CN114349586B - Preparation method of trans-alkyl bicyclohexane liquid crystal monomer - Google Patents
Preparation method of trans-alkyl bicyclohexane liquid crystal monomer Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 73
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 50
- 239000000178 monomer Substances 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 230000002140 halogenating effect Effects 0.000 claims abstract description 5
- -1 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride Chemical compound 0.000 claims description 33
- 229930003779 Vitamin B12 Natural products 0.000 claims description 29
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims description 29
- 239000011715 vitamin B12 Substances 0.000 claims description 29
- 235000019163 vitamin B12 Nutrition 0.000 claims description 29
- HCJWWBBBSCXJMS-UHFFFAOYSA-J copper;dilithium;tetrachloride Chemical compound [Li+].[Li+].[Cl-].[Cl-].[Cl-].[Cl-].[Cu+2] HCJWWBBBSCXJMS-UHFFFAOYSA-J 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012769 display material Substances 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 31
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
- 239000012467 final product Substances 0.000 description 19
- 238000001514 detection method Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 238000002955 isolation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 241000589614 Pseudomonas stutzeri Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The application relates to the technical field of liquid crystal display materials, and particularly discloses a preparation method of a trans-alkyl bicyclohexane liquid crystal monomer. The method specifically comprises the following steps: (1) preparation of Compound I: adding trans-4-alkyl cyclohexane phenol into an organic solvent I, and carrying out hydrogenation reaction by using a catalyst I to prepare a compound I; (2) preparation of Compound II: adding the compound I prepared in the step (1) into an organic solvent II, and dropwise adding a halogenating reagent; carrying out halogenation reaction at 50-60 ℃ to prepare a compound II; (3) preparation of Compound III: mixing manganese powder, a catalyst II and an organic solvent III to form a reaction system, and stirring until the reaction system is black; and (3) adding sulfonate and the compound II obtained in the step (2) into a reaction system to perform a coupling reaction to prepare a compound III. The preparation method provided by the application has the advantages of low cost, short route and high yield.
Description
Technical Field
The application relates to the technical field of liquid crystal display materials, in particular to a preparation method of a trans-alkyl bicyclohexane liquid crystal monomer.
Background
With the continuous development of economy, the demands of people for high-quality life are also increasing, and in particular, the demands of high-quality display devices are also increasing. Liquid crystal display materials are one of important materials for manufacturing high-quality display devices, so that market demands for liquid crystal display materials are large. Therefore, development of high-performance, low-cost liquid crystal display materials has become an important subject to be studied.
The bicyclohexane liquid crystal monomer has the advantages of small viscosity, high response speed, good optical anisotropy, high resistivity, high phase comparison with other liquid crystal monomers at low temperature and the like, and meanwhile, the liquid crystal monomer has good tolerance to light and heat. The bicyclohexane liquid crystal monomer has wide application due to the excellent performance and is used as an important base material for forming a liquid crystal display material, so that the preparation of the bicyclohexane liquid crystal monomer has important research and development value.
The specific synthetic route is shown in figure 3, and the preparation method sequentially carries out esterification reaction, reduction reaction, reaction with toluene sulfonyl chloride under alkaline condition and reaction with formative reagent alkyl halogenated magnesium by taking trans-alkyl cyclohexyl formic acid as a raw material to finally prepare the dicyclohexyl liquid crystal monomer. In the preparation method, the adopted raw material trans-alkyl cyclohexyl formic acid is more expensive, meanwhile, the synthetic route of the whole preparation method is longer, the overall cost is higher, and the yield of the finally prepared dicyclohexyl liquid crystal monomer is lower.
Another preparation method of dicyclohexyl liquid crystal monomer in the related art, the specific synthetic route is shown in fig. 4, and the preparation method takes 1- (4- (4-alkyl cyclohexyl) phenyl) alkyl-1-ketone as a raw material, and sequentially carries out catalytic hydrogenation reaction, isomerization reaction, oxidation reaction and reduction reaction to finally prepare the dicyclohexyl liquid crystal monomer. In the preparation method, the pressure required by the catalytic hydrogenation reaction is high, and the temperature required by the reduction reaction is high. In the whole, the preparation method has higher requirements on the used equipment, and the synthesis route of the whole preparation method is also longer, so that the preparation method is not the preferred method for preparing the dicyclohexyl liquid crystal monomer.
Disclosure of Invention
The application provides a preparation method of a trans-alkyl bicyclohexane liquid crystal monomer, which has the advantages of low cost, short route and high yield.
In a first aspect, the application provides a preparation method of a trans-alkyl bicyclohexane liquid crystal monomer, which adopts the following technical scheme:
the preparation method of the trans-alkyl bicyclohexane liquid crystal monomer specifically comprises the following steps:
(1) Preparation of Compound I: adding trans-4-alkyl cyclohexane phenol into an organic solvent I, and carrying out hydrogenation reaction by using a catalyst I to prepare a compound I; the structural general formula of the compound I is as follows:
R 1 is C1-C14 alkyl;
(2) Preparation of Compound II: adding the compound I prepared in the step (1) into an organic solvent II, and dropwise adding a halogenating reagent; carrying out halogenation reaction at 50-60 ℃ to prepare a compound II; the structural general formula of the compound II is as follows:
R 1 is C1-C14 alkyl, X is halogen element;
(3) Preparation of Compound III: mixing manganese powder, a catalyst II and an organic solvent III to form a reaction system, and stirring until the reaction system is black; adding sulfonate and the compound II obtained in the step (2) into a reaction system to perform a coupling reaction to prepare a compound III; the structural general formula of the compound III is
R 1 Is C1-C14 alkyl, R 2 Is a C1-C14 alkyl group.
By adopting the technical scheme, the preparation method provided by the application adopts trans-4-alkyl cyclohexane phenol as a raw material, and the trans-alkyl cyclohexane liquid crystal monomer is finally prepared through hydrogenation reaction, halogenation reaction and coupling reaction in sequence. In the related art, in the synthesis method using trans-alkyl cyclohexyl formic acid and 1- (4- (4-alkyl cyclohexyl) phenyl) alkyl-1-ketone as raw materials, not only is the cost of the raw materials higher, but also the synthesis route is long, the requirements on equipment are higher, and the yield of the final product is lower.
The preparation method provided by the application has few synthesis steps and short process, has no special requirements on synthesis equipment, and is convenient for realizing the industrial production of the trans-alkyl bicyclohexane liquid crystal monomer. The raw material in the preparation method provided by the application is alkyl cyclohexane phenol, the price is low, and the cost for synthesizing the trans-alkyl bicyclohexane liquid crystal monomer can be effectively reduced.
Based on the above, the preparation method provided by the application has the advantages of low cost, short route and high yield, the yield of the final product in the preparation method provided by the application can reach more than 83.2%, and the highest yield of the trans-alkyl bicyclohexane liquid crystal monomer can reach 89.5%.
Preferably, in the step (3), the catalyst II is 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, dilithium tetrachlorocuprate and vitamin B12 which are mixed in any ratio.
In the preparation method provided by the application, when the coupling reaction is carried out, a catalyst II is adopted, the catalyst II is a nickel, cobalt and copper mixed catalyst, and a trans-form product with lower energy and stability is automatically formed when the compound II reacts to generate a target product compound III through a free radical intermediate state principle. According to experimental analysis, the application selects the catalyst mixed by the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, the lithium tetrachlorocuprate and the vitamin B12, so that the yield of the final product can be obviously improved.
Preferably, in the step (3), the ratio of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, the dilithium tetrachlorocuprate and the vitamin B12 in the catalyst II is (0.5-1.5): (0.5-1.5): (0.5-1.5).
In a specific embodiment, in the catalyst II, the ratio of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, the dilithium tetrachlorocuprate and the vitamin B12 is (0.5-1.5): 1:1.
in a specific embodiment, in the catalyst II, the ratio of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, the dilithium tetrachlorocuprate and the vitamin B12 is 1: (0.5-1.5): 1.
in a specific embodiment, in the catalyst II, the ratio of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, the dilithium tetrachlorocuprate and the vitamin B12 is 1:1: (0.5-1.5).
In some specific embodiments, the catalyst II comprises 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, dilithium tetrachlorocuprate, and vitamin B12 in a ratio of
(0.5-1.0)：(0.5-1.5)：(0.5-1.5)、(1.0-1.5)：(0.5-1.5)：(0.5-1.5)、
(0.5-1.5)：(0.5-1.0)：(0.5-1.5)、(0.5-1.5)：(1.0-1.5)：(0.5-1.5)、、(0.5-1.5)：(0.5-1.5)：
(0.5-1.0)、(0.5-1.5)：(0.5-1.5)：(1.0-1.5)。
Preferably, in the step (3), the molar ratio of the compound ii to the catalyst ii is 1: (0.05-0.1).
In a specific embodiment, in the step (3), the molar ratio of the compound ii to the catalyst ii is 1:0.1.
preferably, in the step (1), the weight ratio of the trans-4-alkyl cyclohexane phenol to the organic solvent I is 1: (4-6).
In a specific embodiment, in said step (1), the weight ratio of trans-4-alkylcyclohexanephenol to organic solvent I is 1:5.
preferably, in the step (1), the weight ratio of the trans-4-alkyl cyclohexane phenol to the catalyst I is 100: (1-5).
In a specific embodiment, in step (1), the weight ratio of trans-4-alkylcyclohexanephenol to catalyst I is 50:1.
preferably, in the step (1), the hydrogenation reaction temperature is 50-90 ℃.
Preferably, in the step (1), the hydrogenation reaction pressure is 0.5-1MPa.
Preferably, the inert gas is one or more of helium, nitrogen and argon, preferably nitrogen or helium.
Preferably, the organic solvent I used in step (1) is preferably toluene or n-heptane.
Preferably, the catalyst I used in the step (1) is one or more of Pd/C with the mass content of 5-10%, ru/C with the mass content of 5-10% and Pt/C with the mass content of 5-10%.
Preferably, the organic solvent II used in the step (2) is one or more of dichloromethane, toluene, tetrahydrofuran, 2-methyltetrahydrofuran and cyclopentyl methyl ether.
Preferably, the halogenating agent used in step (2) is phosphorus tribromide.
Preferably, the organic solvent III used in step (3) is N, N-dimethylformamide.
Preferably, the sulfonate used in the step (3) is one or more of p-toluenesulfonate and trifluoromethanesulfonate.
In a second aspect, the present application provides a trans-bicyclohexane-based liquid crystal monomer prepared by the above-mentioned preparation method.
In a third aspect, the application provides an application of the trans-bicyclohexane liquid crystal monomer prepared by the preparation method in preparation of a liquid crystal display material.
In summary, the application has the following beneficial effects:
the preparation method provided by the application has the advantages of few synthesis steps and short process for synthesizing the trans-alkyl bicyclohexane liquid crystal monomer, and compared with the existing synthesis route, the preparation method at least saves one-step reaction. The preparation method provided by the application has no special requirements on synthesis equipment, and is convenient for realizing the industrial production of the trans-alkyl bicyclohexane liquid crystal monomer. The raw material in the preparation method provided by the application is alkyl cyclohexane phenol, the price is low, and the cost for synthesizing the trans-alkyl bicyclo-hexane liquid crystal monomer can be effectively reduced.
When cross coupling is carried out in the preparation method provided by the application, a catalyst II is adopted, the catalyst II is a nickel, cobalt and copper mixed catalyst, and a trans-form product with lower energy and stability is automatically formed when the compound II reacts to generate a target product compound III through a free radical intermediate state principle.
Meanwhile, the final product prepared by the preparation method provided by the application has higher yield, and particularly, the yield of the final product can be obviously improved by using a catalyst mixed by 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, dilithium tetrachlorocuprate and vitamin B12.
Drawings
FIG. 1 is a general formula of a trans-alkyl bicyclohexane-based liquid crystal monomer according to the present application.
FIG. 2 is a synthetic route for preparing a trans-alkyl bicyclohexane-based liquid crystal monomer according to the present application.
FIG. 3 is a synthetic route of a preparation method of a cyclohexane-based liquid crystal monomer provided in the background art of the application.
FIG. 4 is a synthetic route for another preparation method of a cyclohexane-based liquid crystal monomer provided in the background of the application.
Detailed Description
The application provides a preparation method of a trans-alkyl bicyclohexane liquid crystal monomer, which specifically comprises the following steps:
(1) Preparation of Compound I: adding trans-4-alkyl cyclohexane phenol into an organic solvent I, and carrying out hydrogenation reaction by using a catalyst I to prepare a compound I; the structural general formula of the compound I is as follows:
r1 is C1-C14 alkyl.
Wherein, the weight ratio of the trans-4-alkyl cyclohexane phenol to the organic solvent I is 1: (4-6). The weight ratio of trans-4-alkyl cyclohexane phenol to catalyst I is 100: (1-5). The temperature of the hydrogenation reaction is 50-90 ℃. The pressure of hydrogenation reaction is 0.5-1MPa.
(2) Preparation of Compound II: adding the compound I prepared in the step (1) into an organic solvent II, and dropwise adding a halogenating reagent; carrying out halogenation reaction at 50-60 ℃ to prepare a compound II; the structural general formula of the compound II is as follows:
r1 is C1-C14 alkyl, X is halogen element.
(3) Preparation of Compound III: mixing manganese powder, a catalyst II and an organic solvent III to form a reaction system, and stirring until the reaction system is black; adding sulfonate and the compound II obtained in the step (2) into a reaction system to perform a coupling reaction to prepare a compound III; the structural general formula of the compound III is
R1 is C1-C14 alkyl, R2 is C1-C14 alkyl.
Wherein the catalyst II is 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, lithium tetrachlorocuprate and vitamin B12 which are mixed according to any ratio. Further, in the catalyst II, the proportion of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, the lithium tetrachlorocuprate and the vitamin B12 is (0.5-1.5): (0.5-1.5): (0.5-1.5).
Wherein, the mol ratio of the compound II to the catalyst II is 1: (0.05-0.1).
The preparation method of the trans-alkyl bicyclohexane liquid crystal monomer has the advantages of low cost, short route and high yield. The application also provides a trans-bicyclo-hexane liquid crystal monomer prepared by the preparation method. The trans-alkyl bicyclohexane liquid crystal monomer can be applied to preparation of liquid crystal display materials.
The present application is described in further detail below with reference to examples 1-19 and figures 1-2.
Examples
Example 1
This example provides a process for preparing trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane. The preparation method specifically comprises the following steps:
(1) Preparation of Compound I-trans, trans-4-propyl-4 '-ol-1, 1' -bicyclohexane
A. Adding reactants: adding an organic solvent I into a 1L hydrogenation kettle, adding trans-4-alkyl cyclohexane phenol and a catalyst I into the organic solvent I, covering a kettle cover, and starting stirring;
B. nitrogen replaces air: filling nitrogen into the hydrogenation kettle until the pressure in the kettle is 0.5Mpa, then venting the pressure of the hydrogenation kettle to normal pressure, repeating the operation, and replacing with nitrogen three times;
C. hydrogen replaces nitrogen: filling hydrogen into the hydrogenation kettle to 0.3Mpa in pressure in the kettle, then emptying the pressure of the hydrogenation kettle to normal pressure, repeating the operation, and replacing with hydrogen three times;
D. hydrogenation reaction: increasing the hydrogen pressure in the hydrogenation kettle to required parameters, starting heating, and respectively carrying out reaction according to the parameter requirements of the first reaction stage and the second reaction stage;
E. monitoring the reaction result: when the hydrogen pressure in the hydrogenation kettle is completely unchanged, the temperature in the hydrogenation kettle is reduced to room temperature, the hydrogen in the hydrogenation kettle is fully replaced by nitrogen, and sampling and detection are carried out; stopping the reaction if the GC content of the trans-4-alkyl cyclohexane phenol in the sample is less than or equal to 0.1%; if the GC content of the trans-4-alkyl cyclohexane phenol in the sample is detected to be more than 0.1%, the sample is not qualified, and the reaction is stopped when the GC content of the trans-4-alkyl cyclohexane phenol is continuously reacted until the GC content is less than or equal to 0.1%.
F. Isolation of Compound I: filtering the reaction liquid obtained after the reaction in the hydrogenation kettle to obtain a catalyst I, and obtaining a filtrate; washing the hydrogenation kettle and the catalyst I with 20g of toluene to obtain a washing liquid; combining the filtrate and the washing liquid to obtain a to-be-concentrated liquid A; concentrating the solution A to be concentrated at 60deg.C under pressure less than 0.09mpa to obtain solvent; after the solvent was concentrated to dryness, compound I was obtained in a yield as shown in Table 1 with a purity of 99% or more.
G. Product identification: and (3) carrying out GC-MS detection on the obtained compound I, wherein the detection result is as follows:
after mass spectral decomposition, the product was obtained with m/z=224.
The molecular weight of trans, trans-4-propyl-4 '-ol-1, 1' -bicyclohexane is known to be 224.
Through product identification, the molecular weight of the product obtained in the step is the same as that of trans, trans-4-propyl-4 '-alcohol-1, 1' -bicyclohexane, and the product is presumed to be trans, trans-4-propyl-4 '-alcohol-1, 1' -bicyclohexane.
(2) Preparation of Compound II-trans, trans-4-propyl-4 '-bromo-1, 1' -bicyclohexane
A. Adding reactants: adding a compound I and an organic solvent II into a reaction bottle which is a three-mouth bottle;
B. nitrogen replaces air: b is the same as in the step (1);
C. halogenation reaction: according to the parameter requirements in Table 1, dropwise adding a halogenated reagent into a reaction bottle, and carrying out halogenated reaction after the dropwise adding is finished;
D. monitoring the reaction result: sampling and detecting, and if the GC content of the compound I is less than or equal to 0.1%, performing post-treatment; if the GC content of the compound I is more than 0.1%, the compound I is unqualified, and if the GC content of the compound I is less than or equal to 0.1%, the compound I is continuously reacted, and then the post-treatment is carried out.
E. Post-treatment-isolation of compound ii: the temperature of the reaction bottle is reduced to 10-20 ℃, the reaction liquid obtained by the reaction in the reaction bottle is slowly poured into 200g of ice water, stirred while being inverted, and kept stand for liquid separation, thus obtaining a lower water phase and an upper organic phase;
extracting the lower aqueous phase with 200g toluene once to obtain toluene phase; washing the toluene phase twice with 200g of pure water, washing with 200g of 5% sodium carbonate solution until the toluene phase is weakly alkaline, washing with 200g of pure water until the toluene phase is neutral, and taking the toluene phase after the washing treatment as a washing liquid A; the organic phase is dried for 2 hours by 50g of anhydrous sodium sulfate, the anhydrous sodium sulfate is filtered out, 200g of toluene is used for washing the anhydrous sodium sulfate, and the toluene phase after washing the anhydrous sodium sulfate is used as a washing liquid B;
combining the dried organic phase, the washing liquid A and the washing liquid B to obtain a liquid B to be concentrated; concentrating the solution B to be concentrated at 60deg.C under pressure less than 0.09mpa to obtain solvent; after the solvent was concentrated to dryness, compound II was obtained with a yield as shown in Table 1 and a purity of 95% or more.
F. Product identification: and (3) carrying out GC-MS detection on the obtained compound II, wherein the detection result is as follows:
after mass spectral decomposition, the product of m/z=286, 288 is obtained.
The molecular weight of trans, trans-4-propyl-4 '-bromo-1, 1' -bicyclohexane is known to be 287.
Therefore, through product identification, the molecular weight of the product obtained in the step is the same as that of trans, trans-4-propyl-4 '-bromo-1, 1' -bicyclohexane, and the product is presumed to be trans, trans-4-propyl-4 '-bromo-1, 1' -bicyclohexane.
(3) Preparation of Compound III-trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane
A. Adding reactants: taking a three-mouth bottle as a reaction bottle, and adding metal manganese powder and a catalyst II into the reaction bottle;
B. vacuumizing: vacuumizing for 30min at 80 ℃;
C. coupling reaction: cooling the reaction bottle to room temperature, adding manganese powder, a catalyst II and an organic solvent III into the reaction bottle according to the parameter requirements in Table 1, and stirring for 10min; adding sulfonate and the compound II obtained in the step (2) into a reaction bottle, and carrying out coupling reaction according to parameters in Table 1 to prepare a compound III;
D. monitoring the reaction result: sampling and monitoring, and if the GC content of the compound II is less than or equal to 0.1%, performing post-treatment; if the GC content of the compound II is more than 0.1%, the compound II is unqualified, and the compound II is continuously reacted until the GC content of the compound II is less than or equal to 0.1%, and then the compound II is subjected to post-treatment.
E. Work-up-isolation of Compound III: after the reaction is finished, quenching with 100g of saturated ammonium chloride aqueous solution, stirring for 10min, adding 300g of n-heptane, stirring for 10min, standing and separating to obtain a lower aqueous phase and an upper organic phase;
extracting the lower water phase twice with 300g of n-heptane to obtain an extraction phase; combining the extraction phase and the organic phase, drying for 2 hours by using 50g of anhydrous sodium sulfate, and passing through a 50g silica gel column to obtain column passing liquid; after passing through the column, eluting the chromatographic column by using 200g of n-heptane to obtain eluent;
mixing the column passing liquid and the eluent to obtain a to-be-concentrated liquid C; concentrating the solution C to be concentrated at 60deg.C under pressure less than 0.09mpa to obtain concentrated solution; the concentrate was recrystallized once from 435g of isopropyl alcohol, short path distilled once, and passed through a 10g column of silica gel in the molten state to give compound III, the yield of which is shown in Table 1, and the purity of which is not less than 99.96%.
F. Product identification: and (3) carrying out GC-MS detection on the obtained compound III, wherein the detection result is as follows:
after mass spectral decomposition, the product was obtained with m/z=236.
The molecular weight of trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane is known to be 236.
Further utilize nuclear magnetic resonance to detect, the testing result is: 1 H-NMR(400MHz,CDCl3)：δ:1.58～1.63(4H,m)；1.27～1.54(16H,m)；1.12～1.21(6H,m)；0.88(6H,m)。
through the identification, the obtained product is trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane.
The yield was calculated as follows:
yield = actual mass produced of compound iii/(molar amount of compound ii) molecular weight of compound iii.
The parameters involved in the above steps are shown in table 1.
TABLE 1 examples 1-4 parameters in each step
Example 2
This example provides a process for preparing trans, trans-4-propyl-4 '-propyl-1, 1' -bicyclohexane. The parameters involved in this preparation are shown in Table 1, which differ from example 1 in the following ways:
(3) Preparation of Compound III-trans, trans-4-propyl-4 '-propyl-1, 1' -bicyclohexane
E. Work-up-isolation of Compound III: after the reaction is finished, quenching by using 110g of saturated ammonium chloride aqueous solution, stirring for 10min, adding 300g of n-heptane, stirring for 10min, standing and separating to obtain a lower aqueous phase and an upper organic phase;
extracting the lower water phase twice with 300g of n-heptane to obtain an extraction phase; combining the extraction phase and the organic phase, drying for 2 hours by using 50g of anhydrous sodium sulfate, and passing through a 50g silica gel column to obtain column passing liquid; after passing through the column, eluting the chromatographic column by using 200g of n-heptane to obtain eluent;
mixing the column passing liquid and the eluent to obtain a to-be-concentrated liquid C; concentrating the solution C to be concentrated at 60deg.C under pressure less than 0.09mpa to obtain concentrated solution; the concentrate was recrystallized once from 500g of isopropanol, short path distilled once, and passed through a 12g column of silica gel in the molten state to give compound III, the yield of which is shown in Table 1, and the purity of which is not less than 99.95%.
F. Product identification: and (3) carrying out GC-MS detection on the obtained compound III, wherein the detection result is as follows:
after mass spectral decomposition, the product was obtained with m/z=250.
The molecular weight of trans, trans-4-propyl-4 '-propyl-1, 1' -bicyclohexane is known to be 250.
Further utilize nuclear magnetic resonance to detect, the testing result is: 1 H-NMR(400MHz,CDCl3)：δ:1.57～1.62(4H,m)；1.28～1.54(16H,m)；1.10～1.21(8H,m)；0.89(6H,m)。
through the identification, the obtained product is trans, trans-4-propyl-4 '-propyl-1, 1' -bicyclohexane.
Example 3
This example provides a process for preparing trans, trans-4-propyl-4 '-butyl-1, 1' -bicyclohexane. The parameters involved in this preparation are shown in Table 1, which differ from example 2 in the following way:
(2) Preparation of Compound II-trans, trans-4-propyl-4 '-chloro-1, 1' -bicyclohexane
E. Post-treatment-isolation of compound ii: the purity of the obtained compound II is more than or equal to 95 percent.
F. Product identification: performing GC-MS detection on the obtained compound II, wherein the detection result is as follows:
after mass spectral decomposition, the product of m/z=242, 244 is obtained.
The molecular weight of trans, trans-4-propyl-4 '-chloro-1, 1' -bicyclohexane is known to be 242.8.
Therefore, through product identification, the molecular weight of the product obtained in the step is the same as that of trans, trans-4-propyl-4 '-chloro-1, 1' -bicyclohexane, and the product is presumed to be trans, trans-4-propyl-4 '-chloro-1, 1' -bicyclohexane.
(3) Preparation of Compound III-trans, trans-4-propyl-4 '-butyl-1, 1' -bicyclohexane
E. Work-up-isolation of Compound III: the concentrate obtained by the treatment was recrystallized once with 530g of isopropyl alcohol, short-path distilled once, and passed through 12g of silica gel column in a molten state to obtain compound III, the yield of which is shown in Table 1, and the purity of which is not less than 99.96%.
F. Product identification: and (3) carrying out GC-MS detection on the obtained compound III, wherein the detection result is as follows:
after mass spectral decomposition, the product was obtained with m/z= 264.28.
The molecular weight of trans, trans-4-propyl-4 '-butyl-1, 1' -bicyclohexane is known to be 264.28.
Further utilize nuclear magnetic resonance to detect, the testing result is: 1 H-NMR(400MHz,CDCl3)：δ:1.60～1.65(4H,m)；1.29～1.56(16H,m)；1.11～1.24(10H,m)；0.87(6H,m)。
through the identification, the obtained product is trans, trans-4-propyl-4 '-butyl-1, 1' -bicyclohexane.
Example 4
This example provides a process for the preparation of trans, trans-4-propyl-4 '-heptyl-1, 1' -bicyclohexane. The parameters involved in this preparation are shown in Table 1, which differ from example 3 in the following way:
(3) Preparation of Compound III-trans, trans-4-propyl-4 '-heptyl-1, 1' -bicyclohexane
E. Work-up-isolation of Compound III: the concentrate obtained by the treatment was recrystallized once with 600g of isopropyl alcohol, once by short path distillation, and passed through 12g of silica gel column in a molten state to obtain compound III, the yield of which is shown in Table 1, and the purity of which is not less than 99.96%.
F. Product identification: and (3) carrying out GC-MS detection on the obtained compound III, wherein the detection result is as follows:
after mass spectral decomposition, the product was obtained with m/z=306.
The molecular weight of trans, trans-4-propyl-4 '-heptyl-1, 1' -bicyclohexane is known to be 306.
Further utilize nuclear magnetic resonance to detect, the testing result is: 1 H-NMR(400MHz,CDCl3)：δ:1.64～1.69(4H,m)；1.35～1.61(16H,m)；1.12～1.30(16H,m)；0.88(6H,m)。
through the identification, the obtained product is trans, trans-4-propyl-4 '-heptyl-1, 1' -bicyclohexane.
With reference to table 1, it can be seen from the above preparation results of examples 1 to 4 that the preparation method provided by the present application can use trans-4-alkylcyclohexane phenol as a raw material to prepare a trans-alkylcyclohexane liquid crystal monomer by sequentially performing hydrogenation, halogenation and coupling reactions. The yield of the trans-alkyl bicyclohexane liquid crystal monomer can reach more than 83.2%, and the highest yield of the trans-alkyl bicyclohexane liquid crystal monomer can reach 89.5%.
Examples 5 to 10
Examples 5-10 provide a process for preparing trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane, respectively. The difference from example 1 is the amount of each substance added to catalyst II, as shown in Table 2.
TABLE 2 parameters in the preparation of example 1, examples 5-10-Compound III
Examples 11 to 16
Examples 11-16 provide a process for preparing trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane, respectively. The difference from example 1 is the amount of each substance added to catalyst II, as shown in Table 3.
TABLE 3 parameters in the preparation of example 1, examples 11-16-Compound III
As can be seen from comparison of examples 1, 5 and 6 with examples 11 and 12 by combining tables 2 and 3, the preparation method provided by the application controls the addition ratio of the three components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L of dilithium tetrachlorocuprate and vitamin B12 in the catalyst II to be (0.5-1.5): 1: when 1 is within the range, the yield of the final product trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane can be 80% or more, and the highest yield can be 89.5%. And when the catalyst II is prepared from 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12, the adding ratio of the three is 0.3:1: within the range of 1, the yield of the final product trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane can only reach 59.3%. Meanwhile, when the catalyst II comprises the following components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12, the adding proportion is 1.8:1: within the range of 1, the yield of the final product trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane can only reach 62.3%. Based on the above, the application controls the adding proportion of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L of lithium tetrachlorocuprate and vitamin B12 in the catalyst II to be (0.5-1.5): 1:1.
As can be seen from comparison of examples 1, 7 and 8 with examples 13 and 14, the preparation method provided by the application controls the adding ratio of three components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12 in the catalyst II to be 1: (0.5-1.5): when 1 is within the range, the yield of the trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane as the final product can be 87.5% or more, and the highest yield can be 88%. And when the catalyst II is prepared from 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12, the adding ratio of the three is 1:0.3: within the range of 1, the yield of the final product trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane can only reach 70.5%. Meanwhile, when the catalyst II comprises the following three components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12, the adding proportion is 1:1.8: within the range of 1, the yield of the final product trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane can only reach 68.2%. Based on the above, the application controls the adding proportion of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L of lithium tetrachlorocuprate and vitamin B12 in the catalyst II to be 1: (0.5-1.5): 1.
As can be seen from comparison of examples 1, 9 and 10 with examples 15 and 16, the preparation method provided by the application controls the adding ratio of three components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12 in the catalyst II to be 1:1: when the ratio is within the range of (0.5-1.5), the yield of trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane as the final product can be 80.2% or more, and the highest yield can be 88.9%. And when the catalyst II is prepared from 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12, the adding ratio of the three is 1:1: within the range of 0.3, the yield of trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane as the final product can only reach 39.2%. Meanwhile, when the catalyst II comprises the following three components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L lithium tetrachlorocuprate and vitamin B12, the adding proportion is 1:1: within the range of 1.8, the yield of the final product trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane can only reach 73.5%. Based on the above, the application controls the adding proportion of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L of lithium tetrachlorocuprate and vitamin B12 in the catalyst II to be 1:1: (0.5-1.5).
Therefore, the application provides the method for controlling the adding proportion of the three components of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L of lithium tetrachlorocuprate and vitamin B12 in the catalyst II to be (0.5-1.5): (0.5-1.5): (0.5-1.5).
Examples 17 to 19
Examples 17-19 provide, inter alia, a process for preparing trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane. It differs from example 1 in the type of catalyst II, as shown in Table 4.
TABLE 4 parameters in the preparation of example 1, examples 17-19-Compound III
As can be seen from a comparison of example 1 and example 17, using only two components of 4,4 '-di-tert-butyl-2, 2' -bipyridyl nickel dichloride and 2mol/L dilithium tetrachlorocuprate as catalyst II, the yield of the final product trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane was only 25.0%; as can be seen from a comparison of example 1 and example 18, the use of only two components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride and vitamin B12 as catalyst II resulted in a yield of only 36.0% of trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane; as can be seen from a comparison of example 1 and example 19, the use of only two components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride and vitamin B12 as catalyst II resulted in a yield of only 36.0% of trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane; is far less than the yield of the final product when three components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L of lithium tetrachlorocuprate and vitamin B12 are used together.
Meanwhile, when any two of the above are adopted as the catalyst II, the yield and purity of the final product are not ideal, the raw material conversion rate is low, and the byproducts are also more. Based on the above, the preparation method provided by the application can obviously improve the yield of the trans, trans-4-propyl-4 '-ethyl-1, 1' -bicyclohexane of the final product when the catalyst II is prepared from three components of 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, 2mol/L dilithium tetrachlorocuprate and vitamin B12. Meanwhile, the purity of the final product can be obviously improved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (5)
1. The preparation method of the trans-alkyl bicyclohexane liquid crystal monomer is characterized by comprising the following steps of:
(1) Preparation of Compound I: adding trans-4-alkyl cyclohexane phenol into an organic solvent I, and carrying out hydrogenation reaction by using a catalyst I to prepare a compound I; the structural general formula of the compound I is as follows:
R 1 is C 1 -C 14 An alkyl group;
the temperature of the hydrogenation reaction is 50-90 ℃; the pressure of the hydrogenation reaction is 0.5-1MPa;
the catalyst I is one or more of Pd/C with the mass content of 5-10%, ru/C with the mass content of 5-10% and Pt/C with the mass content of 5-10%;
(2) Preparation of Compound II: adding the compound I prepared in the step (1) into an organic solvent II, and dropwise adding a halogenating reagent; carrying out halogenation reaction at 50-60 ℃ to prepare a compound II; the structural general formula of the compound II is as follows:
R 1 is C 1 -C 14 Alkyl, X is a halogen element;
(3) Preparation of Compound III: mixing manganese powder, a catalyst II and an organic solvent III to form a reaction system, and stirring until the reaction system is black; adding sulfonate and the compound II obtained in the step (2) into a reaction system to perform a coupling reaction to prepare a compound III; the structural general formula of the compound III is
R 1 Is C 1 -C 14 Alkyl, R 2 Is C 1 -C 14 An alkyl group;
the catalyst II is 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, dilithium tetrachlorocuprate and vitamin B12 which are mixed according to any ratio;
the temperature of the coupling reaction is 20-30 ℃.
2. The method for preparing the trans-alkyl bicyclohexane liquid crystal monomer according to claim 1, wherein the method comprises the following steps: in the step (3), in the catalyst II, the proportion of the 4,4 '-di-tert-butyl-2, 2' -bipyridine nickel dichloride, the lithium tetrachlorocuprate and the vitamin B12 is (0.5-1.5): (0.5-1.5): (0.5-1.5).
3. The method for preparing the trans-alkyl bicyclohexane liquid crystal monomer according to claim 1, wherein the method comprises the following steps: in the step (3), the molar ratio of the compound II to the catalyst II is 1: (0.05-0.1).
4. The method for preparing the trans-alkyl bicyclohexane liquid crystal monomer according to claim 1, wherein the method comprises the following steps: in the step (1), the weight ratio of the trans-4-alkyl cyclohexane phenol to the organic solvent I is 1: (4-6).
5. The method for preparing the trans-alkyl bicyclohexane liquid crystal monomer according to claim 1, wherein the method comprises the following steps: in the step (1), the weight ratio of the trans-4-alkyl cyclohexane phenol to the catalyst I is 100: (1-5).
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