JP2009096740A - Method for producing hydroxypentafluorosulfanylbenzene compound - Google Patents
Method for producing hydroxypentafluorosulfanylbenzene compound Download PDFInfo
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- JP2009096740A JP2009096740A JP2007268024A JP2007268024A JP2009096740A JP 2009096740 A JP2009096740 A JP 2009096740A JP 2007268024 A JP2007268024 A JP 2007268024A JP 2007268024 A JP2007268024 A JP 2007268024A JP 2009096740 A JP2009096740 A JP 2009096740A
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- JP
- Japan
- Prior art keywords
- group
- compound
- hydroxypentafluorosulfanylbenzene
- formula
- producing
- Prior art date
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- -1 hydroxypentafluorosulfanylbenzene compound Chemical class 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000010511 deprotection reaction Methods 0.000 claims abstract description 11
- 125000006239 protecting group Chemical group 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- FPVXSUWUMQLKCN-UHFFFAOYSA-N 2-(pentafluoro-$l^{6}-sulfanyl)phenol Chemical compound OC1=CC=CC=C1S(F)(F)(F)(F)F FPVXSUWUMQLKCN-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- VFLHXFYEGOPNHV-UHFFFAOYSA-N pentafluoro-(2-phenylmethoxyphenyl)-$l^{6}-sulfane Chemical compound FS(F)(F)(F)(F)C1=CC=CC=C1OCC1=CC=CC=C1 VFLHXFYEGOPNHV-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 3
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000000262 chemical ionisation mass spectrometry Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LWURBRFWJLITKB-UHFFFAOYSA-N pentafluoro-(4-phenylmethoxyphenyl)-$l^{6}-sulfane Chemical compound C1=CC(S(F)(F)(F)(F)F)=CC=C1OCC1=CC=CC=C1 LWURBRFWJLITKB-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XHJLGVIUMCBMHL-UHFFFAOYSA-N 4-(pentafluoro-$l^{6}-sulfanyl)phenol Chemical compound OC1=CC=C(S(F)(F)(F)(F)F)C=C1 XHJLGVIUMCBMHL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- RFTORHYUCZJHDO-UHFFFAOYSA-N 1,3-dimethylimidazolidine-2,4-dione Chemical compound CN1CC(=O)N(C)C1=O RFTORHYUCZJHDO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- MZGZUHNSMNNSRJ-UHFFFAOYSA-N 4-(pentafluoro-$l^{6}-sulfanyl)aniline Chemical compound NC1=CC=C(S(F)(F)(F)(F)F)C=C1 MZGZUHNSMNNSRJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000006027 Birch reduction reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Chemical group CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 150000001639 boron compounds Chemical class 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
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- MHUHQWYOEMJKBC-UHFFFAOYSA-N pentafluoro-(2-fluorophenyl)-$l^{6}-sulfane Chemical compound FC1=CC=CC=C1S(F)(F)(F)(F)F MHUHQWYOEMJKBC-UHFFFAOYSA-N 0.000 description 1
- MURGBRJOSPNBEL-UHFFFAOYSA-N pentafluoro-(4-fluorophenyl)-$l^{6}-sulfane Chemical compound FC1=CC=C(S(F)(F)(F)(F)F)C=C1 MURGBRJOSPNBEL-UHFFFAOYSA-N 0.000 description 1
- AGNCKMHGYZKMLN-UHFFFAOYSA-N pentafluoro-(4-nitrophenyl)-$l^{6}-sulfane Chemical compound [O-][N+](=O)C1=CC=C(S(F)(F)(F)(F)F)C=C1 AGNCKMHGYZKMLN-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tertiry butyl alcohol Natural products CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
Description
本発明は、ヒドロキシペンタフルオロスルファニルベンゼン化合物の製法に関する。ヒドロキシペンタフルオロスルファニルベンゼン化合物は、例えば、医薬や液晶材料として有用な化合物である(例えば、特許文献1参照)。
従来、ヒドロキシペンタフルオロスルファニルベンゼン化合物の製法としては、例えば、4-ニトロペンタフルオロスルファニルベンゼンを還元して4-アミノペンタフルオロスルファニルベンゼンとした後、亜硝酸ナトリウムと反応させてアミノ基をジアゾ化し、次いで加水分解して4-ヒドロキシペンタフルオロスルファニルベンゼン化合物を得る方法が知られている。しかしながら、この方法では、反応工程が多く後処理が煩雑で収率も低い上に、中間体として安全性の低いジアゾ化合物を経由しなければならない等、工業的製法としては不利であった(例えば、特許文献2参照)。
本発明の課題は、上記問題点を解決し、簡便で安全な方法及び容易に入手が可能な原料により、ヒドロキシペンタフルオロスルファニルベンゼン化合物を得ることができる、工業的に好適なヒドロキシペンタフルオロスルファニルベンゼン化合物の製法を提供することにある。 An object of the present invention is to solve the above-mentioned problems, and to obtain a hydroxypentafluorosulfanylbenzene compound from an industrially suitable hydroxypentafluorosulfanylbenzene by a simple and safe method and a readily available raw material. It is to provide a method for producing a compound.
本発明の課題は、一般式(1) The subject of this invention is general formula (1).
(式中、Pは、保護基を示す。なお、ベンゼン環上の任意の水素原子は、アルキル基、シクロアルキル基、アラルキル基又はアリール基で置換されていても良い。)
で示されるオキシペンタフルオロスルファニルベンゼン化合物を脱保護反応させることを特徴とする、一般式(2)
(In the formula, P represents a protecting group. Note that any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.)
A deprotection reaction of the oxypentafluorosulfanylbenzene compound represented by the general formula (2)
で示されるヒドロキシペンタフルオロスルファニルベンゼン化合物の製法によって解決される。 This is solved by a process for producing a hydroxypentafluorosulfanylbenzene compound represented by
本発明により、簡便で安全な方法及び容易に入手が可能な原料により、ヒドロキシペンタフルオロスルファニルベンゼン化合物を得ることができる、工業的に好適なヒドロキシペンタフルオロスルファニルベンゼン化合物の製法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an industrially suitable method for producing a hydroxypentafluorosulfanylbenzene compound, which can obtain a hydroxypentafluorosulfanylbenzene compound with a simple and safe method and easily available raw materials. .
本発明の脱保護反応において使用するオキシペンタフルオロスルファニルベンゼン化合物は、前記の一般式(1)で示される。その一般式(1)において、Pは、保護基であるが、ここでの保護基とは反応性の高い水酸基を不活性化する官能基を保護基と称する。 The oxypentafluorosulfanylbenzene compound used in the deprotection reaction of the present invention is represented by the general formula (1). In the general formula (1), P is a protecting group, and a functional group that inactivates a hydroxyl group highly reactive with the protecting group here is called a protecting group.
前記保護基としては、例えば、ベンジル基、メトキシベンジル基、ジメトキシベンジル基、t-ブチル基、トリチル基等のエーテル系保護基;メトキシメチル基、テトラヒドロピラニル基、エトキシメチル基等のアセタール系保護基;アセチル基、ピバロイル基、ベンゾイル基等のアシル系保護基;トリメチルシリル基、トリエチルシリル基、t-ブチルジメチルシリル基、t-ブチルジフェニルシリル基等のシリルエーテル系保護基などが挙げられるが、好ましくはエーテル系保護基、更に好ましくはアラルキル基、特に好ましくはベンジル基である。 Examples of the protecting group include ether-based protecting groups such as benzyl group, methoxybenzyl group, dimethoxybenzyl group, t-butyl group and trityl group; acetal-based protection such as methoxymethyl group, tetrahydropyranyl group and ethoxymethyl group Groups; acyl protecting groups such as acetyl group, pivaloyl group, benzoyl group; silyl ether protecting groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, etc. An ether-type protecting group is preferred, an aralkyl group is more preferred, and a benzyl group is particularly preferred.
なお、ベンゼン環上の任意の水素原子は、アルキル基、シクロアルキル基、アラルキル基又はアリール基で置換されていても良い。 Any hydrogen atom on the benzene ring may be substituted with an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
前記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の炭素原子数1〜20のアルキル基が挙げられる。なお、これらの基は、各種異性体を含む。 Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. It is done. These groups include various isomers.
前記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等の炭素原子数3〜20のシクロアルキル基が挙げられる。なお、これらの基は、各種異性体を含む。 Examples of the cycloalkyl group include cycloalkyl groups having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. These groups include various isomers.
前記アラルキル基としては、例えば、ベンジル基、フェネチル基、フェニルプロピル基等の炭素原子数7〜20のアラルキル基が挙げられる。なお、これらの基は、各種異性体を含む。 Examples of the aralkyl group include aralkyl groups having 7 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. These groups include various isomers.
前記アリール基としては、例えば、フェニル基、p-トリル基、ナフチル基、アントリル基等の炭素原子数6〜20のアリール基が挙げられる。なお、これらの基は、各種異性体を含む。 Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a p-tolyl group, a naphthyl group, and an anthryl group. These groups include various isomers.
なお、本発明の脱保護反応において使用するオキシペンタフルオロスルファニルベンゼン化合物は、下記の一般式(3)で示されるように、例えば、ハロゲノ又は有機スルホニルオキシペンタフルオロスルファニルベンゼン化合物とヒドロキシ化合物とを反応させることによって得られる(後述の参考例1及び2参照)。 The oxypentafluorosulfanylbenzene compound used in the deprotection reaction of the present invention is, for example, a reaction between a halogeno or organic sulfonyloxypentafluorosulfanylbenzene compound and a hydroxy compound, as shown by the following general formula (3). (Refer to Reference Examples 1 and 2 described later).
(式中、Xは、ハロゲン原子又は有機スルホニルオキシ基を示し、Pは、前記と同義である。なお、ベンゼン環上の任意の水素原子は、アルキル基、シクロアルキル基、アラルキル基又はアリール基で置換されていても良い。) (In the formula, X represents a halogen atom or an organic sulfonyloxy group, and P has the same meaning as described above. The arbitrary hydrogen atom on the benzene ring represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. May be replaced with.)
又、本発明の脱保護反応とは、保護基をはずす反応のことを示すが、その方法としては、例えば、ペンタフルオロスルファニル基に影響を与えない方法が好適に採用されるが、具体的には、金属化合物の存在下にて水素と反応させる方法、金属の存在下にて液体アンモニア中で反応させる方法(バーチ還元)等の還元による方法;トリフルオロ酢酸や濃塩酸等の強酸と反応させる方法;酸性条件下にて水と反応させる方法;2,3-ジシアノ-5,6-ジクロロ-p-ベンゾキノン、硝酸セリウムアンモニウム、酸化クロム等による酸化による方法;三臭化ホウ素等のホウ素化合物と接触させる方法;ヨードトリメチルシリル等のケイ素化合物と接触させる方法等が挙げられるが、好ましくは還元による方法、更に好ましくは金属化合物の存在下にて水素と反応させる方法によって行われる。 In addition, the deprotection reaction of the present invention means a reaction for removing the protecting group. As the method, for example, a method that does not affect the pentafluorosulfanyl group is preferably employed. Is a method of reduction such as a method of reacting with hydrogen in the presence of a metal compound, a method of reacting in liquid ammonia in the presence of a metal (Birch reduction), or a reaction with a strong acid such as trifluoroacetic acid or concentrated hydrochloric acid Method: Method of reacting with water under acidic conditions; Method of oxidation with 2,3-dicyano-5,6-dichloro-p-benzoquinone, ceric ammonium nitrate, chromium oxide, etc .; Boron compounds such as boron tribromide Examples include a method of contacting with a silicon compound such as iodotrimethylsilyl, preferably a method by reduction, and more preferably a reaction with hydrogen in the presence of a metal compound. It carried out by a method of.
本発明の脱保護反応において使用する金属化合物としては、周期表第8族の金属原子を含む化合物、更にはパラジウム原子、白金原子、ニッケル原子、ロジウム原子、ルテニウム原子を含む化合物が望ましく、例えば、具体的には、パラジウム/炭素、パラジウム/硫酸バリウム、水酸化パラジウム/白金、酢酸パラジウム、塩化パラジウム、白金/炭素、硫化白金/炭素、パラジウム-白金/炭素、酸化白金、ラネーニッケル、ロジウム/炭素、ルテニウム/炭素等が挙げられるが、好ましくはパラジウム/炭素、パラジウム-白金/炭素、水酸化パラジウム、白金/炭素、更に好ましくはパラジウム-白金/炭素が使用される。なお、これらの金属化合物は、単独又は二種以上を混合して使用しても良い。 The metal compound used in the deprotection reaction of the present invention is preferably a compound containing a metal atom of Group 8 of the periodic table, more preferably a compound containing a palladium atom, a platinum atom, a nickel atom, a rhodium atom, or a ruthenium atom. Specifically, palladium / carbon, palladium / barium sulfate, palladium hydroxide / platinum, palladium acetate, palladium chloride, platinum / carbon, platinum sulfide / carbon, palladium-platinum / carbon, platinum oxide, Raney nickel, rhodium / carbon, Examples include ruthenium / carbon, but preferably palladium / carbon, palladium-platinum / carbon, palladium hydroxide, platinum / carbon, and more preferably palladium-platinum / carbon. In addition, you may use these metal compounds individually or in mixture of 2 or more types.
前記金属化合物の使用量は、金属原子換算で、オキシペンタフルオロスルファニルベンゼン化合物1モルに対して、好ましくは0.0005〜0.5モル、更に好ましくは0.0003〜0.3モル、特に好ましくは0.0001〜0.1モルである。 The amount of the metal compound used is preferably 0.0005 to 0.5 mol, more preferably 0.0003 to 0.3 mol, and particularly preferably 0.0001 to 0.1 mol with respect to 1 mol of the oxypentafluorosulfanylbenzene compound in terms of metal atoms.
本発明において使用する水素の量は、オキシペンタフルオロスルファニルベンゼン化合物1モルに対して、好ましくは0.5〜50モル、更に好ましくは0.7〜30モル、特に好ましくは1.0〜10モルである。 The amount of hydrogen used in the present invention is preferably 0.5 to 50 mol, more preferably 0.7 to 30 mol, particularly preferably 1.0 to 10 mol, per 1 mol of the oxypentafluorosulfanylbenzene compound.
本発明の反応は、溶媒の存在下で行うのが望ましく、使用される溶媒としては、反応を阻害しないものならば特に限定されないが、例えば、水;メタノール、エタノール、イソプロピルアルコール、t-ブチルアルコール等のアルコール類;ジメチルアミン、ジエチルアミン、ジプロピルアミン、ピリジン、キノリン等の含窒素化合物類;アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類;1,3-ジメチル-2-イミダゾリジノン、1,3-ジメチルイミダゾリジン-2,4-ジオン等の尿素類;ジメチルスルホキシド等のスルホキシド類;スルホラン等のスルホン類;アセトニトリル、プロピオニトリル等のニトリル類;ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類;ベンゼン、トルエン、キシレン等の芳香族炭化水素類が挙げられるが、好ましくはアルコール類、更に好ましくはメタノール、エタノールが使用される。なお、これらの溶媒は、単独又は二種以上を混合して使用しても良い。 The reaction of the present invention is preferably carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction. For example, water; methanol, ethanol, isopropyl alcohol, t-butyl alcohol Alcohols such as dimethylamine, diethylamine, dipropylamine, pyridine, quinoline, etc .; ketones such as acetone, methylethylketone, methylisobutylketone; N, N-dimethylformamide, N, N-dimethylacetamide, Amides such as N-methylpyrrolidone; Ureas such as 1,3-dimethyl-2-imidazolidinone and 1,3-dimethylimidazolidine-2,4-dione; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane Nitriles such as acetonitrile and propionitrile; diethyl ether and diisopropyl Examples include ethers such as pill ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene. Alcohols are preferable, and methanol and ethanol are more preferable. In addition, you may use these solvents individually or in mixture of 2 or more types.
前記溶媒の使用量は、オキシペンタフルオロスルファニルベンゼン化合物1gに対して、好ましくは0.5〜100ml、更に好ましくは0.7〜50ml、特に好ましくは1〜30mlである。 The amount of the solvent used is preferably 0.5 to 100 ml, more preferably 0.7 to 50 ml, and particularly preferably 1 to 30 ml with respect to 1 g of the oxypentafluorosulfanylbenzene compound.
本発明の脱保護反応は、オキシペンタフルオロスルファニルベンゼン化合物を適当な方法により脱保護することによって行われるが、本反応の好ましい態様としては、例えば、オキシペンタフルオロスルファニルベンゼン化合物、金属化合物、水素及び溶媒を混合して、攪拌しながら反応させる等の方法によって行われる。その際の反応温度は、好ましくは-20〜200℃、更に好ましくは-10〜150℃、特に好ましくは0〜100℃であり、反応圧力は特に制限されないが常圧又は加圧下で行う。 The deprotection reaction of the present invention is carried out by deprotecting the oxypentafluorosulfanylbenzene compound by an appropriate method. Preferred embodiments of this reaction include, for example, an oxypentafluorosulfanylbenzene compound, a metal compound, hydrogen and It is carried out by a method of mixing solvents and reacting with stirring. The reaction temperature at that time is preferably −20 to 200 ° C., more preferably −10 to 150 ° C., and particularly preferably 0 to 100 ° C. The reaction pressure is not particularly limited, but the reaction is performed under normal pressure or increased pressure.
本発明の脱保護反応においては、反応性を高めるために、酸を存在させることが望ましく、使用される酸としては、例えば、ギ酸、酢酸、プロピオン酸、クロロ酢酸、トリフルオロ酢酸等の有機酸;塩酸、硫酸等の無機酸が挙げられる。なお、これらの酸は、単独又は二種以上を混合して使用しても良い。 In the deprotection reaction of the present invention, it is desirable that an acid be present in order to increase the reactivity. Examples of the acid used include organic acids such as formic acid, acetic acid, propionic acid, chloroacetic acid, and trifluoroacetic acid. An inorganic acid such as hydrochloric acid or sulfuric acid. In addition, you may use these acids individually or in mixture of 2 or more types.
前記酸の使用量は、オキシペンタフルオロスルファニルベンゼン化合物1モルに対して、好ましくは0.01〜20モル、更に好ましくは0.05〜10モル、特に好ましくは0.1〜6モルである。 The amount of the acid used is preferably 0.01 to 20 mol, more preferably 0.05 to 10 mol, particularly preferably 0.1 to 6 mol, per 1 mol of the oxypentafluorosulfanylbenzene compound.
本発明の脱保護反応によってヒドロキシペンタフルオロスルファニルベンゼン化合物が得られるが、反応終了後、例えば、中和、抽出、濾過、濃縮、蒸留、再結晶、晶析、昇華、カラムクロマトグラフィー等の一般的な製法によって単離・精製される。 A hydroxypentafluorosulfanylbenzene compound is obtained by the deprotection reaction of the present invention. After completion of the reaction, for example, neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, sublimation, column chromatography, etc. It is isolated and purified by a simple manufacturing method.
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
参考例1([P=ベンジル基];4-ベンジルオキシペンタフルオロスルファニルベンゼンの合成)
攪拌装置及び温度計を備えた内容量100mlのガラス製容器に、4-フルオロペンタフルオロスルファニルベンゼン5.0g(22.5mmol)、60%水素化ナトリウム1.35g(33.8mmol)、及び予め乾燥させた1,3-ジメチル-2-イミダゾリジノン25mlを加えた後、攪拌させながら、室温でベンジルアルコール3.65g(33.8mmol)を加え、同温度で12時間反応させた。反応終了後、反応液にトルエン50ml及び酢酸エチル50mlを加えて有機層を飽和食塩水100mlで5回洗浄し、無水硫酸マグネシウムで乾燥させた。濾過後、得られた濾液を濃縮した後、再び水200ml中に添加して混入している1,3-ジメチル-2-イミダゾリジノンを除いて濾過した。得られた濾物を減圧下で乾燥させ、白色固体として、4-ベンジルオキシペンタフルオロスルファニルベンゼン5.62gを得た(単離収率;81%)。
なお、4-ベンジルオキシペンタフルオロスルファニルベンゼンは、以下の物性値で示される新規な化合物である。
Reference Example 1 ([P = benzyl group]; synthesis of 4-benzyloxypentafluorosulfanylbenzene)
In a 100 ml glass container equipped with a stirrer and a thermometer, 5.0 g (22.5 mmol) of 4-fluoropentafluorosulfanylbenzene, 1.35 g (33.8 mmol) of 60% sodium hydride, and 1,1 previously dried After adding 25 ml of 3-dimethyl-2-imidazolidinone, 3.65 g (33.8 mmol) of benzyl alcohol was added at room temperature while stirring, and the mixture was reacted at the same temperature for 12 hours. After completion of the reaction, 50 ml of toluene and 50 ml of ethyl acetate were added to the reaction solution, and the organic layer was washed 5 times with 100 ml of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the obtained filtrate was concentrated, and again added to 200 ml of water, and filtered to remove 1,3-dimethyl-2-imidazolidinone mixed therein. The obtained residue was dried under reduced pressure to obtain 5.62 g of 4-benzyloxypentafluorosulfanylbenzene as a white solid (isolation yield: 81%).
4-Benzyloxypentafluorosulfanylbenzene is a novel compound represented by the following physical property values.
1H-NMR(CDCl3,δ(ppm));5.10(2H,s)、6.96〜6.99(2H,m)、7.29〜7.43(5H,m)、7.65〜7.70(2H,m)
CI-MS;310(M)
1 H-NMR (CDCl 3 , δ (ppm)); 5.10 (2H, s), 6.96 to 6.99 (2H, m), 7.29 to 7.43 (5H, m), 7.65 to 7.70 (2H, m)
CI-MS; 310 (M)
実施例1(4-ヒドロキシペンタフルオロスルファニルベンゼンの合成)
攪拌装置及び温度計を備えた内容量100mlのガラス製容器に、4-ベンジルオキシペンタフルオロスルファニルベンゼン4.0g(12.9mmol)、白金-パラジウム/炭素(50%含水品、商品名;ASCA2(エヌ・イー・ケムキャット製))1.0g、酢酸420mg(6.99mmol)及びエタノール50mlを加え、水素雰囲気下(常圧)、攪拌させながら、70℃で2時間反応させた。反応終了後、反応液を室温まで冷却した後に濾過した。得られた濾液を濃縮し、淡黄色固体として、4-ヒドロキシペンタフルオロスルファニルベンゼン2.67gを得た(単離収率;94%)。
なお、4-ヒドロキシペンタフルオロスルファニルベンゼンの物性値は以下の通りであった。
Example 1 (Synthesis of 4-hydroxypentafluorosulfanylbenzene)
In a glass container with a capacity of 100 ml equipped with a stirrer and thermometer, 4.0 g (12.9 mmol) of 4-benzyloxypentafluorosulfanylbenzene, platinum-palladium / carbon (50% water-containing product, trade name; ASCA2 (N. 1.0 g, acetic acid 420 mg (6.99 mmol) and ethanol 50 ml were added, and the mixture was reacted at 70 ° C. for 2 hours with stirring under a hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction solution was cooled to room temperature and then filtered. The obtained filtrate was concentrated to obtain 2.67 g of 4-hydroxypentafluorosulfanylbenzene as a pale yellow solid (isolated yield; 94%).
The physical properties of 4-hydroxypentafluorosulfanylbenzene were as follows.
1H-NMR(CDCl3,δ(ppm));5.33(1H,s)、6.85(2H,d,J=9.0Hz)、7.62〜7.67(2H,m)
CI-MS;220(M)
1 H-NMR (CDCl 3 , δ (ppm)); 5.33 (1H, s), 6.85 (2H, d, J = 9.0 Hz), 7.62 to 7.67 (2H, m)
CI-MS; 220 (M)
参考例2([P=ベンジル基];2-ベンジルオキシペンタフルオロスルファニルベンゼンの合成)
攪拌装置及び温度計を備えた内容量200mlのガラス製容器に、2-フルオロペンタフルオロスルファニルベンゼン20g(90mmol)、60%水素化ナトリウム5.4g(135mmol)及び予め乾燥させた1,3-ジメチル-2-イミダゾリジノン100mlを加えた後、攪拌させながら、室温でベンジルアルコール14.6g(135mmol)を加え、同温度で18時間反応させた。反応終了後、反応液にトルエン500ml及び飽和塩化ナトリウム水溶液300mlを加えて分液し、有機層(トルエン層)を飽和塩化ナトリウム水溶液300mlで3回、水300mlで2回洗浄し、無水硫酸マグネシウムで乾燥させた。濾過後、濾液を濃縮して得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製(展開溶媒;ヘキサン)し、白色固体として、2-ベンジルオキシペンタフルオロスルファニルベンゼン23.47gを得た(単離収率;84%)。
なお、2-ベンジルオキシペンタフルオロスルファニルベンゼンは、以下の物性値で示される新規な化合物である。
Reference Example 2 ([P = benzyl group]; synthesis of 2-benzyloxypentafluorosulfanylbenzene)
In a 200 ml glass container equipped with a stirrer and a thermometer, 20 g (90 mmol) of 2-fluoropentafluorosulfanylbenzene, 5.4 g (135 mmol) of 60% sodium hydride and 1,3-dimethyl- After adding 100 ml of 2-imidazolidinone, 14.6 g (135 mmol) of benzyl alcohol was added at room temperature while stirring, and the mixture was reacted at the same temperature for 18 hours. After completion of the reaction, 500 ml of toluene and 300 ml of saturated sodium chloride aqueous solution were added to the reaction liquid and the phases were separated. The organic layer (toluene layer) was washed 3 times with 300 ml of saturated aqueous sodium chloride solution and twice with 300 ml of water, and then with anhydrous magnesium sulfate. Dried. After filtration, the concentrate obtained by concentrating the filtrate was purified by silica gel column chromatography (developing solvent: hexane) to obtain 23.47 g of 2-benzyloxypentafluorosulfanylbenzene as a white solid (isolated yield) 84%).
2-Benzyloxypentafluorosulfanylbenzene is a novel compound represented by the following physical property values.
1H-NMR(CDCl3,δ(ppm));5.19(2H,s)、6.98〜7.10(2H,m)、7.31〜7.46(6H,m)、7.75〜7.88(1H,m)
CI-MS;310(M)
1 H-NMR (CDCl 3 , δ (ppm)); 5.19 (2H, s), 6.98 to 7.10 (2H, m), 7.31 to 7.46 (6H, m), 7.75 to 7.88 (1H, m)
CI-MS; 310 (M)
実施例2(2-ヒドロキシペンタフルオロスルファニルベンゼンの合成)
攪拌装置及び温度計を備えた内容量200mlのガラス製容器に、2-ベンジルオキシペンタフルオロスルファニルベンゼン22g(70.9mmol)、白金-パラジウム/炭素(50%含水品、商品名;ASCA2(エヌ・イー・ケムキャット製))4.4g、トリフルオロ酢酸33.8g(297mmol)及びメタノール100mlを加え、水素雰囲気下(常圧)、攪拌させながら、室温で2時間反応させた。反応終了後、反応液を室温まで冷却した後に濾過した。得られた濾液を濃縮し、10%塩化ナトリウム水溶液300mlを加えた後に分液し、有機層を無水硫酸マグネシウムで乾燥させた。濾物をクロロホルム200mlで洗浄した後に、濾液を減圧下で濃縮して、薄紫色固体として、2-ヒドロキシペンタフルオロスルファニルベンゼン10.3gを得た(単離収率;66%)。
なお、2-ヒドロキシペンタフルオロスルファニルベンゼンは以下の物性値で示される新規な化合物である。
Example 2 (Synthesis of 2-hydroxypentafluorosulfanylbenzene)
In a glass container with an internal capacity of 200 ml equipped with a stirrer and a thermometer, 22 g (70.9 mmol) of 2-benzyloxypentafluorosulfanylbenzene, platinum-palladium / carbon (50% water-containing product, trade name; ASCA2) (Chemcat)) 4.4 g, 33.8 g (297 mmol) of trifluoroacetic acid and 100 ml of methanol were added, and the mixture was allowed to react at room temperature for 2 hours under stirring in a hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction solution was cooled to room temperature and then filtered. The obtained filtrate was concentrated, 300 ml of a 10% aqueous sodium chloride solution was added and the layers were separated, and the organic layer was dried over anhydrous magnesium sulfate. After washing the residue with 200 ml of chloroform, the filtrate was concentrated under reduced pressure to obtain 10.3 g of 2-hydroxypentafluorosulfanylbenzene as a pale purple solid (isolated yield; 66%).
2-Hydroxypentafluorosulfanylbenzene is a novel compound represented by the following physical property values.
1H-NMR(CDCl3,δ(ppm));5.98(1H,brs)、6.96〜7.09(2H,m)、7.37〜7.43(1H,m)、7.63〜7.67(1H,m)
CI-MS;220(M)
1 H-NMR (CDCl 3 , δ (ppm)); 5.98 (1H, brs), 6.96 to 7.09 (2H, m), 7.37 to 7.43 (1H, m), 7.63 to 7.67 (1H, m)
CI-MS; 220 (M)
本発明は、ヒドロキシペンタフルオロスルファニルベンゼン化合物の製法に関する。ヒドロキシペンタフルオロスルファニルベンゼン化合物は、例えば、医薬や液晶材料として有用な化合物である。 The present invention relates to a method for producing a hydroxypentafluorosulfanylbenzene compound. A hydroxypentafluorosulfanylbenzene compound is a compound useful as, for example, a medicine or a liquid crystal material.
Claims (10)
で示されるオキシペンタフルオロスルファニルベンゼン化合物を脱保護反応させることを特徴とする、一般式(2)
A deprotection reaction of the oxypentafluorosulfanylbenzene compound represented by the general formula (2)
で示されるハロゲノ又は有機スルホニルオキシペンタフルオロスルファニルベンゼン化合物と一般式(5)
で示されるヒドロキシ化合物とを反応させてオキシペンタフルオロスルファニルベンゼン化合物とした後、これを脱保護反応させる請求項1記載の一般式(2)
で示されるヒドロキシペンタフルオロスルファニルベンゼン化合物の製法。 In the presence of a base, general formula (4)
And an organic sulfonyloxypentafluorosulfanylbenzene compound represented by the general formula (5)
The oxypentafluorosulfanylbenzene compound is reacted with a hydroxy compound represented by the formula (2), followed by deprotection reaction.
A process for producing a hydroxypentafluorosulfanylbenzene compound represented by the formula:
で示されるハロゲノ又は有機スルホニルオキシペンタフルオロスルファニルベンゼン化合物と一般式(5)
で示されるヒドロキシ化合物とを反応させることを特徴とする、ヒドロキシペンタフルオロスルファニルベンゼン化合物の製法。 In the presence of a base, general formula (4)
And an organic sulfonyloxypentafluorosulfanylbenzene compound represented by the general formula (5)
A process for producing a hydroxypentafluorosulfanylbenzene compound, characterized by reacting with a hydroxy compound represented by the formula:
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Cited By (4)
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CZ303004B6 (en) * | 2010-10-07 | 2012-02-15 | Ústav organické chemie a biochemie Akademie ved CR v.v.i. | Process for preparing substituted 3- and 4-(pentafluorosulfanyl)benzenes |
WO2014163156A1 (en) * | 2013-04-04 | 2014-10-09 | 味の素株式会社 | Deprotection method |
CN109071984A (en) * | 2016-05-10 | 2018-12-21 | 阪东化学株式会社 | Electric conductivity ink |
WO2019044215A1 (en) * | 2017-08-29 | 2019-03-07 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separation device, gas separation method, and polyimide compound |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CZ303004B6 (en) * | 2010-10-07 | 2012-02-15 | Ústav organické chemie a biochemie Akademie ved CR v.v.i. | Process for preparing substituted 3- and 4-(pentafluorosulfanyl)benzenes |
WO2012045290A1 (en) * | 2010-10-07 | 2012-04-12 | ÚSTAV ORGANICKÉ CHEMIE A BIOCHEMIE AKADEMIE VĚD ČESKÉ REPUBLIKY, v.v.i. | Process for the preparation of 3- and 4-(pentafluorosulfanyl)benzenes |
WO2014163156A1 (en) * | 2013-04-04 | 2014-10-09 | 味の素株式会社 | Deprotection method |
JPWO2014163156A1 (en) * | 2013-04-04 | 2017-02-16 | 味の素株式会社 | Deprotection method |
US10442834B2 (en) | 2013-04-04 | 2019-10-15 | Ajinomoto Co., Inc. | Deprotection method |
CN109071984A (en) * | 2016-05-10 | 2018-12-21 | 阪东化学株式会社 | Electric conductivity ink |
WO2019044215A1 (en) * | 2017-08-29 | 2019-03-07 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separation device, gas separation method, and polyimide compound |
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