CN113024375B - Preparation method of trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer - Google Patents
Preparation method of trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 21
- 239000000178 monomer Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005917 acylation reaction Methods 0.000 claims abstract description 10
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 238000006722 reduction reaction Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 20
- 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 description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000007818 Grignard reagent Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000004795 grignard reagents Chemical class 0.000 claims description 14
- 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 description 13
- YTKRILODNOEEPX-NSCUHMNNSA-N crotyl chloride Chemical compound C\C=C\CCl YTKRILODNOEEPX-NSCUHMNNSA-N 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 8
- 230000010933 acylation Effects 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- AVMHMVJVHYGDOO-NSCUHMNNSA-N (e)-1-bromobut-2-ene Chemical compound C\C=C\CBr AVMHMVJVHYGDOO-NSCUHMNNSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002897 diene group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000012769 display material Substances 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- 239000012074 organic phase Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- 238000010791 quenching Methods 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- HCJWWBBBSCXJMS-UHFFFAOYSA-J copper;dilithium;tetrachloride Chemical compound [Li+].[Li+].[Cl-].[Cl-].[Cl-].[Cl-].[Cu+2] HCJWWBBBSCXJMS-UHFFFAOYSA-J 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- SRQNIPUSSAISTC-UHFFFAOYSA-N [Ni].CCCCCC Chemical compound [Ni].CCCCCC SRQNIPUSSAISTC-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- -1 1-chloro-2-butene Grignard reagent Chemical class 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/322—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a sulfur atom
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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Abstract
The invention relates to the technical field of liquid crystal display material synthesis, and particularly discloses a preparation method of a trans, trans-4-alkyl-4 ' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer, which takes trans, trans-4-alkyl-4 ' -formic acid-bicyclohexane and alkyl alcohol as starting materials, and prepares the trans, trans-4-alkyl-4 ' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer through esterification reaction, reduction reaction, acylation reaction and cross coupling reaction in sequence. The method has the advantages of short synthetic route and low production cost, and is suitable for industrial production.
Description
Technical Field
The application relates to the technical field of liquid crystal display material synthesis, in particular to a preparation method of a trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer.
Background
The trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer has the advantages of small viscosity, high response speed, better optical anisotropy, high compatibility with other liquid crystal monomers and the like, and meanwhile, the liquid crystal monomer has high clear point and good tolerance to light and heat. The trans-4-alkyl-4 '-amyl-3 (E) alkene-bicyclo hexane liquid crystal monomer is used as a very important liquid crystal base material, and the usage amount of the trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclo hexane liquid crystal monomer in mixed crystals is large.
The prior patent document with the authority of 2018, 11, 13 and CN106753423B discloses a preparation method of trans, trans-4-alkyl-4 '-amyl-3 (E) alkene-bicyclohexane liquid crystal monomer, which takes trans-4' -alkylbicyclohexyl-4-ketone as a starting material and sequentially carries out six steps of reactions such as Grignard reaction, hydrogenation reaction, deprotection reaction, isomerization, wittig reaction and isomerization reaction to obtain a target product.
The preparation method has the following defects: the first step, the synthesis step is longer, the total yield is low, and the industrialized production is not facilitated; second, hydrogenation requires special equipment and is subject to physical and chemical explosion hazards, and deprotected materials are easily produced during hydrogenation, which can be further reduced to harmful impurities.
Disclosure of Invention
In order to simplify the synthetic route and reduce the production cost, and is suitable for industrial production, the application provides a preparation method of a trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer, which adopts the following technical scheme:
a preparation method of a trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer comprises the following steps:
(i) Adding trans, trans-4-alkyl-4' -formic acid-bicyclohexane and alkyl alcohol with a molar ratio of 1 (20-25) into an organic solvent I at 110-120 ℃ to perform a concentrated sulfuric acid catalytic esterification reaction to generate a compound I, wherein the structural formula is as follows
R 1 Is C1-C7 alkyl, R 2 Is C1-C4 alkyl;
(ii) Under the condition of inert atmosphere and 55-65 ℃, the mol ratio of 1 (1.3-2): (1.3-2) of compound I, potassium borohydride and lithium chloride are subjected to reduction reaction in an organic solvent I I to generate a compound I I, and the structural general formula of the compound is
R 1 Is C1-C7 alkyl;
(iii) Dropwise adding a mixture containing tosyl chloride and an organic solvent III into the mixture containing the compound II, a binding agent, an acylation catalyst and the organic solvent III in an inert atmosphere at 0-5 ℃, and heating to 20-30 ℃ after the completion of dropwise adding to carry out acylation reaction to obtain the compound III, wherein the structural general formula is as follows
R 1 Is C1-C7 alkyl; the mol ratio of the compound I I to the binding agent to the acylation catalyst to the p-toluenesulfonyl chloride is 1 (1.1-1.5) (0.008-0.020) (1-1.1);
(iv) Adding Grignard reagent prepared from magnesium and 1-halogen-2-butene into a mixture of a compound III, a diene ligand catalyst and an organic solvent IV in an inert atmosphere at the temperature of 30 ℃ below zero to 40 ℃ for 3 to 6 hours, neutralizing a reaction system, and purifying to obtain the trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer with the structural general formula of
R 1 Is C1-C7 alkyl; the mol ratio of the compound III, the diene ligand catalyst, the magnesium and the 1-halogen-2-butene is 1 (0.04-0.1): 1.7-2.1): 1-1.5.
Preferably, the alkyl alcohol comprises at least one of methanol, ethanol, n-propanol and n-butanol.
Preferably, the organic solvent I is toluene.
Preferably, the weight ratio of the alkyl alcohol to the organic solvent I is 1 (4-8).
Preferably, the organic solvent II is tetrahydrofuran.
Preferably, the binding agent comprises at least one of pyridine, triethylamine and diisopropylethylamine, and the acylation catalyst is 4-dimethylaminopyridine.
Preferably, the organic solvent III is dichloromethane.
Preferably, the diene ligand catalyst is at least one selected from the group consisting of nickel bis allyl and palladium bis allyl.
Preferably, the 1-halo-2-butene comprises at least one of 1-chloro-2-butene and 1-bromo-2-butene.
Preferably, the organic solvent IV is tetrahydrofuran.
In summary, the present application has the following beneficial effects:
first, this application simplifies synthetic route, reduces manufacturing cost, is suitable for industrial production.
Secondly, the application adopts the bis (allyl) nickel or bis (allyl) palladium as a catalyst in the step (iv), and can obtain higher yield and higher purity of a target product when catalyzing the coupling reaction of the compound III and the 1-chloro-2-butene Grignard reagent. However, when dilithium tetrachlorocuprate is used as a catalyst, the yield and purity of the obtained target product are not ideal, because carbon-carbon double bonds in the Grignard reagent affect the cross coupling reaction, promote the occurrence of side reactions and affect the yield and purity of the target product.
Detailed Description
The present application is described in further detail below with reference to examples.
A synthetic route of trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer:
the trans, trans-4-alkyl-4 '-amyl-3 (E) alkene-bicyclohexane liquid crystal monomer is prepared by taking trans, trans-4-alkyl-4' -formic acid-bicyclohexane as an initiator and sequentially carrying out esterification reaction, reduction reaction, acylation reaction and cross coupling reaction.
Example 1
When R is 1 In the case of n-propyl, the target product is trans, trans-4-n-propyl-4' -pentyl-3 (E) alkene-bicyclohexane.
Synthesis of Compound I: adding 80g of toluene and 320g of methanol into a 1L three-necked flask, adding 80g of trans, trans-4-n-propyl-4' -formic acid-bicyclohexane, slowly adding 8g of concentrated sulfuric acid, and carrying out reflux reaction for 3 hours; the methanol is distilled off by rotating, the temperature is reduced to 40 ℃, 80g of toluene is added, the mixture is washed twice, dried by anhydrous sodium sulfate, and the solvent is evaporated by decompression concentration, thus 84.5g of compound I is obtained, and the yield is 100%.
Synthesis of Compound II: into a 1L three-necked flask, 400g of tetrahydrofuran and 84.5g (0.316 mol) of Compound I were charged, 27.1g (0.475 mol) of potassium borohydride and 20.1g (0.475 mol) of anhydrous lithium chloride were added under stirring, the mixture was replaced with nitrogen, the reaction was carried out at 60℃for 5 hours under a controlled temperature, and the reaction was terminated by GC.
Cooling to room temperature, neutralizing the reaction system with 10% hydrochloric acid, extracting with 140g toluene, standing for separating, extracting the lower water phase with 70g toluene, mixing the organic phases, drying with anhydrous sodium sulfate, concentrating under negative pressure to obtain 75.6g of compound II, and the yield is 100%.
Synthesis of Compound III: to a 1L three-necked flask, 300g of methylene chloride and 75.6g of compound II were added, 41.6g of triethylamine and 0.38g of 4-dimethylaminopyridine were further added, the temperature was lowered to 0℃under nitrogen protection, a solution of 63.2g of p-toluenesulfonyl chloride in methylene chloride (250 mL) was added dropwise, the temperature was raised to 25℃after the completion of the dropwise addition, and the reaction was continued for 10 hours, followed by HPLC monitoring.
160g of water was added to the reaction system, stirred for 10 minutes, left to stand for separation, the aqueous phase was extracted with 100g of methylene chloride, the organic phases were combined, washed twice with water, and the organic phases were dried over anhydrous sodium sulfate. The dried organic phase was concentrated to dryness, to which 330g of n-heptane was added, and the mixture was stirred at 60℃for 1 hour, cooled to 0℃and filtered, followed by drying to give compound III,116.3g, in a white form, in a yield of 93.5% (without mother liquor recovery).
Synthesizing a target product: under the protection of nitrogen, 13.8g (0.57 mol) of magnesium chips and 30mL of anhydrous tetrahydrofuran are added into a 500mL three-necked flask to prepare 34.8g (0.38 mol) of tetrahydrofuran (105 mL) solution of 1-chloro-2-butene, the temperature is controlled to be 0-20 ℃, the tetrahydrofuran solution of 1-chloro-2-butene is dripped into the three-necked flask, and after the dripping is finished, the reaction is carried out for 1 hour under the condition of heat preservation, so as to obtain the Grignard reagent.
620g of tetrahydrofuran, 116.3g (0.30 mol) of compound III and nitrogen are added into a 2L three-necked flask, the temperature is reduced to minus 30 ℃, 30mL of 1mol/L of bis (allyl) nickel n-hexane solution is added, the Grignard reagent is added dropwise, and after the dropwise addition, the reaction is carried out for 3 hours under heat preservation. After the reaction is finished, hydrochloric acid with the weight percentage concentration of 10% is slowly dripped to neutralize the reaction system so as to quench the reaction.
Extracting with n-heptane after quenching, washing the organic phase with water to neutrality, drying with anhydrous sodium sulfate, concentrating under reduced pressure, evaporating to dryness to obtain solvent, recrystallizing with n-heptane/ethanol system with volume ratio of 1:4 for three times, and oven drying to obtain target product 68.8g with purity of 99.9% and yield of 73%.
Characterization of the target product:
1 H-NMR(400MHz,CDCl 3 )：δ:5.34-5.45(m,2H)；1.95-1.99(m,2H)；1.67-1.75(q,8H)；1.62-1.64(m,3H)；1.10-1.30(m,8H)；0.93-0.99(m,6H)；0.84-0.88(t,7H)；
MS：m/z 276(M + )。
example 2
When R is 1 In the case of ethyl, the target product is trans, trans-4-ethyl-4' -pentyl-3 (E) ene-bicyclohexane.
Synthesis of Compound I: 80g of toluene and 320g of methanol are added into a 1L three-necked flask, 75.65g of trans, trans-4-n-propyl-4' -formic acid-bicyclohexane is added, 8g of concentrated sulfuric acid is slowly added, and reflux reaction is carried out for 3 hours; the methanol is distilled off by rotating, the temperature is reduced to 40 ℃, 80g of toluene is added, the mixture is washed twice, dried by anhydrous sodium sulfate, and the solvent is evaporated by decompression concentration, thus 80.1g of compound I is obtained, and the yield is 100%.
Synthesis of Compound II: into a 1L three-necked flask, 400g of tetrahydrofuran and 79.85g (0.316 mol) of Compound I were charged, 27.1g (0.475 mol) of potassium borohydride and 20.1g (0.475 mol) of anhydrous lithium chloride were added under stirring, the mixture was replaced with nitrogen, the reaction was carried out at 60℃for 5 hours under a controlled temperature, and the reaction was terminated by GC.
Cooling to room temperature, neutralizing the reaction system with 10% hydrochloric acid, extracting with 140g toluene, standing for separating, extracting the lower water phase with 70g toluene, mixing the organic phases, drying with anhydrous sodium sulfate, concentrating under negative pressure, and drying the solvent to obtain 71.0g of compound II with 100% yield.
Synthesis of Compound III: to a 1L three-necked flask, 300g of methylene chloride and 71.0g of compound II were added, 41.6g of triethylamine and 0.38g of 4-dimethylaminopyridine were further added, the temperature was lowered to 0℃under nitrogen protection, a solution of 63.2g of p-toluenesulfonyl chloride in methylene chloride (250 mL) was added dropwise, the temperature was raised to 25℃after the completion of the dropwise addition, and the reaction was continued for 10 hours, followed by HPLC monitoring.
160g of water was added to the reaction system, stirred for 10 minutes, left to stand for separation, the aqueous phase was extracted with 100g of methylene chloride, the organic phases were combined, washed twice with water, and the organic phases were dried over anhydrous sodium sulfate. The dried organic phase was concentrated to dryness, to which 330g of n-heptane was added, and the mixture was stirred at 60℃for 1 hour, cooled to 0℃and filtered, followed by drying to give white compound III (113.49 g, yield 95.3% (without mother liquor recovery).
Synthesizing a target product: under the protection of nitrogen, 13.8g (0.57 mol) of magnesium chips and 30mL of anhydrous tetrahydrofuran are added into a 500mL three-necked flask to prepare 34.8g (0.38 mol) of tetrahydrofuran (105 mL) solution of 1-chloro-2-butene, the temperature is controlled to be 0-20 ℃, the tetrahydrofuran solution of 1-chloro-2-butene is dripped into the three-necked flask, and after the dripping is finished, the reaction is carried out for 1 hour under the condition of heat preservation, so as to obtain the Grignard reagent.
620g of tetrahydrofuran, 113.05g (0.30 mol) of compound III and nitrogen are added into a 2L three-necked flask, the temperature is reduced to-30 ℃, 30mL of 1mol/L of bis (allyl) nickel n-hexane solution is added, the Grignard reagent is added dropwise, and after the dropwise addition is finished, the reaction is carried out for 3 hours under heat preservation. After the reaction is finished, hydrochloric acid with the weight percentage concentration of 10% is slowly dripped to neutralize the reaction system so as to quench the reaction.
Extracting with n-heptane after quenching, washing the organic phase with water to neutrality, drying with anhydrous sodium sulfate, concentrating under reduced pressure, evaporating to dryness to obtain solvent, recrystallizing with n-heptane/ethanol system with volume ratio of 1:4 for three times, and oven drying to obtain 59.1g of target product with purity of 99.9% and yield of 75%.
Characterization of the target product:
1 H-NMR(400MHz,CDCl3)：δ:5.44(2H,m)；2.05(2H,m)；1.64(3H,m)；1.35～1.61(14H,m)；1.12～1.30(10H,m)；0.88(3H,m)；
MS,m/z 262(M + )。
example 3
When R is 1 In the case of n-pentyl, the target product is trans, trans-4-n-pentyl-4' -pentyl-3 (E) ene-bicyclohexane.
Synthesis of Compound I: 80g of toluene and 320g of methanol are added into a 1L three-necked flask, 88g of trans, trans-4-n-propyl-4' -formic acid-bicyclohexane is added, 8g of concentrated sulfuric acid is slowly added, and reflux reaction is carried out for 3 hours; the methanol is distilled off by rotating, the temperature is reduced to 40 ℃, 80g of toluene is added, the mixture is washed twice, dried by anhydrous sodium sulfate, and the solvent is evaporated by decompression concentration, thus 92.4g of compound I is obtained, and the yield is 100%.
Synthesis of Compound II: into a 1L three-necked flask, 400g of tetrahydrofuran and 93.1g (0.316 mol) of Compound I were charged, 27.1g (0.475 mol) of potassium borohydride and 20.1g (0.475 mol) of anhydrous lithium chloride were added under stirring, the mixture was replaced with nitrogen, the reaction was carried out at 60℃for 5 hours under a controlled temperature, and the reaction was terminated by GC.
Cooling to room temperature, neutralizing the reaction system with 10% hydrochloric acid, extracting with 140g toluene, standing for separating, extracting the lower water phase with 70g toluene, mixing the organic phases, drying with anhydrous sodium sulfate, concentrating under negative pressure, and drying the solvent to obtain 84.2g of compound II with 100% yield.
Synthesis of Compound III: to a 1L three-necked flask, 300g of methylene chloride and 84.2g of compound II were added, 41.6g of triethylamine and 0.38g of 4-dimethylaminopyridine were further added, the temperature was lowered to 0℃under nitrogen protection, a solution of 63.2g of p-toluenesulfonyl chloride in methylene chloride (250 mL) was added dropwise, the temperature was raised to 25℃after the completion of the dropwise addition, and the reaction was continued for 10 hours, followed by HPLC monitoring.
160g of water was added to the reaction system, stirred for 10 minutes, left to stand for separation, the aqueous phase was extracted with 100g of methylene chloride, the organic phases were combined, washed twice with water, and the organic phases were dried over anhydrous sodium sulfate. The dried organic phase was concentrated to dryness, to which 330g of n-heptane was added, and the mixture was stirred at 60℃for 1 hour, cooled to 0℃and filtered, followed by drying to give compound III (122.0 g) in white form in 92.2% yield (without mother liquor recovery).
Synthesizing a target product: under the protection of nitrogen, 13.8g (0.57 mol) of magnesium chips and 30mL of anhydrous tetrahydrofuran are added into a 500mL three-necked flask to prepare 34.8g (0.38 mol) of tetrahydrofuran (105 mL) solution of 1-chloro-2-butene, the temperature is controlled to be 0-20 ℃, the tetrahydrofuran solution of 1-chloro-2-butene is dripped into the three-necked flask, and after the dripping is finished, the reaction is carried out for 1 hour under the condition of heat preservation, so as to obtain the Grignard reagent.
620g of tetrahydrofuran, 125.6g (0.30 mol) of compound III and nitrogen are added into a 2L three-necked flask, the temperature is reduced to minus 30 ℃, 30mL of 1mol/L of bis-allylnickel n-hexane solution is added, the Grignard reagent is added dropwise, and after the dropwise addition, the reaction is carried out for 3 hours under heat preservation. After the reaction is finished, hydrochloric acid with the weight percentage concentration of 10% is slowly dripped to neutralize the reaction system so as to quench the reaction.
Extracting with n-heptane after quenching, washing the organic phase with water to neutrality, drying with anhydrous sodium sulfate, concentrating under reduced pressure, evaporating to dryness to obtain solvent, recrystallizing with n-heptane/ethanol system with volume ratio of 1:4 for three times, and oven drying to obtain target product with 65.8g, purity of 99.9% and yield of 72%.
Characterization of the target product:
1 H-NMR(400MHz,CDCl 3 )：δ:5.43(2H,m)；2.07(2H,m)；1.47-1.63(11H,m)；1.15-1.45(18H,m)；1.00(2H,m)；0.89(3H,m)；
MS,m/z 290(M+)。
comparative example 1
When R is 1 In the case of n-propyl, the target product is trans, trans-4-n-propyl-4' -pentyl-3 (E) alkene-bicyclohexane.
Synthesizing a target product: the procedure is as in example 1, except that the catalyst bis (allylic) nickel is replaced by bis (lithium) tetrachlorocuprate.
The specific synthesis steps are as follows: into a 500mL three-necked flask, 13.8g (0.57 mol) of magnesium turnings and 30mL of anhydrous tetrahydrofuran were added to prepare a solution of 34.8g (0.38 mol) of 1-chloro-2-butene in tetrahydrofuran (105 mL), the temperature was controlled at 0-20℃and the solution of 1-chloro-2-butene in tetrahydrofuran was added dropwise to the three-necked flask, followed by a reaction at a constant temperature for 1 hour after the completion of the dropwise addition to obtain a Grignard reagent.
To a 2L three-necked flask were added 620g of tetrahydrofuran, 116.3g (0.30 mol) of compound III and 80mL of 0.2mol/L of a dilithium tetrachlorocuprate solution, the temperature was lowered to 0℃under nitrogen protection, the Grignard reagent was added dropwise, and after the dropwise addition was completed, the temperature was raised to 25℃for reaction for 12 hours. After the reaction is finished, the temperature is reduced to 0 ℃, hydrochloric acid with the weight percentage concentration of 10% is slowly dripped to neutralize the reaction system, so that the reaction is quenched.
Extracting with n-heptane after quenching, washing the organic phase with water to neutrality, drying with anhydrous sodium sulfate, concentrating under reduced pressure, evaporating to dryness to obtain solvent, recrystallizing with n-heptane/ethanol system with volume ratio of 1:4 for three times, and oven drying to obtain target product 49.0g with purity of 97.2% and yield of 52%.
As can be seen from the combination of example 1 and comparative example 1, the present application uses a cross-coupling reaction of the bis-allylic nickel catalytic compound III and the Grignard reagent made of magnesium and 1-chloro-2-butene to obtain higher yields and higher purity of the desired product. However, the use of dilithium tetrachlorocuprate to catalyze the cross-coupling reaction of compound III with a grignard reagent made of magnesium and 1-chloro-2-butene does not provide an ideal yield and purity of the target product, since the carbon-carbon double bonds in the grignard reagent affect the cross-coupling reaction, promote side reactions, and affect the yield and purity of the target product.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. A preparation method of a trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer is characterized by comprising the following steps:
(i) Adding trans, trans-4-alkyl-4' -formic acid-bicyclohexane and alkyl alcohol with a molar ratio of 1 (20-25) into an organic solvent I at 110-120 ℃ to perform a concentrated sulfuric acid catalytic esterification reaction to generate a compound I, wherein the structural formula is as follows
R 1 Is C1-C7 alkyl, R 2 Is C1-C4 alkyl;
(ii) Under the condition of inert atmosphere and 55-65 ℃, the mol ratio of (1.3-2) is that (1.3-2) of compound I, potassium borohydride and lithium chloride undergo reduction reaction in an organic solvent II to generate a compound II, and the structural general formula is
R 1 Is C1-C7 alkyl;
(iii) Dropwise adding a mixture containing tosyl chloride and an organic solvent III into the mixture containing the compound II, a binding agent, an acylation catalyst and the organic solvent III in an inert atmosphere at 0-5 ℃, and heating to 20-30 ℃ after the completion of dropwise adding to carry out acylation reaction to obtain the compound III, wherein the structural general formula is as follows
R 1 Is C1-C7 alkyl; the mol ratio of the compound II, the binding agent, the acylation catalyst and the p-toluenesulfonyl chloride is 1 (1.1-1.5) (0.008-0.020) (1-1.1);
(iv) Adding Grignard reagent prepared from magnesium and 1-halogen-2-butene into a mixture of a compound III, a diene ligand catalyst and an organic solvent IV in an inert atmosphere at the temperature of 30 ℃ below zero to 40 ℃ for 3 to 6 hours, neutralizing a reaction system, and purifying to obtain the trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer with the structural general formula of
R 1 Is C1-C7 alkyl; the mol ratio of the compound III to the diene ligand catalyst to the magnesium to the 1-halogen-2-butene is 1 (0.04-0.1): 1.7-2.1): 1-1.5;
the diene ligand catalyst is diene nickel.
2. The method according to claim 1, wherein the alkyl alcohol comprises at least one of methanol, ethanol, n-propanol, and n-butanol.
3. The preparation method according to claim 1, wherein the organic solvent I is toluene.
4. The process according to claim 1, wherein the weight ratio of alkyl alcohol to organic solvent I is 1 (4-8).
5. The preparation method according to claim 1, wherein the organic solvent II is tetrahydrofuran.
6. The method according to claim 1, wherein the binding agent comprises at least one of pyridine, triethylamine, and diisopropylethylamine, and the acylation catalyst is 4-dimethylaminopyridine.
7. The preparation method according to claim 1, wherein the organic solvent III is methylene chloride.
8. The method according to claim 1, wherein the 1-halo-2-butene comprises at least one of 1-chloro-2-butene and 1-bromo-2-butene.
9. The preparation method according to claim 1, wherein the organic solvent IV is tetrahydrofuran.
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