrystallization, recycle silicon glue column chromatography is separated, and gets white solid 4-butyl-4 ' bromine tolane 16.8g, gas chromatographic analysis purity: 98.8%, productive rate: 77.8%
Reaction makes by similar approach following compounds by corresponding alkynes and to bromo-iodobenzene:
4-methyl-4 ' bromine tolane
4-ethyl-4 ' bromine tolane
4-propyl group-4 ' bromine tolane
4-amyl group-4 ' bromine tolane
4-fluoro-4 ' bromine tolane
3,4 two fluoro-4 ' bromine tolane
3,4,5-three fluoro-4 ' bromine tolane
8, the preparation 1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base-4-[4-butyl phenyl ethynyl] benzene
In the 100ml reaction flask, add the 40ml triethylamine, 0.5g (instead)-4-[(that above-mentioned steps 4 obtains is anti-)-4-propyl group cyclohexyl] cyclohexyl-acetylene, 0.6g 4-butyl-4 ' the bromine tolane that above-mentioned steps 7 obtains, four 0.02g (triphenyl) phosphorus palladium chloride, 0.02g cuprous iodide, 0.04g triphenyl phosphorus, stirring and refluxing 12 hours, be cooled to room temperature, add 20ml saturated ammonium chloride solution and 20ml methylene dichloride, stir several minutes, separatory, water layer is with 3 * 20ml washed with dichloromethane, merge organic layer, with 3 * 50ml washing organic layer, collected organic layer, with one night of anhydrous sodium sulfate drying, revolve to steam to remove and desolvate, after residuum is used the normal hexane recrystallization, recycle silicon glue column chromatography is separated, white solid 1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base-4-[4-butyl phenyl ethynyl] benzene 0.6g, gas chromatographic analysis purity: 99.7%, productive rate: 66.5%.
Structure is identified: MS (M/Z): 464 (M
+); Ultimate analysis: calculated value C99.91 H0.09 measured value C99.89H0.09; HNMR (CDCl
3/ TMS): 7.39 (d, 4H), 7.31 (d, 2H), 7.15 (d, 2H), 2.62 (t, 2H) 0.88,2.34 (d, 2H), 0.83～2.03 (m, 32H)
Transformation temperature: C 79.21S127.98 N 176.67I
Qualification result shows that the compound that obtains is the purpose compound really.
Following compounds is made by similar approach by the respective reaction thing:
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene
Embodiment 2, the preparation 1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base-4-[3,4-difluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-in preparation)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene may further comprise the steps:
1, preparation 2-methyl-4-(3, the 4-difluorophenyl)-3-butyne-2-alcohol
In the 250ml reaction flask, add the 100ml triethylamine, 8.4g 2-methyl-3-butyne-2-alcohol, 19.2g to 3,4-two fluorine-based bromobenzenes, four 0.4g (triphenyl) phosphorus palladium chloride, 0.4g cuprous iodide, 0.8g triphenyl phosphorus, stirring and refluxing 12 hours, be cooled to room temperature, add 50ml saturated ammonium chloride solution and 50ml methylene dichloride, stir several minutes, separatory, water layer merges organic layer with 3 * 40ml washed with dichloromethane, with 3 * 50ml washing organic layer, collected organic layer, with one night of anhydrous sodium sulfate drying, revolve to steam to remove and desolvate the underpressure distillation residuum, collect 95 ℃/150Pa cut, get colourless liquid 2-methyl-4-(3, the 4-difluorophenyl)-3-butyne-2-alcohol 18.3g, gas chromatographic analysis purity: 98.4%, productive rate; 82.1%
Can make following compounds with similar approach by the respective reaction thing:
2-methyl-4-(4-fluorophenyl)-3-butyne-2-alcohol
2-methyl-4-(3,4, the 5-trifluorophenyl)-3-butyne-2-alcohol
2, preparation 3,4-difluoro phenylacetylene
2-methyl-4-(3 that adding 100ml toluene, 18.3g above-mentioned steps 1 obtain in the 250ml reaction flask, the 4-difluorophenyl)-3-butyne-2-alcohol, 4g NaOH, refluxed 4 hours, revolve to steam to remove and desolvate, the underpressure distillation residuum, the cut of 35 ℃/150Pa of collection gets colourless liquid 3,4-difluoro phenylacetylene 8.6g, gas chromatographic analysis purity: productive rate 98.2%: 77.5%
Can make following compounds with similar approach by the respective reaction thing:
4-fluorobenzene acetylene
3,4,5-trifluoro-benzene acetylene
3, preparation 3,4 two fluoro-4 ' bromine tolane
In the 250ml reaction flask, add the 100ml triethylamine, 8.6g above-mentioned steps 6 obtain 3,4-difluoro phenylacetylene, 17.9g to bromo-iodobenzene, four 0.3g (triphenyl) phosphorus palladium chloride, 0.3g cuprous iodide, 0.6g triphenyl phosphorus, stirring and refluxing 12 hours, be cooled to room temperature, add 50ml saturated ammonium chloride solution and 50ml methylene dichloride, stir several minutes, separatory, water layer merges organic layer with 3 * 40ml washed with dichloromethane, with 3 * 50ml washing organic layer, collected organic layer, with one night of anhydrous sodium sulfate drying, revolve to steam to remove and desolvate, residuum with the normal hexane recrystallization after, recycle silicon glue column chromatography is separated, get white solid 3,4 two fluoro-4 ' bromine tolane 13.9g, gas chromatographic analysis purity: 98.8%, productive rate: 77.8%
Can make following compounds with similar approach by the respective reaction thing:
4-fluoro-4 ' bromine tolane
3,4,5-three fluoro-4 ' bromine tolane
4, the preparation 1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base-4-[3,4-difluorophenyl ethynyl] benzene
In the 100ml reaction flask, add the 40ml triethylamine, 0.5g (instead)-4-[(that step 4 obtains among the embodiment 1 is anti-)-4-propyl group cyclohexyl] cyclohexyl-acetylene, 0.6g above-mentioned steps 3 obtain 3,4 two fluoro-4 ' bromine tolane, four 0.02g (triphenyl) phosphorus palladium chloride, 0.02g cuprous iodide, 0.04g triphenyl phosphorus, stirring and refluxing 12 hours, be cooled to room temperature, add 20ml saturated ammonium chloride solution and 20ml methylene dichloride, stir several minutes, separatory, water layer is with 3 * 20ml washed with dichloromethane, merge organic layer, with 3 * 50ml washing organic layer, collected organic layer, with one night of anhydrous sodium sulfate drying, revolve to steam to remove and desolvate, residuum with the normal hexane recrystallization after, recycle silicon glue column chromatography is separated, white solid 1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base-4-[3,4-difluorophenyl ethynyl] benzene 0.6g, gas chromatographic analysis purity: 99.2%, productive rate: 65.9%.
Structure is identified: MS (M/Z): 444 (M
+); Ultimate analysis: calculated value C83.78 H7.66 F8.56 measured value C83.56 H7.71 F8.73; HNMR (CDCl
3/ TMS): 7.07～7.41 (m, 7H), 2.34 (d, 2H), 0.83～2.03 (m, 25H)
Transformation temperature: C 82.68S117.21 N 138.27I
Qualification result shows that the compound that obtains is the purpose compound really.
Can make following compounds with similar approach by the respective reaction thing:
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene
Claims (8)
1, the compound of logical formula V:
Wherein, n=2-5; R=F or H; I=F or C
mH
2m+1, m=2-5; X=F or H.
2, compound according to claim 1 is characterized in that: described compound is the compound of general formula (I)
Wherein, n=2-5; M=2-5.
3, compound according to claim 1 is characterized in that: described compound is the compound of general formula (II)
Wherein, n=2-5.
4, compound according to claim 1 is characterized in that: described compound is the compound of general formula (III)
Wherein, n=2-5.
5, compound according to claim 1 is characterized in that: described compound is the compound of general formula (IV)
Wherein, n=2-5.
6, compound according to claim 1 is characterized in that described compound is a kind of among the following family member:
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-aminomethyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-ethylphenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-propylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-butyl phenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-amylbenzene ethyl-acetylene base] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-ethyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-propyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-butyl cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene;
1-{ (instead)-4-[(is anti-)-4-amyl group cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene.
7, the method for the described compound of a kind of production claim 1 may further comprise the steps;
1) preparation (instead)-4-[(is anti-respectively)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene and 4-alkyl-4 ' bromine tolane or 4-fluoro-4 ' bromine tolane or 3,4-two fluoro-4 ' bromine tolane or 3,4,5-three fluoro-4 ' bromine tolane; Described alkyl is methyl, ethyl, propyl group, butyl or amyl group;
2) (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene and 4-alkyl-4 ' bromine tolane or 4-fluoro-4 ' bromine tolane or 3,4 two fluoro-4 ' bromine tolane or 3,4, ' the bromine tolane is at four (triphenyl) phosphorus palladium chloride for 5-three fluoro-4,1-{ (instead)-4-[(is anti-for the following generation of the catalysis of cuprous iodide and triphenyl phosphorus)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[4-alkyl phenyl ethynyl] benzene, 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene, 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] or 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4,5-trifluorophenyl ethynyl] benzene; Described alkyl is methyl, ethyl, propyl group, butyl or amyl group.
8, method according to claim 7 is characterized in that:
Described preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene may further comprise the steps:
1) anti-with (instead)-4-[()-the 4-alkyl-cyclohexyl] hexahydrobenzoic acid is raw material, (instead)-4-[(is anti-in preparation)-4-ethyl cyclohexyl] hexahydrobenzyl alcohol;
2) preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] hexahydrobenzaldehyde;
3) preparation (instead) (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane;
4) preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene;
Described preparation 4-alkyl-4 ' the bromine tolane may further comprise the steps:
1) pure and mild with 2-methyl-3-alkane alkynes-2-is raw material to the alkyl bromobenzene, generates 2-methyl-4-(4-alkyl phenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;
2) preparation is to alkylbenzene acetylene;
3) preparation 4-alkyl-4 ' bromine tolane;
Described preparation 4-fluoro-4 ' the bromine tolane may further comprise the steps:
1) is raw material with 2-methyl-fluorine-based bromobenzene of the pure and mild 4-of 3-alkane alkynes-2-, under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus, generates 2-methyl-4-(4-fluorophenyl)-3-alkane alkynes-2-alcohol;
2) preparation 4-fluorobenzene acetylene;
3) preparation 4-fluoro-4 ' bromine tolane;
Described preparation 3,4-two fluoro-4 ' the bromine tolane may further comprise the steps:
1) pure and mild 3 with 2-methyl-3-alkane alkynes-2-, 4-two fluorine-based bromobenzenes are raw material, generate 2-methyl-4-(3, the 4-difluorophenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;
2) preparation 3,4-difluoro phenylacetylene;
3) preparation 3,4-two fluoro-4 ' bromine tolane;
Described preparation 3,4,5-three fluoro-4 ' the bromine tolane may further comprise the steps:
1) pure and mild 3,4 with 2-methyl-3-alkane alkynes-2-, 5-three fluorine-based bromobenzenes are raw material, generate 2-methyl-4-(3, the 4-difluorophenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;
2) preparation 3,4,5-trifluoro-benzene acetylene;
3) preparation 3,4,5-three fluoro-4 ' bromine tolane.
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| CNB021038988A CN1185189C (en) | 2002-04-10 | 2002-04-10 | Alkyl dicyclohexyl alkyne group liquid crystal and production method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101671242B (en) * | 2009-09-02 | 2013-06-05 | 烟台显华化工科技有限公司 | Method for synthesizing trans-4-(trans-4'-alkyl cyclohexyl) cyclohexanal |
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2002
- 2002-04-10 CN CNB021038988A patent/CN1185189C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101671242B (en) * | 2009-09-02 | 2013-06-05 | 烟台显华化工科技有限公司 | Method for synthesizing trans-4-(trans-4'-alkyl cyclohexyl) cyclohexanal |
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| CN1185189C (en) | 2005-01-19 |
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