CN101565363B - Preparation method of 4- [2 '- (trans-4' -alkylcyclohexyl) ethyl ] cyclohexanone liquid crystal intermediate compound - Google Patents
Preparation method of 4- [2 '- (trans-4' -alkylcyclohexyl) ethyl ] cyclohexanone liquid crystal intermediate compound Download PDFInfo
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- CN101565363B CN101565363B CN2009100154901A CN200910015490A CN101565363B CN 101565363 B CN101565363 B CN 101565363B CN 2009100154901 A CN2009100154901 A CN 2009100154901A CN 200910015490 A CN200910015490 A CN 200910015490A CN 101565363 B CN101565363 B CN 101565363B
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title claims abstract description 50
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 cyclohexanone compound Chemical class 0.000 claims abstract description 10
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 6
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000543 intermediate Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004508 fractional distillation Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- GHQVTZQYEFAURL-UHFFFAOYSA-N N#CC#N.C(C1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound N#CC#N.C(C1=CC=CC=C1)OC1=CC=CC=C1 GHQVTZQYEFAURL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 235000019396 potassium bromate Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims 1
- 239000004153 Potassium bromate Substances 0.000 claims 1
- 229940094037 potassium bromate Drugs 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract 2
- MKYMYZJJFMPDOA-UHFFFAOYSA-N 1-(4-phenylmethoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1OCC1=CC=CC=C1 MKYMYZJJFMPDOA-UHFFFAOYSA-N 0.000 abstract 1
- UDAOJHAASAWVIQ-UHFFFAOYSA-N 4-phenylmethoxybenzonitrile Chemical compound C1=CC(C#N)=CC=C1OCC1=CC=CC=C1 UDAOJHAASAWVIQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005194 fractionation Methods 0.000 abstract 1
- 229940050176 methyl chloride Drugs 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 10
- 125000002243 cyclohexanonyl group Chemical class *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 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 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PAWNEPWFHAMWEZ-UHFFFAOYSA-N C1C(ClC)CCCC1 Chemical compound C1C(ClC)CCCC1 PAWNEPWFHAMWEZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000526 short-path distillation Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- KZUODEMJNGXTCG-UHFFFAOYSA-N C1(CCCCC1)C1=C(C=CC(=C1)OCC1=CC=CC=C1)C(C)=O Chemical compound C1(CCCCC1)C1=C(C=CC(=C1)OCC1=CC=CC=C1)C(C)=O KZUODEMJNGXTCG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HAFVQBQRXQUJBJ-HDJSIYSDSA-N CCCCCCC[C@H](CC1)CC[C@@H]1ClC Chemical group CCCCCCC[C@H](CC1)CC[C@@H]1ClC HAFVQBQRXQUJBJ-HDJSIYSDSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UURNLXIWBYIBFP-ZKCHVHJHSA-N ClC[C@@H]1CC[C@H](CC1)C Chemical group ClC[C@@H]1CC[C@H](CC1)C UURNLXIWBYIBFP-ZKCHVHJHSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000008423 fluorobenzenes Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- OCATYIAKPYKMPG-UHFFFAOYSA-M potassium bromate Chemical class [K+].[O-]Br(=O)=O OCATYIAKPYKMPG-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A preparation method of a 4- [2 ' - (trans-4 ' -alkylcyclohexyl) ethyl ] cyclohexanone liquid crystal intermediate compound is characterized in that trans-4-alkylcyclohexyl methyl chloride reacts with magnesium chips in an organic solvent to obtain a Grignard reagent, then the Grignard reagent reacts with p-benzyloxy benzonitrile, and then the Grignard reagent is subjected to acidic hydrolysis to obtain trans-4 ' -alkylcyclohexyl acetyl-4-benzyloxy benzene (B); (B) carrying out step hydrogenation reaction in an organic solvent under the catalysis of a catalyst to prepare 4- [2 '- (trans-4' -alkylcyclohexyl) ethyl ] cyclohexyl alcohol (C), and carrying out precise fractionation and purification; in an organic solvent, preparing a 4- [2 '- (trans-4' -alkylcyclohexyl) ethyl ] cyclohexanone compound in the presence of an environment-friendly oxidant, and then precisely fractionating, purifying and recrystallizing to obtain the product. The invention can meet the requirements of TFT-LCD on high purity and high quality of liquid crystal intermediate.
Description
Technical field
The present invention relates to a kind of preparation method of liquid crystal intermediates compound, relate more specifically to the preparation method of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog liquid crystal intermediates compound.
Background technology
Thin Film Transistor-LCD (TFT-LCD) is most important a kind of in the liquid-crystal display (LCD); Its output value and influence power have critical role in liquid-crystal display family, be widely used in all respects such as televisor, notebook computer, watch-dog, mobile phone.
Liquid crystal material is one of several big materials that constitute by liquid-crystal display (LCD), and, being accompanied by the difference of display format, required liquid crystal material is also different.Therefore; Also be accompanied by the development of liquid-crystal display and grow in strength as the liquid crystal material that shows usefulness; A large amount of novel liquid crystalline cpds have appearred; Like: cyclohexyl (couplet) benzene class, ethane bridged bond class, end alkene class with contain fluorobenzene class liquid crystalline cpd etc., constantly to satisfy display devices such as TN-LCD, STN-LCD, TFT-LCD to performance demands.
It is generally acknowledged, contain the center bridged bond in the liquid crystal molecule, (liquid crystal molecule CH2CH2-) is referred to as ethane class liquid crystalline cpd, and it is very important one type of liquid crystal compound, wherein, is divided into several hypotype groups again promptly to contain ethylene.The introducing of ethane bridged bond has given liquid crystal molecule many advantageous properties, and like optical anisotropy little (Δ n), viscosity is lower, and response speed is fast, and chemicalstability is good, and good light stability, low temperature mutual solubility are good etc.Therefore, ethane class liquid crystalline cpd in high-grade liquid crystal material, as: have among STN, the TFT widely and to use, become wherein indispensable composition.
In order to obtain the required various characteristics of display format, liquid crystal material uses with the form of mixtures of plurality of liquid crystals compound usually, therefore, needs liquid crystalline cpd to have good mutual solubility, particularly at low temperatures.
Open the liquid crystalline cpd that all is mentioned to alkyl-cyclohexyl ethyl cyclohexyl polyfluorobenzene in the patents such as flat 9-71779 and US5728319 disclosed US20030001138, US6682784, spy:
These liquid crystalline cpds constitute the mixed liquid crystal material that STN-LCD and TFT-LCD use with other liquid crystalline cpd, and become wherein very important integral part, in TFT-LCD, have widely and use, and become wherein indispensable composition.
And to prepare above-mentioned ethane class monomer liquid crystal compound, just must use 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog liquid crystal intermediates.EP0; 280; 902 patents are thought: 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog liquid crystal intermediates is a kind of important midbody of synthetic ethane class liquid crystal, it can with corresponding grignard reagent reaction, go out a series of ethane class liquid crystalline cpds through dehydration, hydrogenation preparing.
At present; Preparation report about 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog liquid crystal intermediates is few; only have < fine chemistry industry>2002 the 19th the 07th phases of volume to report one piece of article that the Zhang Xiaojun, Tang Hong etc. of Tsing-Hua University deliver; with trans-4-amyl group hexahydrobenzoic acid is raw material; synthesized 4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] pimelinketone through 8 step reaction such as lithium aluminium hydride reduction, bromo, grignard reaction, dehydration of alcohols, catalytic hydrogenation, demethylation, high pressure catalytic hydrogenation and sodium dichromate 99 oxidation, 40.9 ℃ of fusing points, and its massfraction of gas chromatograph for determination is 99.1%.This kind compound can be used as the important intermediate of preparation ethane class polycyclic system liquid crystal.But this operational path is not only oversize, processing condition are harsh, but also with sodium dichromate 99 as the oxygenant contaminate environment; Very easily produce by product in its preparation process, be difficult for purifying, make the purity of the finished product relatively poor; Be merely 99.1%; TFT-LCD can not be satisfied to liquid crystal intermediates high purity, high-quality requirement, simultaneously, the theory that current environmental protection is produced can not be satisfied and adapt to.
Summary of the invention
The objective of the invention is to overcome the deficiency that exists in the above-mentioned prior art; The novel preparation method of simple, the high yield of a kind of technology, highly purified 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog liquid crystal intermediates compound is provided; satisfy TFT-LCD to liquid crystal intermediates high purity, high-quality requirement, adapt to the needs of TFT-LCD with the liquid crystal material fast development.
General formula (I) structure of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog liquid crystal intermediates compound is following:
Wherein:
R is C
1-C
10Alkyl; Further, R is preferably C
1-C
10Straight chained alkyl;
More preferably, R is C
1-C
7Straight chained alkyl;
Most preferably, R is-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11Or-C
7H
15
For realizing that the object of the invention provides a kind of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] novel preparation method of cyclohexanone analog liquid crystal intermediates compound (general formula (I)), its synthetic route is following:
Preparing method's step of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog liquid crystal intermediates compound general formula (I) is following:
(1) with trans-4-alkyl-cyclohexyl methyl chloride (A) in organic solvent with magnesium chips reaction, obtain grignard reagent, again with to the reaction of benzyloxy benzene cyanogen, then carry out acidic hydrolysis obtain trans accordingly-4 '-alkyl-cyclohexyl ethanoyl-4-benzyloxy benzene (B);
(2) trans-4 '-alkyl-cyclohexyl ethanoyl-4-benzyloxy benzene (B) in organic solvent under the catalysis of catalyzer; Carry out highly compressed ladder hydrogenation reaction after the first low pressure; Reduce the generation of side reaction; Obtain corresponding 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C), carry out precision fractional distillation, purification again;
(3) in organic solvent; 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C) is in the presence of the environmental protection oxygenant; oxidation makes 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog compound (I); Carry out precision fractional distillation, purification, recrystallization again, obtain target product with high purity.
Organic solvent described in the step of the present invention (1) is at least a in ether, THF, methyltetrahydrofuran, benzene, toluene and the YLENE, and it is preferably the mixture of THF and toluene.
Acidic hydrolysis described in the step of the present invention (1); Be in the presence of acid, to implement; Preferred randomly hydrochloric acid, sulfuric acid, the glacial acetic acid of dilute with water, the more preferably hydrochloric acid of dilute with water, sulfuric acid most preferably are the sulfuric acid of dilute with water; Generally speaking, the concentration after the various acid dilutions is 10-50%.
Step of the present invention (1) can be implemented in wide relatively TR, and typical temperature is 10 ℃ to 105 ℃, and preferred temperature is 20 ℃ to 105 ℃.Most preferably the reaction of each reactive component further is reflected at 70 ℃ to 85 ℃ and carries out earlier 60 ℃ to 75 ℃ following initiation reactions in the step (1), then, under 90 ℃ to 105 ℃, carries out acidic hydrolysis again.
In the enforcement of step of the present invention (1), for trans-4-alkyl-cyclohexyl methyl chloride (A) of 1mol, employed magnesium chips is generally 0.7mol to 1.5mol, is preferably 0.9mol to 1.3mol, more preferably 1.0mol to 1.1mol; Employed benzyloxy benzene cyanogen is generally 0.6mol to 1.4mol, more preferably 0.8mol to 1.2mol most preferably is 0.9mol to 1.0mol.
In the step of the present invention (1), the reaction times is not crucial, can how much in the scope of broad, selecting according to production lot.Generally speaking, time of gathering in (1) each reaction in step combines and reaches 15 hours most, and its preferred time is 10 hours, and more preferably the time is 8 hours.
Catalyzer described in the step of the present invention (2) is at least a among Raney's nickel catalyst, active nickel catalyst, Pd/C, the Pt/C, is preferably Raney's nickel catalyst, most preferably is neutral Raney's nickel catalyst.
Organic solvent described in the step of the present invention (2) is at least a in ETHYLE ACETATE, ethanol, methyl alcohol, Virahol, toluene, YLENE and the methylene dichloride, is preferably ethanol and methyl alcohol, most preferably is ethanol.
The present invention step gathers the ladder hydrogenation reaction described in (2) and is meant highly compressed hydrogenation process after the first low pressure: the first step is that 0.5Mpa, temperature heated hydrogenation reaction 2～3 hours when being 95～100 ℃ at hydrogen pressure earlier; In second step, being warmed up to 125～135 ℃, pressure is under the condition of 3.6～4.0Mpa, repeated hydrogenation reaction 5～6 hours.
Step of the present invention (2) can be implemented in wide relatively temperature and pressure scope.Typical temperature is that 50 ℃ to 200 ℃, pressure are 0.1Mpa to 10.0Mpa.Preferred temperature is that 60 ℃ to 180 ℃, pressure are 0.2Mpa to 8.0Mpa, and more preferably temperature is that 80 ℃ to 150 ℃, pressure are 0.3Mpa to 6.0Mpa.Most preferably in the step (2); The reaction of each reactive component is divided into two stages and carries out: earlier under 85 ℃ to 110 ℃ of temperature, pressure 0.3Mpa to 0.7Mpa reaction 1-3 hour; Then, again under 110 ℃ to 150 ℃ of temperature, pressure 2.5Mpa to 5.0Mpa reaction 3-7 hour.
Reaction times in the step of the present invention (2) is not crucial, can how much in the scope of broad, selecting according to production lot.Generally speaking, the reaction times that each reactant combines reaches 12 hours most, and the preferred reaction time is 10 hours, and more preferably the reaction times is 8 hours.More concrete is is 1-3 hour in reaction times fs, and the subordinate phase reaction times is 3-7 hour.
Environmental protection oxygenant described in the step of the present invention (3) is at least a in Youxiaolin, Losantin, Manganse Dioxide, potassium permanganate, ydrogen peroxide 50 and the additive oxygenants such as (as: ammonium vanadate, potassium bromates); Be preferably Youxiaolin and Losantin, more preferably Youxiaolin.And for the 4-of 1mol [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C); the molar weight of used oxygenant generally is the 40-100% of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C); Be preferably 40-70%, most preferably be 40-50%.
Organic solvent described in the step of the present invention (3) is at least a in methylene dichloride, chloroform, tetracol phenixin, dithiocarbonic anhydride, tetrachloroethane, 1,4-diox, THF, ether, MTBE, acetone, butanone, glacial acetic acid and the propionic acid; Be preferably at least a in chloroform, glacial acetic acid, 1,4-diox, MTBE, acetone, the butanone, more preferably at least a in chloroform, glacial acetic acid, 1,4-diox, the acetone.
Step of the present invention (3) can be implemented in wide relatively TR.Typical temperature is-10 ℃ to 50 ℃, and preferred temperature is-5 ℃ to 40 ℃, and more preferably temperature is 0 ℃ to 30 ℃, and most preferably temperature is 0 ℃ to 20 ℃.
Step of the present invention (3), the reaction times is not crucial, can how much in the scope of broad, selecting according to production lot.Generally speaking, each reactant combines maximum response time and reaches 10 hours, and the preferred reaction time is 8 hours, and most preferably the reaction times is 6 hours.Adopt gas chromatograph to monitor in the reaction process always and follow the tracks of reaction.
In the step of the present invention (3); Carry out the used organic solvent of last recrystallization and be at least a in acetone, butanone, pimelinketone, ETHYLE ACETATE, ethanol, methyl alcohol, Virahol, toluene and the YLENE; Be preferably at least a in butanone, pimelinketone, ETHYLE ACETATE, ethanol, toluene, the Virahol, more preferably butanone, pimelinketone, ETHYLE ACETATE, alcoholic acid mixture.
The precision fractional distillation of being carried out in step of the present invention (2) and the step (3) preferably adopts the short-path distillation appearance to carry out precision fractional distillation.
Advantage of the present invention and positively effect are following:
(1) in the process of the second step preparation 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C); owing to adopted highly compressed ladder hydrogenation process after the first low pressure; the product that obtains carries out precise distillation again; reached the technology of very optimizing, make by product in the product reduce to technology acceptable degree like the amount of: 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl alcohol] cyclohexyl alcohol and 4-[2 '-(trans-4 "-alkyl-cyclohexyl) ethyl] hexanaphthene;
(2) in the preparation process in the 3rd step; 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C) is employed under the condition of oxygenant of relative environmental protection; prepare 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog compound (I); In conjunction with precise distillation and purification, can obtain purity and reach the white crystal product more than 99.8%;
(3) synthetic route of the present invention's design is unique, has adopted the material and the technological line of environmental protection, and operational path is shorter; Processing condition are reasonable, and treatment process is suitable, and product quality is excellent; Purity is high, and yield is high, is suitable for the quality requirements of TFT-LCD liquid crystal material to midbody; Can satisfy TFT-LCD fully to liquid crystal intermediates high purity, high-quality requirement, to adapt to TFT-LCD with the fast-developing needs of liquid crystal material.
Embodiment
Below in conjunction with specific embodiment the present invention is done further detailed description, yet said embodiment should not explain with the mode of restriction.
Embodiment 1:
Present embodiment is the preparation of 4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] pimelinketone, and its preparation step gathers as follows:
Step 1: trans-4 '-amyl group cyclohexyl ethanoyl-4-benzyloxy benzene (B) synthetic.
In there-necked flask, add 4.8g (0.2mol) magnesium chips, 250ml exsiccant THF and 100ml toluene; Reflux; Add two milliliters of trans-4-amyl group cyclohexyl methyl chlorine and two iodine, after the initiation reaction, begin to drip 36.5g (0.18mol) trans-4-amyl group cyclohexyl methyl chlorine; Be advisable with little backflow, approximately drip half a hour; Finish heating reflux reaction 3 hours.Drip the solution of 33.5g (0.16mol) to benzyloxy benzene cyanogen and 50ml toluene, approximately dripped 1 hour, after finishing, heating begins to steam solvent, ends for 105 ℃ to temperature, adds 100ml toluene, and back flow reaction is 3 hours again; Be cooled to 20 ℃, drip the solution of the 20ml vitriol oil and 50ml water, finish reheat to 95 ℃ left and right sides back flow reaction 2 hours; Be cooled to 20 ℃, separatory with 100ml * 2 extracted in toluene secondaries, merges organic layer, uses 200ml * 3 warm water to wash again three times, uses anhydrous MgSO
4Dry; The filtering siccative, evaporated under reduced pressure gets bullion, uses 500mL * 2 absolute ethyl alcohol recrystallization secondaries again, gets white crystal 49.0g, product gas chromatograph purity assay>=99.5%, yield 81%.
Step 2:4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] cyclohexyl alcohol (C) synthetic.
Add in the autoclave 500g (1.32mol) trans-4 '-amyl group cyclohexyl ethanoyl-4-benzyloxy benzene (B), 1500ml absolute ethyl alcohol, Raney's nickel catalyst 150g; The lid kettle cover; With nitrogen replacement air three times; Use hydrogen exchange nitrogen again three times, hydrogen pressure is decided to be 0.5Mpa, temperature is decided to be 95～100 ℃, begins to heat hydrogenation; Control hydrogenation reaction after 2 hours, being warmed up to 125～135 ℃, pressure is under the condition of 3.6～4.0Mpa, repeated hydrogenation reaction 5 hours～6 hours (gas chromatograph is followed the tracks of reaction to having reacted).Reaction solution is reduced to room temperature, carry out press filtration under the nitrogen protection, with 100mL * 2 alcohol flushing catalyzer secondaries; Merge all filtrating, neat solvent is removed in decompression, and excess carries out precise distillation with the short-path distillation appearance; Collect the cut of 145 ± 2 ℃/1mmHg, get white solid 351.1g.Products obtained therefrom is used the gas chromatograph analysis, purity >=99.2%, yield: 95%.
Step 3:4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] pimelinketone synthetic.
Adding 80ml methylene dichloride, 100ml glacial acetic acid, 100ml 1,4-diox, 30ml THF and 4-in the there-necked flask [2 '-(trans-4 " the amyl group cyclohexyl) ethyl] cyclohexyl alcohol (C) 50.4g (0.18mol); stirring and dissolving; controlled temperature is at 7～10 ℃; begin to drip an amount of (available chlorine 10%) Youxiaolin, gas chromatograph is followed the tracks of reaction while dripping, and approximately drips 2 hours; Finish, again insulation reaction 2～3 hours (gas chromatograph is followed the tracks of the response analysis terminal point); Separatory with 100ml * 2 extracted in toluene secondaries, merges organic layer, uses 200ml * 3 sodium hydrogencarbonates (10%) solution washing again three times, washes neutrality again, uses anhydrous MgSO
4Dry; The filtering siccative, underpressure distillation gets bullion, and excess carries out precise distillation with the short-path distillation appearance, collects the cut of 140 ± 1 ℃/1mmHg, uses 200mL ETHYLE ACETATE and 30mL butanone recrystallization secondary again, gets white crystal 35.5g.Products obtained therefrom is used the gas chromatograph analysis, purity >=99.8%, yield 71%, melting point compound: 41.7 ℃.
Embodiment 2:
Present embodiment is the preparation of 4-[2 '-(trans-4 " propyl group cyclohexyl) ethyl] pimelinketone.
The preparation process is with embodiment 1, and difference is: the trans-4-amyl group cyclohexyl methyl chlorine raw material in the step 1 is replaced with trans-4-propyl group cyclohexyl methyl chlorine, prepares title product 4-[2 '-(trans-4 " propyl group cyclohexyl) ethyl] pimelinketone.
The result is following in preparation: products obtained therefrom is used the gas chromatograph analysis, and purity >=99.8%, yield are 71%, melting point compound: 45.3 ℃.
Embodiment 3
Present embodiment is the preparation of 4-[2 '-(trans-4 " heptyl cyclohexyl) ethyl] pimelinketone.
The preparation process is with embodiment 1, and difference is: the trans-4-amyl group cyclohexyl methyl chlorine raw material in the step 1 is replaced with trans-4-heptyl cyclohexyl methyl chlorine, prepares title product 4-[2 '-(trans-4 " heptyl cyclohexyl) ethyl] pimelinketone.
The result is following in preparation: products obtained therefrom is used the gas chromatograph analysis, purity >=99.8%, yield 71%, melting point compound: 44.3 ℃.
Embodiment 4
Present embodiment is the preparation of 4-[2 '-(trans-4 " methylcyclohexyl) ethyl] pimelinketone.
The preparation process is with embodiment 1, and difference is: the trans-4-amyl group cyclohexyl methyl chlorine raw material in the step 1 is replaced with trans-4-methylcyclohexyl methyl chloride, prepares title product 4-[2 '-(trans-4 " methylcyclohexyl) ethyl] pimelinketone.
The result is following in preparation: products obtained therefrom is used the gas chromatograph analysis, purity >=99.8%, yield 71%, melting point compound: 57.3 ℃.
With the preparation product 4-identical with embodiment 1 [2 '-(trans-4 " amyl group cyclohexyl) ethyl] pimelinketone is example, following with prior art:
By < fine chemistry industry>2002 the 19th volumes the 07th phase reported method; Prepare 4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] pimelinketone; the title product of preparing---4-[2 '-(trans-4 " the amyl group cyclohexyl) ethyl] pimelinketone; Its product gas chromatograph purity assay is 98.5%, and total recovery is: 11.2%.Product has the big impurity of a coupling 1%, and product is yellowish white, and melting point compound is: 38.9 ℃.This shows, the present invention compared with prior art, not only preparation technology is simple, and prepared product purity is high, yield is high, melting point compound is high, quality better is compared than prior art and to be had tangible substantive distinguishing features and obvious improvement.
Claims (9)
1. the preparation method of a 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound is characterized in that following these steps to carry out:
(1) with trans-4-alkyl-cyclohexyl methyl chloride in organic solvent with magnesium chips reaction, obtain Grignard reagent, again with to the reaction of benzyloxy benzene cyanogen, carry out acidic hydrolysis then and make 1-[2 '-(trans-4 " alkyl-cyclohexyl) ethanoyl]-4-(benzyloxy) benzene;
(2) 1-[2 '-(trans-4 " alkyl-cyclohexyl) ethanoyl]-4-(benzyloxy) benzene in organic solvent under the catalysis of catalyzer; carry out highly compressed ladder hydrogenation reaction after the first low pressure; make 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol, carry out precision fractional distillation, purification again;
(3) in organic solvent; 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol is in the presence of the environmental protection oxygenant; oxidation makes 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone compound; Carry out precision fractional distillation, purification, recrystallization again, obtain target product with high purity, the alkyl that more than occurs all is to refer to C
1-C
10Straight chained alkyl.
2. according to the preparation method of the described 4-of claim 1 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound, it is characterized in that the organic solvent described in the step (1) is at least a in ether, THF, methyltetrahydrofuran, benzene, toluene and the YLENE; Described acidic hydrolysis is in the presence of acid, to implement, and described acid is that the concentration of dilute with water is at least a in the hydrochloric acid, sulfuric acid, glacial acetic acid of 10-50%.
3. according to the preparation method of the described 4-of claim 1 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound; it is characterized in that in the step (1) trans-4-alkyl-cyclohexyl methyl chloride; employed magnesium chips is 0.7mol to 1.5mol, and employed is 0.6mol to 1.4mol to benzyloxy benzene cyanogen for 1mol; The temperature of reaction of step (1) is 10 ℃ to 105 ℃.
4. according to the preparation method of the described 4-of claim 1 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound; it is characterized in that the step gather the first low pressure described in (2) after highly compressed ladder hydrogenation process be: the first step is 0.5MPa at hydrogen pressure, when temperature is 95～100 ℃ hydrogenation reaction 2--3 hour; In second step, being warmed up to 125～135 ℃, pressure is under the condition of 3.6～4.0MPa, repeated hydrogenation reaction 5 hours～6 hours.
5. according to the preparation method of the described 4-of claim 1 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound, it is characterized in that step (2) is that 50 ℃ to 200 ℃, pressure are to implement under the condition of 0.1MPa to 10.0MPa in temperature.
6. according to the preparation method of the described 4-of claim 5 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound; the reaction that it is characterized in that each reactive component of step (2) divides two stages to carry out: the fs under 85 ℃ to 110 ℃ of temperature, pressure 0.3MPa to 0.7MPa reaction 1-3 hour down, subordinate phase under 110 ℃ to 150 ℃ of temperature, pressure 2.5MPa to 5.0MPa reaction 3-7 hour down.
7. according to the preparation method of the described 4-of claim 1 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound, it is characterized in that the environmental protection oxygenant described in the step (3) is at least a in Youxiaolin, Losantin, Manganse Dioxide, potassium permanganate, ydrogen peroxide 50 and ammonium vanadate, the potassium bromate additive; Described organic solvent is at least a in methylene dichloride, chloroform, tetracol phenixin, dithiocarbonic anhydride, tetrachloroethane, 1,4-diox, THF, ether, MTBE, acetone, butanone, glacial acetic acid and the propionic acid; Carry out the used organic solvent of last recrystallization and be at least a in acetone, butanone, pimelinketone, ETHYLE ACETATE, ethanol, methyl alcohol, Virahol, toluene and the YLENE.
8. according to the preparation method of the described 4-of claim 1 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound; it is characterized in that in the step (3) 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol for 1mol, the molar weight of the environmental protection oxygenant that is added is the 40-100% of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol.
9. according to the preparation method of the described 4-of claim 1 [2 '-(trans-4 " alkyl-cyclohexyl) ethyl] pimelinketone liquid crystal intermediates compound, it is characterized in that the enforcement temperature of step (3) is-10 ℃ to 50 ℃.
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| 张晓军 等.4-[2’-(反式-4’’-戊基环己基)乙基]环己酮的合成.《精细化工》.2002,第19卷(第7期),400-402. * |
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