JP2007176818A - ジフルオロベンゼン誘導体の製造方法 - Google Patents
ジフルオロベンゼン誘導体の製造方法 Download PDFInfo
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- JP2007176818A JP2007176818A JP2005374735A JP2005374735A JP2007176818A JP 2007176818 A JP2007176818 A JP 2007176818A JP 2005374735 A JP2005374735 A JP 2005374735A JP 2005374735 A JP2005374735 A JP 2005374735A JP 2007176818 A JP2007176818 A JP 2007176818A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical class FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 p-toluenesulfonyloxy group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000005948 methanesulfonyloxy group Chemical group 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims description 5
- 229940031826 phenolate Drugs 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 claims description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 24
- 239000000543 intermediate Substances 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 11
- 239000007806 chemical reaction intermediate Substances 0.000 abstract 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004210 ether based solvent Substances 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- DUTIYVOXQFBHJK-NUUBBLISSA-N C(=O)[C@@H]1CC[C@H](CC1)C1=C(C(=C(C=C1OC)OC[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CC)F)F Chemical compound C(=O)[C@@H]1CC[C@H](CC1)C1=C(C(=C(C=C1OC)OC[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CC)F)F DUTIYVOXQFBHJK-NUUBBLISSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000003849 aromatic solvent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- NGCJAOOKFUSYHM-IFSQOONMSA-N C1(OCCO1)[C@@H]1CC[C@H](CC1)COC=1C(=C(C(=C(C1)OC)F)F)[C@@H]1CC[C@H](CC1)CCCC Chemical compound C1(OCCO1)[C@@H]1CC[C@H](CC1)COC=1C(=C(C(=C(C1)OC)F)F)[C@@H]1CC[C@H](CC1)CCCC NGCJAOOKFUSYHM-IFSQOONMSA-N 0.000 description 6
- KIDXLNATSYCVRC-NYUFXJCHSA-N CC[C@H](CC1)CC[C@@H]1[C@H](CC1)CC[C@@H]1C(C(OC[C@H](CC1)CC[C@@H]1C1OCCO1)=CC(OC)=C1F)=C1F Chemical compound CC[C@H](CC1)CC[C@@H]1[C@H](CC1)CC[C@@H]1C(C(OC[C@H](CC1)CC[C@@H]1C1OCCO1)=CC(OC)=C1F)=C1F KIDXLNATSYCVRC-NYUFXJCHSA-N 0.000 description 6
- SJXSFIMCESAFBK-MGCOHNPYSA-N COC(C([C@H](CC1)CC[C@@H]1C1OCCO1)=C1F)=CC(O)=C1F Chemical compound COC(C([C@H](CC1)CC[C@@H]1C1OCCO1)=C1F)=CC(O)=C1F SJXSFIMCESAFBK-MGCOHNPYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- CHEWJFZUNBFWOB-UBBSCCEASA-N C(=O)[C@@H]1CC[C@H](CC1)C1=C(C(=C(C=C1OC)OC[C@@H]1CC[C@H](CC1)CCCC)F)F Chemical compound C(=O)[C@@H]1CC[C@H](CC1)C1=C(C(=C(C=C1OC)OC[C@@H]1CC[C@H](CC1)CCCC)F)F CHEWJFZUNBFWOB-UBBSCCEASA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZYGIGCGQXNTERG-IFSQOONMSA-N FC1=C(C=C(C(=C1F)[C@@H]1CC[C@H](CC1)C=C)OC[C@@H]1CC[C@H](CC1)CCCC)OC Chemical compound FC1=C(C=C(C(=C1F)[C@@H]1CC[C@H](CC1)C=C)OC[C@@H]1CC[C@H](CC1)CCCC)OC ZYGIGCGQXNTERG-IFSQOONMSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BNIPVJNRPRBAQL-NYUFXJCHSA-N FC1=C(C=C(C(=C1F)[C@@H]1CC[C@H](CC1)C=C)OC[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CC)OC Chemical compound FC1=C(C=C(C(=C1F)[C@@H]1CC[C@H](CC1)C=C)OC[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CC)OC BNIPVJNRPRBAQL-NYUFXJCHSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000005595 deprotonation Effects 0.000 description 3
- 238000010537 deprotonation reaction Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GPDVWUFHUWBSGD-HAQNSBGRSA-N FC1=C(C(=CC=C1)OC[C@@H]1CC[C@H](CC1)C1OCCO1)F Chemical compound FC1=C(C(=CC=C1)OC[C@@H]1CC[C@H](CC1)C1OCCO1)F GPDVWUFHUWBSGD-HAQNSBGRSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 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 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VXGDOXAULQMWOI-UBBSCCEASA-N C(=O)[C@@H]1CC[C@H](CC1)C=1C(=C(C(=C(C1)OC[C@@H]1CC[C@H](CC1)CCCC)F)F)OC Chemical compound C(=O)[C@@H]1CC[C@H](CC1)C=1C(=C(C(=C(C1)OC[C@@H]1CC[C@H](CC1)CCCC)F)F)OC VXGDOXAULQMWOI-UBBSCCEASA-N 0.000 description 1
- MVMZKLKIUWBNCA-XYPYZODXSA-N CCCC[C@H]1CC[C@H](CBr)CC1 Chemical compound CCCC[C@H]1CC[C@H](CBr)CC1 MVMZKLKIUWBNCA-XYPYZODXSA-N 0.000 description 1
- QXVWHHVNWXGCQG-OPMHRUBESA-N COC1=C(C(=C(C=C1)OC[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CC)F)F Chemical compound COC1=C(C(=C(C=C1)OC[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CC)F)F QXVWHHVNWXGCQG-OPMHRUBESA-N 0.000 description 1
- OODLFCMOONDUHP-JOCQHMNTSA-N COC=1C(=C(C(=C(C1)OC)F)F)[C@@H]1CC[C@H](CC1)CCCC Chemical compound COC=1C(=C(C(=C(C1)OC)F)F)[C@@H]1CC[C@H](CC1)CCCC OODLFCMOONDUHP-JOCQHMNTSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000336896 Numata Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000062 cyclohexylmethoxy group Chemical group [H]C([H])(O*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- CZFNISFYDPIDNM-UHFFFAOYSA-N n,n-dimethylformamide;oxolane Chemical compound CN(C)C=O.C1CCOC1 CZFNISFYDPIDNM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、一般式(1)
反応温度は溶媒の凝固点から還流温度範囲で行うことができるが、0℃から100℃が好ましく、30℃から60℃がより好ましい。
化合物記載に下記の略号を使用する。
THF :テトラヒドロフラン
DMF :N, N-ジメチルホルムアミド
Me :メチル基
Et :エチル基
Bu :ブチル基
Ph :フェニル基
Ms :メタンスルホニル基
(実施例1)4-(トランス-4-(2,5-ジオキサシクロペンチル)シクロヘキシル)メトキシ-2,3-ジフルオロフェノール (Ib)の合成
MS m/z : 314 (M+)
1H-NMR (60 MHz, CDCl3)
δ: 1.3 1.5 (m, 8 H), 1.8 2.2 (m, 2 H), 3.8 4.0 (m, 6 H), 4.0 6.0 (s, 1 H), 4.7 5.0 (m, 1 H), 6.3 6.4 (m, 2 H)
(実施例2)1-(トランス-4-(2,5-ジオキサシクロペンチル)シクロヘキシル)メトキシ-4-(トランス-4-(トランス-4-エチルシクロヘキシル)シクロヘキシル)メトキシ-2,3-ジフルオロベンゼン (Ic)の合成
MS m/z : 520 (M+)
1H-NMR (60 MHz, CDCl3)
δ: 0.9 1.0 (m, 3 H), 1.2 1.6 (m, 29 H), 1.8 2.2 (m, 3 H), 3.8 4.0 (m, 8 H), 4.7 5.0 (m, 1 H), 6.4 6.5 (m, 2 H)
(実施例3)4-(トランス-4-ホルミルシクロヘキシル)メトキシ-2,3-ジフルオロ-1-(トランス-4-(トランス-4-エチルシクロヘキシル)シクロヘキシル)メトキシベンゼン(Id)の合成
MS m/z : 476 (M+)
1H-NMR (60 MHz, CDCl3)
δ: 0.9 2.0 (m, 34 H), 2.2 2.4 (m, 1 H), 3.8 4.0 (m, 4 H), 6.3 6.5 (m, 2 H), 9.6 9.8 (m, 1 H)
(実施例4)2,3-ジフルオロ-1-(トランス-4-(トランス-4-エチルシクロヘキシル)シクロヘキシル)メトキシ-4-(トランス-4-ビニルシクロヘキシル)メトキシベンゼン(Ie)の合成
相転移温度 : C 75.6 N 195.2 I
MS m/z : 474 (M+), 146 (100)
1H-NMR (400 MHz, CDCl3)
δ: 0.75 1.25 (m, 17 H), 0.86 (t, J = 7.2 Hz, 3 H), 1.65 2.00 (m, 15 H), 3.75 (d, J = 6.8 Hz, 2 H), 3.78 (d, J = 6.4 Hz, 2 H), 4.87 5.03 (m, 2 H), 5.79 (ddd, J = 6.8 Hz, J = 10.4 Hz, J = 17.2 Hz, 1 H), 6.59 (d, J = 5.2 Hz, 2 H)
(実施例5)1-(トランス-4-(2,5-ジオキサシクロペンチル)シクロヘキシル)メトキシ-4-(トランス-4-ブチルシクロヘキシル)メトキシ-2,3-ジフルオロベンゼン (IIc)の合成
MS m/z : 466 (M+)
1H-NMR (60 MHz, CDCl3)
δ: 0.9 1.0 (m, 3 H), 1.2 1.6 (m, 23 H), 1.8 2.2 (m, 3 H), 3.8 4.0 (m, 8 H), 4.7 5.0 (m, 1 H), 6.4 6.5 (m, 2 H)
(実施例6)4-(トランス-4-ホルミルシクロヘキシル)メトキシ-2,3-ジフルオロ-1-(トランス-4-ブチルシクロヘキシル)メトキシベンゼン(IId)の合成
MS m/z : 422 (M+)
1H-NMR (60 MHz, CDCl3)
δ: 0.9 2.0 (m, 28 H), 2.2 2.4 (m, 1 H), 3.8 4.0 (m, 4 H), 6.3 6.5 (m, 2 H), 9.6 9.8 (m, 1 H)
(実施例7)2,3-ジフルオロ-1-(トランス-4-ブチルシクロヘキシル)メトキシ-4-(トランス-4-ビニルシクロヘキシル)メトキシベンゼン(IIe)の合成
相転移温度 : C 55.2 N 95.8 I
MS m/z : 420 (M+), 146 (100)
1H-NMR (400 MHz, CDCl3)
δ: 0.80 1.35 (m, 15 H), 0.889 (t, J = 6.8 Hz, 3 H), 1.65 2.00 (m, 11 H), 3.76 (d, J = 6.4 Hz, 2 H), 3.78 (d, J = 6.4 Hz, 2 H), 4.85 5.05 (m, 2 H), 5.79 (ddd, J = 6.8 Hz, J = 10.4 Hz, J = 17.2 Hz, 1 H), 6.59 (d, J = 5.6 Hz, 2 H)
Claims (12)
- 一般式(1)
- 一般式(2)
- 一般式(4)
- アルキルリンイリドがアルキルトリフェニルホスホニウム塩より調製されるイリドである請求項1、2又は3記載の製造方法。
- 一般式(1)で表される化合物を酸化する方法が、一般式(1)で表される化合物の4位を有機金属試薬により脱プロトン化し、ほう酸トリアルキルと反応させた後、酸化剤を反応させることによる請求項1又は5記載の製造方法。
- 有機金属試薬としてn-ブチルリチウムまたはsec-ブチルリチウムを用い、ほう酸トリアルキルとしてほう酸トリメチルを用いる請求項6の製造方法。
- 酸化剤として過酸化水素、過ギ酸または過酢酸を用いる請求項6または7記載の製造方法。
- X1が臭素またはメタンスルホニルオキシ基を表す請求項1又は2記載の製造方法。
- R1およびR2が共にメチル基を表すかまたは、R1およびR2が-CH2CH2-または-CH2CH2CH2-を表す請求項1、2、3又は5に記載の製造方法。
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JP2007204389A (ja) * | 2006-01-31 | 2007-08-16 | Dainippon Ink & Chem Inc | ジフルオロベンゼン誘導体の製造方法 |
JP2007291093A (ja) * | 2006-03-31 | 2007-11-08 | Dainippon Ink & Chem Inc | ジフルオロベンゼン誘導体の製造方法 |
JP2008133244A (ja) * | 2006-11-29 | 2008-06-12 | Dic Corp | ジフルオロベンゼン誘導体の製造方法及び製造中間体 |
JP2010018540A (ja) * | 2008-07-10 | 2010-01-28 | Dic Corp | フルオロフェノール誘導体の製造方法 |
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DE102011009691A1 (de) * | 2010-02-09 | 2011-08-11 | Merck Patent GmbH, 64293 | Flüssigkristallines Medium |
CN106318403B (zh) * | 2015-06-26 | 2018-09-21 | 江苏和成显示科技有限公司 | 具有负介电各向异性的液晶化合物及其合成方法与应用 |
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