CN112811995A - Synthesis method of 4-substituent cyclohexanone liquid crystal intermediate - Google Patents
Synthesis method of 4-substituent cyclohexanone liquid crystal intermediate Download PDFInfo
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- CN112811995A CN112811995A CN202110047524.6A CN202110047524A CN112811995A CN 112811995 A CN112811995 A CN 112811995A CN 202110047524 A CN202110047524 A CN 202110047524A CN 112811995 A CN112811995 A CN 112811995A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title abstract description 16
- 238000001308 synthesis method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 229950009390 symclosene Drugs 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 36
- -1 4-substituted cyclohexanone Chemical class 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims description 2
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- FSNCEEGOMTYXKY-JTQLQIEISA-N Lycoperodine 1 Natural products N1C2=CC=CC=C2C2=C1CN[C@H](C(=O)O)C2 FSNCEEGOMTYXKY-JTQLQIEISA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VBGMDGDDOADTCY-UHFFFAOYSA-N 4-(4-ethoxyphenyl)cyclohexan-1-one Chemical compound C1=CC(OCC)=CC=C1C1CCC(=O)CC1 VBGMDGDDOADTCY-UHFFFAOYSA-N 0.000 description 2
- XDHMORMQXOUOHT-UHFFFAOYSA-N 4-(4-methylphenyl)cyclohexan-1-one Chemical compound C1=CC(C)=CC=C1C1CCC(=O)CC1 XDHMORMQXOUOHT-UHFFFAOYSA-N 0.000 description 2
- DFXWFFHIZJDOFZ-UHFFFAOYSA-N 4-(4-propylcyclohexyl)cyclohexan-1-ol Chemical compound C1CC(CCC)CCC1C1CCC(O)CC1 DFXWFFHIZJDOFZ-UHFFFAOYSA-N 0.000 description 2
- AKCZQKBKWXBJOF-UHFFFAOYSA-N 4-(4-propylcyclohexyl)cyclohexan-1-one Chemical compound C1CC(CCC)CCC1C1CCC(=O)CC1 AKCZQKBKWXBJOF-UHFFFAOYSA-N 0.000 description 2
- IPQDZFUZVJKAKZ-UHFFFAOYSA-N 4-(trifluoromethyl)cyclohexan-1-one Chemical compound FC(F)(F)C1CCC(=O)CC1 IPQDZFUZVJKAKZ-UHFFFAOYSA-N 0.000 description 2
- PFTGXSGDFZZZFY-UHFFFAOYSA-N 4-methoxycyclohexan-1-ol Chemical compound COC1CCC(O)CC1 PFTGXSGDFZZZFY-UHFFFAOYSA-N 0.000 description 2
- XADCKKKOYZJNAR-UHFFFAOYSA-N 4-methoxycyclohexan-1-one Chemical compound COC1CCC(=O)CC1 XADCKKKOYZJNAR-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QQBOKMULHZBKQZ-UHFFFAOYSA-N 4-(4-ethoxyphenyl)cyclohexan-1-ol Chemical compound C1=CC(OCC)=CC=C1C1CCC(O)CC1 QQBOKMULHZBKQZ-UHFFFAOYSA-N 0.000 description 1
- DIGZGQLFWXXTJZ-UHFFFAOYSA-N 4-(4-methylphenyl)cyclohexan-1-ol Chemical compound C1=CC(C)=CC=C1C1CCC(O)CC1 DIGZGQLFWXXTJZ-UHFFFAOYSA-N 0.000 description 1
- OUXLUHHXKDPSOZ-UHFFFAOYSA-N 4-(4-propylphenyl)phenol Chemical compound C1=CC(CCC)=CC=C1C1=CC=C(O)C=C1 OUXLUHHXKDPSOZ-UHFFFAOYSA-N 0.000 description 1
- VJUJYNJEPPWWHS-UHFFFAOYSA-N 4-(trifluoromethyl)cyclohexan-1-ol Chemical compound OC1CCC(C(F)(F)F)CC1 VJUJYNJEPPWWHS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical class OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 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 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses a synthesis method of a 4-substituent cyclohexanone liquid crystal intermediate, which comprises the step of carrying out oxidation catalytic reaction on 4-substituent cyclohexanol under the action of trichloroisocyanuric acid to obtain the 4-substituent cyclohexanone liquid crystal intermediate. The method has the advantages of high reaction selectivity, high yield, environmental friendliness and simple post-treatment, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing a 4-substituent cyclohexanone liquid crystal intermediate.
Background
In recent years, with the development of liquid crystal material research technology and the increasing demand of people for liquid crystal material properties, and in order to meet the higher and higher quality requirements of liquid crystal displays, the development of liquid crystal compounds with high definition of bright points, low viscosity and low threshold has become a major focus of synthetic chemists. The liquid crystal compound containing the cyclohexane structure has wide application in the field of liquid crystal materials due to high bright points, low viscosity and wide nematic phase temperature region, and gradually becomes an indispensable component of medium-high grade mixed liquid crystal materials.
Cyclohexane liquid crystal compounds are mainly classified into cyclohexanoic acids, cyclohexanols, polycyclocyclohexanes and other cyclohexanes, and researchers in each category have conducted a great deal of research and development on the compounds. Wherein, the 4-substituted cyclohexanone compound is an important intermediate and monomer for synthesizing liquid crystal materials and has important application value.
In the prior art method for producing the cyclohexanone liquid crystal intermediate, the cyclohexanone liquid crystal intermediate is usually prepared by one-step oxidation reaction of a cyclohexanol compound, expensive and toxic oxidants such as a chromium reagent, a manganese reagent, other transition metal oxides, a high-valence iodine reagent and the like are mostly used in the reaction, and most of the oxidants are in an excessive state, so that a large amount of waste pollutants are generated, and great pressure is caused on environmental protection.
Wushengxi et al (Wushengxi, Dongbai constant, etc., synthesis of 4- (2, 3-dichloro-4-butoxy) phenylcyclohexanone and research of byproducts, applied chemistry, 2011, 40(2), 262-. The method uses chromium oxide as an oxidant, so that the production cost is high, the reaction selectivity is low, a large number of byproducts are produced, and the environmental pollution is great.
Disclosure of Invention
In order to solve the problems of low reaction selectivity and large environmental pollution caused by the use of expensive and toxic oxidants in the prior art, the invention provides a synthetic method for preparing a 4-substituent cyclohexanone liquid crystal intermediate by adopting an environment-friendly and pollution-free oxidant trichloroisocyanuric acid for oxidation reaction, which has the advantages of high reaction selectivity, high yield, environmental friendliness and suitability for industrial production.
In order to solve the above technical problems, the technical solution of the present invention is as follows.
A method for synthesizing a 4-substituted cyclohexanone liquid crystal intermediate comprises the following steps: in the presence of a first organic solvent, the compound of the formula (I) reacts under the action of a catalyst and an oxidant and optionally sodium bicarbonate to obtain a compound of the formula (II).
The reaction formula is as follows:
wherein R is one of the following structural formulas:
wherein X is alkylene, and R1 is C1-C5 alkyl.
The catalyst is at least one of the following structural formulas:
the oxidant is trichloroisocyanuric acid.
The solvent for the oxidation reaction is one or the combination of any two of dichloromethane, dichloroethane, toluene, acetonitrile, chlorobenzene, chloroform, fluorobenzene and trifluorotoluene.
The dosage of the catalyst is 1-10%, preferably 5-10% of the molar weight of the 4-substituted cyclohexanol compound; the amount of the oxidizing agent is 0.5 to 3 times, preferably 0.5 to 1 time the molar amount of the 4-substituted cyclohexanol.
The temperature of the oxidation reaction is-10 to 50 ℃, preferably 0 to 10 ℃.
The time of the oxidation reaction is 2 to 30 hours, preferably 5 to 10 hours.
After the oxidation reaction is finished, the post-treatment can be directly carried out in a filtering mode.
In some embodiments, a method of synthesizing a 4-substituted cyclohexanone liquid crystal intermediate, comprising: in the presence of a second organic solvent, carrying out hydrogenation reaction on the compound of the formula (III) under the condition of a hydrogenation catalyst to obtain a compound of the formula (IV); in the presence of a first organic solvent, reacting the compound of the formula (IV) under the action of a catalyst and an oxidant to obtain the compound of the formula (V).
The reaction formula is as follows:
r3 and R4 are the same structural formula as follows:
wherein X is alkylene, and R1 is C1-C5 alkyl.
In some embodiments, R3 is
R4 is
R1 is C1-C5 alkyl.
The hydrogenation catalyst is a Raney type catalyst and/or a transition metal supported catalyst. The Raney type catalyst is preferably one or the combination of any two of Raney nickel, Raney cobalt, Raney palladium and Raney copper; the transition metal supported catalyst is preferably one or the combination of any two of palladium/carbon, platinum/carbon, ruthenium/carbon, nickel/alumina, platinum/alumina, palladium/ferroferric oxide, nickel-copper/alumina, rhodium/silica and platinum-rhodium/alumina.
The pressure of the hydrogen is 1-8MPa, and the temperature of the hydrogenation reaction is preferably 50-150 ℃.
The second organic solvent is an alcohol, preferably methanol, ethanol, isopropanol, or the like.
The catalyst is as described above.
The oxidant is trichloroisocyanuric acid.
The first solvent for the oxidation reaction is one or the combination of any two of dichloromethane, dichloroethane, toluene, acetonitrile, chlorobenzene, chloroform, fluorobenzene and trifluorotoluene.
The dosage of the catalyst is 1-10%, preferably 5-10% of the molar weight of the 4-substituted cyclohexanol compound; the amount of the oxidizing agent is 0.5 to 3 times, preferably 0.5 to 1 time the molar amount of the 4-substituted cyclohexanol.
The temperature of the oxidation reaction is-10 to 50 ℃, preferably 0 to 10 ℃.
The time of the oxidation reaction is 2 to 30 hours, preferably 5 to 10 hours.
The term "alkylene" refers to a saturated straight or branched chain aliphatic hydrocarbon group having 2 residues derived from the parent alkane by removal of two hydrogen atoms from the same carbon atom or two different carbon atoms, preferably an alkylene group containing 1 to 5 carbon atoms. Non-limiting examples of alkylene groups include, but are not limited to, methylene (-CH)2-), 1-ethylidene (-CH (CH)3) -), 1, 2-ethylene (-CH)2CH2-), 1-propylene (-CH (CH)2CH3) -), 1, 2-propylene (-CH)2CH(CH3) -), 1, 3-propylene (-CH)2CH2CH2-) 1, 1-butylene (-CH (CH)2CH2CH3) -) 1, 2-butylene (-CH2CH(CH2CH3) -) 1, 3-butylene (-CH2CH2CH(CH3) -) 1, 4-butylene (-CH2CH2CH2CH2-), 1-pentylene (-CH (CH)2CH2CH2CH3) -), 1, 2-pentylene (-CH)2CH(CH2CH2CH3) -), 1, 3-pentylene (-CH)2CH2CH(CH2CH3) -), 1, 4-pentylene (-CH)2CH2CH2CH(CH3) -), 1, 5-pentylene (-CH)2CH2CH2CH2CH2-)。
The term "C1-C5 alkyl" denotes alkyl groups having 1-5 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and the like.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts trichloroisocyanuric acid as an oxidant, has good selectivity and high yield, and can reduce the reaction cost due to the low price of trichloroisocyanuric acid; in addition, trichloroisocyanuric acid is adopted as an oxidant to carry out oxidation reaction, isocyanuric acid is generated after the reaction, the substance is insoluble in other solvents, can be directly filtered, and is simple in aftertreatment, thus being suitable for industrial production. In addition, as the trichloroisocyanuric acid is used as an oxidant to carry out oxidation reaction, no waste water is generated in the whole oxidation process, and the effect of environmental protection and no pollution is achieved.
Detailed Description
The term "TCAA" refers to trichloroisocyanuric acid.
The invention is further illustrated, but not limited, by the following specific examples.
Example 1: synthesis method of 4-methylcyclohexanone
(1) Adding 10.8g (0.1mol) of 4-methylphenol, 1.1g of ruthenium/carbon catalyst and 100mL of methanol into a 500mL autoclave, sealing the autoclave, then introducing hydrogen for evacuation, then introducing nitrogen for replacing the air in the autoclave for three times, repeating the steps for three times, introducing hydrogen, adding the hydrogen to the required pressure, checking to ensure that the autoclave is airtight, stirring, heating to 70 ℃, maintaining the hydrogen pressure at 5MPa, reacting for 6 hours, stopping the reaction, cooling, slowly discharging the evacuated hydrogen till the hydrogen is exhausted, stopping stirring, extracting the reaction liquid in the autoclave, filtering to remove the catalyst, and carrying out reduced pressure distillation and concentration to obtain 11.2g of colorless liquid, namely 4-methylcyclohexanol, wherein the yield is 98.1%;
(2) in a four-necked flask equipped with a mechanical stirrer, 11.4g of 4-methylcyclohexanol (0.1mol), 1.6g of a methylene chloride solution (200mL) of a catalyst (represented by formula 15, 0.01mol), 58.8g of sodium bicarbonate (0.7mol), and 200mL of water were sequentially added, stirred at 0 ℃ for 15min, 23.2g of TCCA (0.1mol) was slowly added in portions, the reaction was continued for 5 hours after the completion of the dropwise addition, followed by filtration, the filtrate was extracted with methylene chloride for 3 times, washed with 10% sodium sulfite and 10% sodium bicarbonate solution, dried with sodium sulfate, and concentrated to obtain 10.2g of colorless liquid 4-methylcyclohexanone with a yield of 90.9%.
1H NMR(DMSO)δ＝2.37(m,2H),2.15(m,2H),1.89(m,3H),1.32(m,2H),0.96(d,3H).
Example 2: synthesis method of 4-methoxycyclohexanone
(1) Adding 12.4g (0.1mol) of 4-methoxyphenol, 1.0g of Raney-Ni catalyst and 100mL of isopropanol into a 500mL high-pressure kettle, sealing the high-pressure kettle, introducing nitrogen, replacing air in the kettle for three times, introducing hydrogen, adding to a required pressure, checking to ensure that the reaction kettle is airtight, then introducing hydrogen to evacuate, repeating for three times, stirring, heating to 150 ℃, maintaining the hydrogen pressure at 5MPa, reacting for 6 hours, stopping the reaction, cooling, evacuating the hydrogen, extracting reaction liquid in the kettle, filtering to remove the catalyst, and carrying out reduced pressure distillation and concentration to obtain 12.3g of white solid, namely 4-methoxycyclohexanol, wherein the yield is 94.5%;
(2) 13.0g of 4-methoxycyclohexanol (0.1mol), 200mL of toluene and 0.9g of catalyst (shown in formula 2, 5mmol) are sequentially added into a four-neck flask with mechanical stirring, the mixture is stirred for 15min at 10 ℃, 11.6g of TCCA (0.05mol) is slowly added in batches, the reaction is continuously kept for 10h after the dropwise addition is finished, then the mixture is filtered, the filtrate is quenched by sodium thiosulfate, and the organic phase is washed by saturated sodium carbonate, dried and concentrated to obtain 11.4g of white solid 4-methoxycyclohexanone, wherein the yield is 88.9%.
1H NMR(DMSO)δ＝3.58(m,1H),3.30(s,3H),2.35(m,2H),2.20(m,2H),1.91(m,4H).
Example 3: synthesis method of 4- (4-propylcyclohexyl) cyclohexanone
(1) Adding 21.2g (0.1mol) of 4- (4-propylphenyl) phenol, 1.0g of palladium/carbon catalyst and 250mL of ethanol into a 500mL autoclave, sealing the autoclave, introducing nitrogen, replacing the air in the autoclave for three times, introducing hydrogen, adding to the required pressure, checking to ensure that the autoclave is airtight, then introducing hydrogen for emptying, repeating for three times, stirring, heating to 100 ℃, maintaining the hydrogen pressure at 8MPa, reacting for 8 hours, stopping the reaction, cooling, then evacuating the hydrogen, extracting the reaction liquid in the autoclave, filtering to remove the catalyst, and carrying out reduced pressure distillation and concentration to obtain 20.9g of white solid, namely 4- (4-propylcyclohexyl) cyclohexanol, wherein the yield is 93.3%;
(2) 22.4g of 4- (4-propylcyclohexyl) cyclohexanol (0.1mol), 200mL of dichloroethane and 1.4g of catalyst (shown in formula 1, 8mmol) were sequentially added into a four-necked flask with mechanical stirring, stirred at 5 ℃ for 15min, 18.6g of TCCA (0.08mol) were slowly added in portions, the reaction was continued for 8h after the completion of the dropwise addition, and then filtered, the filtrate was quenched with sodium thiosulfate, and the organic phase was washed with saturated sodium carbonate, dried and concentrated to give 19.8g of white solid 4- (4-propylcyclohexyl) cyclohexanone, with a yield of 89.0%.
1HNMR(DMSO)δ＝2.32(m,2H),2.18(d,2H),1.93(m,2H),1.73(m,4H),1.52(m,1H),1.39(m,2H),1.30(m,2H),1.14(m,4H),0.98(m,2H),0.85(m,5H).
Example 4: synthesis method of 4-trifluoromethyl cyclohexanone
16.8g of 4-trifluoromethylcyclohexanol (0.1mol), 1.9g of a chloroform solution (200mL) of a catalyst (represented by formula 13, 0.01mol), 67.2g of sodium bicarbonate (0.8mol) and 300mL of water were sequentially added to a four-necked flask equipped with a mechanical stirrer, stirred at 20 ℃ for 15min, slowly added with 23.2g of TCCA (0.1mol) in portions, the reaction was continued for 6h after the completion of the dropwise addition, followed by filtration, the filtrate was extracted with dichloromethane for 3 times, washed with 10% sodium sulfite and 10% sodium bicarbonate solution, dried with sodium sulfate, and concentrated to obtain 14.7g of colorless liquid 4-trifluoromethylcyclohexanone with a yield of 88.5%.
1H NMR(DMSO)δ＝2.80(m,1H),2.49(m,2H),2.26(d,2H),2.12(m,2H),1.69(m,2H).
Example 5: synthesis method of 4- (4-methylphenyl) cyclohexanone
19.0g of 4- (4-methylphenyl) cyclohexanol (0.1mol), 1.7g of a dichloromethane solution (200mL) of a catalyst (represented by formula 5, 0.01mol), 50.4g of sodium bicarbonate (0.6mol) and 200mL of water were sequentially charged into a four-necked flask equipped with a mechanical stirrer, stirred at 10 ℃ for 15min, slowly added with 23.2g of TCCA (0.1mol) in portions, the reaction was continued for 5 hours after the completion of the dropwise addition, and then filtered, the filtrate was extracted with dichloromethane 3 times, washed with 10% sodium sulfite and 10% sodium bicarbonate solution, dried with sodium sulfate, and concentrated to obtain 16.9g of 4- (4-methylphenyl) cyclohexanone as a white solid with a yield of 89.8%.
1HNMR(CDCl3)δ＝1.93(m,2H),2.20(m,2H),2.32(s,3H),2.50(m,4H),2.99(m,1H),7.13(s,4H).
Example 6: synthesis method of 4- (4-ethoxyphenyl) cyclohexanone
22.0g of 4- (4-ethoxyphenyl) cyclohexanol (0.1mol), 250mL of toluene and 1.0g of catalyst (shown in formula 6, 5mmol) are sequentially added into a four-neck flask with mechanical stirring, the mixture is stirred at 15 ℃ for 20min, 11.6g of TCCA (0.05mol) is slowly added in batches, the reaction is continuously kept for 9h after the dropwise addition is finished, then the reaction is carried out for filtration, the filtrate is quenched by sodium thiosulfate, and the organic phase is washed by saturated sodium carbonate, dried and concentrated to obtain 19.2g of white solid 4- (4-ethoxyphenyl) cyclohexanone, wherein the yield is 88.0%.
1HNMR(CDCl3)δ＝7.17(m,2H),6.87(m,2H),4.04(m,2H),3.00(m,1H),2.52(m,4H),2.22(m,2H),1.93(m,2H),1.43(t,3H).
Example 7: synthesis method of methyl benzene bicyclohexanone
27.2g of methylbenzbicyclohexyl (0.1mol), 1.8g of a dichloroethane solution (300mL) of a catalyst (8 mmol shown in formula 14), 58.8g of sodium bicarbonate (0.7mol) and 200mL of water were sequentially charged into a four-necked flask equipped with a mechanical stirrer, stirred at 0 ℃ for 15min, 18.6g of TCCA (0.08mol) was slowly added in portions, the reaction was continued for 10h after the completion of the dropwise addition, and then filtered, the filtrate was extracted 3 times with dichloromethane, washed with 10% sodium sulfite and 10% sodium bicarbonate solution, dried with sodium sulfate, and concentrated to obtain 23.9g of white solid methylbenzbicyclohexanone, with a yield of 88.4%.
1HNMR(CDCl3)δ＝7.10(s,4H),2.42(m,3H),2.32(m,5H),2.07(m,2H),1.94(m,2H),1.88(m,2H),1.59(m,1H),1.49(m,4H),1.32(d,1H),1.21(m,2H).
Example 8: synthesis method of trans-4' - (3, 4-difluorophenyl) dicyclohexyl-4-ketone
29.4g of trans-4 '- (3, 4-difluorophenyl) dicyclohexyl-4-ol (0.1mol), 300mL of chloroform and 2.5g of a catalyst (0.01 mol shown in formula 11) are sequentially added to a four-necked flask with mechanical stirring, stirred at 5 ℃ for 20min, 23.2g of TCCA (0.1mol) is slowly added in batches, the reaction is continuously kept for 10h after the dropwise addition is finished, then the mixture is filtered, the filtrate is quenched by sodium thiosulfate, and the organic phase is washed by saturated sodium carbonate, dried and concentrated to obtain 25.6g of white solid trans-4' - (3, 4-difluorophenyl) dicyclohexyl-4-one, wherein the yield is 87.6%.
1HNMR(CDCl3)δ＝7.02(m,2H),6.90(m,1H),2.38(m,5H),2.07(m,2H),1.91(m,4H),1.60(m,1H),1.52(m,2H),1.39(m,3H),1.20(m,2H).
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the invention is not limited to the embodiments described above, which are described in the specification only to illustrate the principles of the invention. The invention also includes various insubstantial changes and modifications within the spirit of the invention, as claimed by those skilled in the art.
Claims (9)
1. A method for synthesizing a 4-substituted cyclohexanone liquid crystal intermediate comprises the following steps: in the presence of a first organic solvent, under the action of a catalyst and an oxidant, optionally adding sodium bicarbonate to react the compound of the formula (I) to obtain a compound of a formula (II);
wherein the structural formula of the compound of the formula (I) and the compound of the formula (II) is as follows:
wherein R is one of the following structural formulas:
wherein X is alkylene, and R1 is C1-C5 alkyl.
2. The method of claim 1, wherein the catalyst is at least one of the following formulas,
3. the method according to claim 1 or 2, characterized in that the oxidizing agent is trichloroisocyanuric acid.
4. The method according to any one of claims 1 to 3, wherein the first organic solvent is selected from one or a combination of any two of dichloromethane, dichloroethane, toluene, acetonitrile, chlorobenzene, chloroform, fluorobenzene and trifluorotoluene.
5. A process according to any one of claims 1 to 4, characterised in that the catalyst is used in an amount of 1 to 10%, preferably 5 to 10%, based on the molar amount of 4-substituted cyclohexanol; the dosage of the oxidant is 0.5 to 3 times of the molar weight of the 4-substituted cyclohexanol compound, and is preferably 0.5 to 1; the temperature of the oxidation reaction is-10 to 50 ℃, preferably 0 to 10 ℃.
6. The method of claim 1, comprising: in the presence of a second organic solvent, carrying out hydrogenation reaction on the compound of the formula (III) under the condition of a hydrogenation catalyst to obtain a compound of the formula (IV); in the presence of a first organic solvent, reacting the compound of the formula (IV) under the action of a catalyst and an oxidant to obtain the compound of the formula (V).
The reaction formula is as follows:
r3 and R4 are the same and are one of the following structural formulas:
wherein n is 0 to 6, X is an alkylene group, and R1 is a C1 to C5 alkyl group.
7. The process according to claim 6, wherein R3 is
R4 is
R1 is C1-C5 alkyl.
8. The process according to claim 6, characterized in that the hydrogenation catalyst is a Raney-type catalyst and/or a transition metal supported catalyst; preferably, the Raney type catalyst is one or the combination of any two of Raney nickel, Raney cobalt, Raney palladium and Raney copper; the transition metal supported catalyst is preferably one or the combination of any two of palladium/carbon, platinum/carbon, ruthenium/carbon, nickel/alumina, platinum/alumina, palladium/ferroferric oxide, nickel-copper/alumina, rhodium/silica and platinum-rhodium/alumina.
9. The process according to claim 6, characterized in that the pressure of the hydrogen is between 1 and 8MPa, and the temperature of the hydrogenation reaction is preferably between 50 and 150 ℃; the second organic solvent is an alcohol, preferably methanol, ethanol, isopropanol, or the like.
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