JP6005625B2 - アルキン誘導体の部分水素化反応 - Google Patents
アルキン誘導体の部分水素化反応 Download PDFInfo
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- JP6005625B2 JP6005625B2 JP2013503510A JP2013503510A JP6005625B2 JP 6005625 B2 JP6005625 B2 JP 6005625B2 JP 2013503510 A JP2013503510 A JP 2013503510A JP 2013503510 A JP2013503510 A JP 2013503510A JP 6005625 B2 JP6005625 B2 JP 6005625B2
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- group
- palladium
- sulfoxide
- general formula
- phenyl
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- 238000005984 hydrogenation reaction Methods 0.000 title description 51
- 150000001345 alkine derivatives Chemical class 0.000 title description 47
- 230000036961 partial effect Effects 0.000 title description 28
- -1 methylsulfinylmethylene group Chemical group 0.000 claims description 150
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 144
- 229910052763 palladium Inorganic materials 0.000 claims description 48
- 125000003375 sulfoxide group Chemical group 0.000 claims description 37
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- BVMKBCXVDFOVMD-UHFFFAOYSA-N 1-ethenylsulfinylpropane Chemical group CCCS(=O)C=C BVMKBCXVDFOVMD-UHFFFAOYSA-N 0.000 claims description 2
- UDDBCWCQRQREBI-UHFFFAOYSA-N 1-methylsulfinylethene Chemical group CS(=O)C=C UDDBCWCQRQREBI-UHFFFAOYSA-N 0.000 claims description 2
- HNXMKNMCALMEPP-UHFFFAOYSA-N 1-ethenylsulfinylethane Chemical group CCS(=O)C=C HNXMKNMCALMEPP-UHFFFAOYSA-N 0.000 claims 1
- 241000255925 Diptera Species 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 102
- 150000001336 alkenes Chemical class 0.000 description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 41
- 239000000377 silicon dioxide Substances 0.000 description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 38
- 229910004298 SiO 2 Inorganic materials 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000002904 solvent Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 30
- 231100000572 poisoning Toxicity 0.000 description 29
- 230000000607 poisoning effect Effects 0.000 description 29
- 238000000034 method Methods 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 25
- 150000001344 alkene derivatives Chemical class 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 150000003464 sulfur compounds Chemical class 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229960003986 tuaminoheptane Drugs 0.000 description 9
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 7
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 150000001639 boron compounds Chemical class 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 235000010724 Wisteria floribunda Nutrition 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000002941 palladium compounds Chemical class 0.000 description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000003462 sulfoxides Chemical class 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VQEKDXDBLOHXDZ-UHFFFAOYSA-N CC(CCS(=O)CCC(C)[Si](OC)(OC)OC)[Si](OC)(OC)OC Chemical compound CC(CCS(=O)CCC(C)[Si](OC)(OC)OC)[Si](OC)(OC)OC VQEKDXDBLOHXDZ-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 3
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 3
- 125000005916 2-methylpentyl group Chemical group 0.000 description 3
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 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 3
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000036962 time dependent Effects 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- VOHWEKIUKSUIDT-UHFFFAOYSA-N 2-iodoethynylbenzene Chemical compound IC#CC1=CC=CC=C1 VOHWEKIUKSUIDT-UHFFFAOYSA-N 0.000 description 2
- NKTDTMONXHODTI-UHFFFAOYSA-N 2-pentyne Chemical compound CCC#CC NKTDTMONXHODTI-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KKCHYFNEIVRAOP-UHFFFAOYSA-N C(CC)C(CCS(=O)CCC(CCC)[Si](OC)(OC)OC)[Si](OC)(OC)OC Chemical compound C(CC)C(CCS(=O)CCC(CCC)[Si](OC)(OC)OC)[Si](OC)(OC)OC KKCHYFNEIVRAOP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 description 1
- DUVLJBQCIZCUMW-UHFFFAOYSA-N ethylsulfinylbenzene Chemical compound CCS(=O)C1=CC=CC=C1 DUVLJBQCIZCUMW-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- MLRKYSNODSLPAB-UHFFFAOYSA-N hex-1-yn-1-ol Chemical compound CCCCC#CO MLRKYSNODSLPAB-UHFFFAOYSA-N 0.000 description 1
- VBRLZTLFLNZEPZ-UHFFFAOYSA-N hex-1-ynylbenzene Chemical compound CCCCC#CC1=CC=CC=C1 VBRLZTLFLNZEPZ-UHFFFAOYSA-N 0.000 description 1
- MELUCTCJOARQQG-UHFFFAOYSA-N hex-2-yne Chemical compound CCCC#CC MELUCTCJOARQQG-UHFFFAOYSA-N 0.000 description 1
- OOXGRFLHBJNDOL-UHFFFAOYSA-N hex-2-ynylbenzene Chemical compound CCCC#CCC1=CC=CC=C1 OOXGRFLHBJNDOL-UHFFFAOYSA-N 0.000 description 1
- UBBUCFIBKFCZGM-UHFFFAOYSA-N hex-3-ynylbenzene Chemical compound CCC#CCCC1=CC=CC=C1 UBBUCFIBKFCZGM-UHFFFAOYSA-N 0.000 description 1
- BYQGPSNMZZGRQP-UHFFFAOYSA-N hex-4-ynylbenzene Chemical compound CC#CCCCC1=CC=CC=C1 BYQGPSNMZZGRQP-UHFFFAOYSA-N 0.000 description 1
- GOQJMMHTSOQIEI-UHFFFAOYSA-N hex-5-yn-1-ol Chemical compound OCCCCC#C GOQJMMHTSOQIEI-UHFFFAOYSA-N 0.000 description 1
- OUKGMSINNZGXLT-UHFFFAOYSA-N hex-5-ynylbenzene Chemical compound C#CCCCCC1=CC=CC=C1 OUKGMSINNZGXLT-UHFFFAOYSA-N 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000005932 isopentyloxycarbonyl group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000005933 neopentyloxycarbonyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- YGZOULCHFVIQAW-UHFFFAOYSA-N non-4-en-1-yne Chemical compound CCCCC=CCC#C YGZOULCHFVIQAW-UHFFFAOYSA-N 0.000 description 1
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 1
- QCQALVMFTWRCFI-UHFFFAOYSA-N oct-2-yne Chemical compound CCCCCC#CC QCQALVMFTWRCFI-UHFFFAOYSA-N 0.000 description 1
- IYMBQFYRCIOKCQ-UHFFFAOYSA-N oct-2-ynylbenzene Chemical compound CCCCCC#CCC1=CC=CC=C1 IYMBQFYRCIOKCQ-UHFFFAOYSA-N 0.000 description 1
- UDEISTCPVNLKRJ-UHFFFAOYSA-N oct-3-yne Chemical compound CCCCC#CCC UDEISTCPVNLKRJ-UHFFFAOYSA-N 0.000 description 1
- VZVVYAUTQFCRPB-UHFFFAOYSA-N oct-3-ynylbenzene Chemical compound CCCCC#CCCC1=CC=CC=C1 VZVVYAUTQFCRPB-UHFFFAOYSA-N 0.000 description 1
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 description 1
- FHBNGKMJWYSKTC-UHFFFAOYSA-N oct-4-ynylbenzene Chemical compound CCCC#CCCCC1=CC=CC=C1 FHBNGKMJWYSKTC-UHFFFAOYSA-N 0.000 description 1
- FLOLAPNKXHAGOU-UHFFFAOYSA-N oct-5-ynylbenzene Chemical compound CCC#CCCCCC1=CC=CC=C1 FLOLAPNKXHAGOU-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-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
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- DEGIOKWPYFOHGH-UHFFFAOYSA-N pent-1-ynylbenzene Chemical compound CCCC#CC1=CC=CC=C1 DEGIOKWPYFOHGH-UHFFFAOYSA-N 0.000 description 1
- DHNQYXLXBUSWEY-UHFFFAOYSA-N pent-2-ynylbenzene Chemical compound CCC#CCC1=CC=CC=C1 DHNQYXLXBUSWEY-UHFFFAOYSA-N 0.000 description 1
- IDYNOORNKYEHHO-UHFFFAOYSA-N pent-3-yn-1-ol Chemical compound CC#CCCO IDYNOORNKYEHHO-UHFFFAOYSA-N 0.000 description 1
- JOJLWNAJZCJFOL-UHFFFAOYSA-N pent-3-ynylbenzene Chemical compound CC#CCCC1=CC=CC=C1 JOJLWNAJZCJFOL-UHFFFAOYSA-N 0.000 description 1
- KOSORCNALVBYBP-UHFFFAOYSA-N pent-4-ynylbenzene Chemical compound C#CCCCC1=CC=CC=C1 KOSORCNALVBYBP-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- NGKSKVYWPINGLI-UHFFFAOYSA-N prop-2-ynylbenzene Chemical compound C#CCC1=CC=CC=C1 NGKSKVYWPINGLI-UHFFFAOYSA-N 0.000 description 1
- SNOAHAUUBQMVGW-UHFFFAOYSA-N propan-2-ylsulfanylbenzene Chemical compound CC(C)SC1=CC=CC=C1 SNOAHAUUBQMVGW-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NWYDLOBJQIJDGH-UHFFFAOYSA-N propylsulfanylbenzene Chemical compound CCCSC1=CC=CC=C1 NWYDLOBJQIJDGH-UHFFFAOYSA-N 0.000 description 1
- QBIZDMOIIFLQKR-UHFFFAOYSA-N propylsulfanylsilane Chemical compound C(CC)S[SiH3] QBIZDMOIIFLQKR-UHFFFAOYSA-N 0.000 description 1
- QVRZWGALJMYTDQ-UHFFFAOYSA-N propylsulfinylbenzene Chemical compound CCCS(=O)C1=CC=CC=C1 QVRZWGALJMYTDQ-UHFFFAOYSA-N 0.000 description 1
- VZKQFTXAHQVZKR-UHFFFAOYSA-N propylsulfinylsilane Chemical compound C(CC)S(=O)[SiH3] VZKQFTXAHQVZKR-UHFFFAOYSA-N 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005922 tert-pentoxy group Chemical group 0.000 description 1
- 125000005934 tert-pentyloxycarbonyl group Chemical group 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- YUPAWYWJNZDARM-UHFFFAOYSA-N tri(butan-2-yl)borane Chemical compound CCC(C)B(C(C)CC)C(C)CC YUPAWYWJNZDARM-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Description
(II)粒子径0.3〜10nmのパラジウムを担持し、且つスルホキシド基を有するシリカ又は酸化チタンの存在下、
一般式[1]
一般式[4]
本発明のアルケン誘導体の製造方法で用いられる、パラジウムを担持した、シリカ又は酸化チタン(以下、本発明に係るパラジウム担持担体と略記する場合がある)としては、シリカ又は酸化チタンが、粒径0.3〜10nm、好ましくは1〜10nm、より好ましくは2〜8 nmのパラジウムを担持しているものである。
本発明に係るパラジウム担持担体の製造方法としては、例えば適当な溶媒に上記本発明に係るパラジウムを溶解又は懸濁させ、該溶液に上記シリカ又は上記酸化チタンを混合して、通常1〜30時間、好ましくは1〜20時間、10〜40℃、好ましくは20〜30℃でパラジウム化合物を含浸させ、次いで、当該シリカ又は酸化チタンを乾燥させ、その後担持されたパラジウムをアルコール、ホウ素化合物又は水素化アルミニウムリチウム、水素等で還元することによりパラジウム担持担体が得られる。なお、パラジウム化合物をイオン結合によりシリカ又は酸化チタンに担持させる場合には、溶媒のpHを8〜12、好ましくは9〜10に調整する以外は、上記と同様に反応させればよい。
本発明のアルケンの製造方法で用いられる、本発明に係るスルホキシド基含有パラジウム担持担体は、上記本発明に係るパラジウム担持担体にスルホキシド基を導入したものである。該導入は、本発明に係るパラジウム担持担体のシリカ又は酸化チタンにスルホキシド基が導入されればよく、例えばスルホキシド基を有するシランカップリング剤を用いて導入すればよく、より具体的には、例えばスルホキシド基を有するトリアルコキシシラン等をパラジウム担持担体のシリカ又は酸化チタンと反応させることにより、スルホキシド基を導入することができる。該スルホキシド基の導入量は、本発明に係るパラジウム担持担体中のパラジウム1mmolに対して通常1〜1000mmol、好ましくは1〜100mmol、より好ましくは10〜50mmol、更に好ましくは10〜30mmolである。
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本発明に係るスルホキシド基含有パラジウム担持担体の製造方法としては、例えば適当な溶媒に、上記本発明に係るパラジウム担持担体と、例えば下記一般式[6]で示される化合物(スルホキシド基を有するシランカップリング剤)と水とを添加して混合し、通常1〜20時間、50〜100℃で反応させることにより得られる。
等が挙げられるが、スルホキシド基を溶解しにくい溶媒が好ましく、例えばペンタン、ヘキサン、シクロヘキサン、ヘプタン、オクタン、イソオクタン、ノナン、デカン等の脂肪族炭化水素系溶媒が好ましく、中でもヘプタンが特に好ましい。これらの溶媒は、1種単独で用いて、複数種を適宜組み合わせて用いてもよい。上記溶媒の使用量は、パラジウムを担持した、シリカ又は酸化チタン1gに対して、通常1〜1000mL、好ましくは1〜100mLである。
即ち、下記一般式[7]で示される化合物と例えばナトリウムメトキシド等を反応させ、
(式中、R7及びR9〜R11は、上記と同じ。)
下記一般式[8]で示される化合物を反応させ、
R8−X [8]
(式中、R8は上記と同じ。Xは、ハロゲン原子を表す。)
通常1〜10時間、0〜20℃で反応させ、得られたスルフィド化合物を還元することにより得られる。
即ち、パラジウムを担持したシリカ1g(パラジウム量として約0.05mmol)をn-ヘプタン10〜50mL中に溶解した後、水1〜10mmol、及び、一般式[6]で示される化合物0.5〜5mmolを添加混合し、通常10〜20時間、50〜100℃で撹拌しながら反応させることにより得られる。反応後、必要に応じて沈殿物をろ過し、アセトン等で洗浄してもよい。
本発明のアルケン誘導体の製造方法(以下、本発明の製造方法と略記する場合がある)においては、上記パラジウム担持担体、及びパラジウム担持担体中のパラジウムに対して1〜1000mol倍、好ましくは1〜500mol倍、より好ましくは1〜200mol倍、更に好ましくは1〜100mol倍の上記硫黄化合物の存在下、或いは、上記本発明に係るスルホキシド基含有パラジウム担持担体の存在下、上記一般式[1]で示されるアルキン誘導体を水素源と接触させて還元し、一般式[4]で示されるアルケン誘導体を得ることによりなされる。
(1) Pd(NH3)4Cl2・H2Oの調製
濃アンモニア水(28 wt%) 5mLをフラスコに取り、塩化パラジウム(PdCl2)0.2 gを加え、100 oCで30分よく撹拌し、塩化パラジウムを溶解させた。得られた淡黄色透明溶液をろ過し、溶け残った塩化パラジウムを除去する。ろ液に50 mLのエタノールを注ぐと白色のPd(NH3)4Cl2・H2Oが析出するのでこれをろ過し、真空下1時間乾燥させ、Pd(NH3)4Cl2を得た。
(2)Pd担持シリカ(Pd/SiO2)の合成
得られたPd(NH3)4Cl2・H2O 13.1mg(0.05 mmol)を脱イオン水50 mLに溶解させ、次いでSiO2 (CARiACT Q-30 :FUJI Silysia Chemical, Ltd.)1.0 gを加えた後、濃アンモニア水を用いてpHを10に調整し、30℃の空気雰囲気下、12時間撹拌した。得られたPd担持シリカ (PdIISiO2) をろ過し、脱イオン水1Lで洗浄後、室温にて6時間真空乾燥させた。得られた白色粉末をエタノール20 mLに加え、アルゴン雰囲気下、85℃で2時間加熱撹拌した。加熱開始後10分ほどで触媒が白から黒茶色に変化した。得られた粉末を吸引ろ過、エタノールで洗浄後、室温にて真空乾燥し、Pd/SiO2を得た。尚、このようにして得られたPd/SiO2中のPd含量は0.5wt%であった。
またPd/SiO2のTEM観察の結果(図1)、SiO2表面にPdナノ粒子の生成を確認した。その粒子径は、図2のグラフのような分布を示し、平均粒子径は5.3 nmであった。
1-フェニル-1-プロピンを基質とし、実験例1で得たPd/SiO2を用いて水素化反応を行った。具体的には、以下の如く実施した。
即ち、シュレンク管に合成例1で得たPd/SiO2 0.01 g (Pd量として0.5 μmol)を加え、水素ガスを充填した風船を装着した。反応管内を30分真空引きした後、反応管内を3回水素置換した。次いで、ジメチルスルホキシドを被毒化剤として0.01mmol溶解させたn-ヘキサン5 mLを反応管に加え、該溶液を30℃で1時間撹拌した。その後、基質として1-フェニル-1-プロピン 0.5 mmolを加え、30℃にて90分間水素化反応を行った。反応後、ろ過により触媒を除去し、ろ液をエバポレーターにより蒸発させて生成物を回収した。残留物をシリカゲルカラムクロマトグラフィー(WAKOGEL C-200、展開溶媒n-hexane:AcOEt)にかけ、純粋な生成物を得た。生成物の同定はガスクロマトグラフィー(GC)、GC-MS、NMRを用い、定量は内部標準としてナフタレンを用いて、GCにて行った(実施例1)。
また、被毒化剤としてジメチルスルホキシドの代わりに、メチルフェニルスルホキシド、ジフェニルスルホキシド、ジメチルスルフィド、メチルフェニルスルフィド又はジフェニルスルフィドを用いて、それぞれ同様に実験を行い、生成物の同定を行った(実施例2〜6)。尚、水素化反応は、表1中の所定時間行った。これらの結果を表1に示す。
被毒化剤としてジメチルスルホン、メチルフェニルスルホン又はジフェニルスルホンを用い、水素化反応を表1中の所定時間とした以外は実施例1と同様の方法により、1-フェニル-1-プロピンの部分水素化反応を行い、実施例1と同様に生成物の定量を行った(比較例1〜3)。
また、同様に、被毒化剤を添加しなかった場合についても実験を行い、生成物の定量を行った(比較例4)。これらの結果を、実施例1の結果と併せて示す。
反応時間を10分間隔で10〜180分間に設定した以外は実施例1と同じ方法で各種被毒化剤を用いた場合のアルケン生成物の収率を測定し、アルケン収率の経時変化を測定した。その結果を図3のグラフに示す。
被毒化剤を用いなかった以外は実施例7と同じ方法でアルケン生成物の収率を測定し、アルケン収率の経時変化を測定した。その結果を実施例7の結果と併せて図3のグラフに示す。尚、図3中の縦軸はアルケンの収率を、横軸は時間を表す。−◆−は被毒化剤としてジメチルスルホキシドを用いた場合の結果を、−▲−は被毒化剤としてメチルフェニルスルホキシドを用いた場合の結果を、−■−は被毒化剤としてジフェニルスルホキシドを用いた場合の結果を、−◇−は被毒化剤としてジメチルスルフィドを用いた場合の結果を、−△−は被毒化剤としてメチルフェニルスルフィドを用いた場合の結果を、−□−は被毒化剤としてジフェニルスルフィドを用いた場合の結果を、−■−は被毒化剤を添加しなかった場合の結果をそれぞれ示す。
[Pd(NH3)4]Cl2・H2O 131mg(0.5 mmol)を脱イオン水50 mLに溶解させ、次いでSiO2 (CARiACT Q-30 :FUJI Silysia Chemical, Ltd.)1.0 gを加えた後、30℃の空気雰囲気下、1時間撹拌した。次いで、得られた溶液に水素化ホウ素カリウム0.3gを加え、アルゴン雰囲気下、室温で1時間加熱撹拌した。得られた黒色粉末を吸引ろ過した後、脱イオン水1Lで洗浄後、室温にて6時間真空乾燥し、Pd担持SiO2を得た。尚、このようにして得られたPd担持SiO2中のPd含量は5wt%であった。該Pd担持SiO2を以下5%PdSiO2と記載する。
反応時間を10分間隔で10〜60分間に設定し、被毒化触媒としてジメチルスルホキシドを用い、担体として5%PdSiO2又は5%PdTiO2を用いた以外は、実施例1と同じ方法でアルケン生成物の収率を測定し、各種触媒によるアルケン収率の経時変化を測定した。その結果を図4に示す。
担体として5%PdAl2O3又は5%PdHAPを用いた以外は、実施例8と同じ方法でアルケン生成物の収率を測定し、各種触媒によるアルケン収率の計時変化を測定した。その結果を図4に実施例8の結果と併せて示す。尚、図中の縦軸はアルケンの収率を、横軸は時間を表し、−■−は5%PdSiO2を用いた場合の結果を、−●−は5%PdAl2O3を用いた場合の結果を、−▲−は5%PdTiO2を用いた場合の結果を、−◆−は5%PdHAPを用いた場合の結果をそれぞれ表す。
反応溶媒としてn-ヘキサンの代わりに、ジエチルエーテルを用い、反応時間を20〜150分の間で設定した以外は実施例1と同じ方法でアルケン生成物の収率を測定し、アルケン収率の経時変化を測定した。その結果を、実施例1、比較例7の結果と併せて表2及び図5のグラフに示す。尚、図5中の縦軸はアルケンの収率を、横軸は時間を表し、−●−はn-ヘキサンを用いた場合の結果を、−▲−はジエチルエーテルを用いた場合の結果を、それぞれ表す。
比較例7 メタノールを溶媒として用いたアルキンの部分水素化反応
反応溶媒としてメタノールを用いた以外は実施例9と同じ方法でアルケン生成物の収率を測定し、アルケン収率の経時変化を測定した。その結果を、実施例1、実施例9の結果と併せて表2及び図5のグラフに示す。尚、図5において、−◆−はメタノールを用いた場合の結果を表す。
添加剤としてジメチルスルホキシドを用い、基質として1-フェニル-1-プロピンの代わりに表3中の各種基質を用い、反応時間を表3記載の所定時間とした以外は、実施例1と同様の方法により、各種アルキンの部分水素化反応を行った。但し、実施例13〜17の水素化反応においては、反応温度を40℃とし、実施例18〜25の水素化反応においては、ジメチルスルホキシドを0.2mmol用いて反応を行った。
基質として10 mmolの1-フェニル-1-プロペンを用い、触媒として0.1 gのPd/SiO2(Pd: 5μmol)触媒を用い、被毒化剤として0.5 mmolのジメチルスルホキシドを用いて、反応時間を3時間とした以外は、実施例1と同様の方法により反応を行った。結果を反応式と共に示す。
基質として10 mmolの4-ノニン-1-オール又は5-ノニン-1-オールを用い、触媒として0.01 gのPd/SiO2(Pd: 0.5 μmol)触媒を用い、被毒化剤として0.1 mmolのジメチルスルホキシドを用いて、反応時間を18時間とした以外は、実施例1と同様の方法により反応を行った。結果を反応式と共に示す。
(1) メチル−トリメトキシシリルプロピルスルホキシド(MeSOPrTMS)の合成
MPTMS(メルカプトプロピルトリメトキシシラン、東京化成工業(株)製) 19.6 g(100 mmol)、ナトリウムメトキシドを28%含有するメタノール溶液 20g(NaOMeとして100mmol)の混合溶液を100 mL三つ口フラスコに加え、滴下ロートを装着し反応容器内をアルゴン置換した後、氷冷した。滴下ロートにヨウ化メチル(和光純薬工業(株)製) 16.6 g(110 mmol)を加え、1秒間に1滴の割合で滴下した。滴下終了後、室温で1時間撹拌した後、反応管内を真空引きし、メタノールを蒸発させた。生成物をヨウ化メチレン(CH2Cl2)で抽出してろ過によりナトリウムメトキシド(NaOMe)およびヨウ化ナトリウム(NaI)を分離し、液相をエバポレーターにより濃縮後、減圧蒸留し、メチルトリメトキシシリルプロピルスルフィド(MeSPrTMS、沸点:95℃, 4mmHg)を得た(収率:80%)。
次いで、100 mLナス型フラスコに、得られたMeSPrTMS 2.26 g(10 mmol)、メタノール20 mL、2,6-ターシャルブチル-p-クレゾール(和光純薬工業(株)製) 0.01 gを加え、アルゴン置換した後、反応器を氷冷し、過ヨウ素酸ナトリウム(NaIO4、和光純薬工業(株)製)2.4 g(12 mmol)を加え、氷浴中で24時間撹拌した。得られた液体を濾過後、エバポレーターにより濃縮し、メチル−トリメトキシシリルプロピルスルホキシド(MeSOPrTMS)を得た(収率:62%)
100 mLナス型フラスコに、合成例1の(1)で得たPd(NH3)4Cl2・H2O 0.0131 g(0.05 mmol)を加えて脱イオン蒸留水50 mLに溶解させ、SiO2[CARiACT Q-30(200-350 mesh), 富士シリシア化学(株)製]1.0 gを加えた後、溶液を撹拌しながら濃アンモニア水をピペットを用いて滴下し、pHを10に調整した。フラスコに栓をし、そのまま空気雰囲気下で30 oCにて12時間撹拌した。得られたスラリーをろ過し、ろ液が中性になるまで脱イオン蒸留水約1Lを用いて洗浄後、デシケーターにて30 oC、6時間真空乾燥させることにより、白色粉末のPd担持シリカ (PdIISiO2, 0.95 g)を得た。
次いで、調製したPd担持シリカを100 mL枝付きナスフラスコに加え、還流管、ガスバック付き三方コックを装着し、30分間ポンプにより真空引きした後、反応管内をアルゴン置換し、エタノール 20 mLを加え、85 oCで2時間加熱撹拌した。得られた粉末を吸引ろ過、エタノール 200 mLで洗浄後、デシケーターにて30 oC、2時間真空乾燥し、茶色味を帯びた灰色粉末であるPd/SiO2 (Pd: 0.047 mmol/g : 0.85g)を得た。
更に、得られたPd/SiO2(1.0 g, Pd: 0.047 mmol)を100 mL枝付きナスフラスコに加え、ガススバック付き三方コックを装着し、30分間ポンプにより真空引きした後、反応管内をアルゴン置換し、n-ヘプタン 20 mL、水0.090 g(5 mmol)を加え1時間室温にて撹拌した。続いて(1)で合成したMeSOPrTMS 0.226 g(1 mmol)を加えた後、80 oCにて12時間撹拌した。得られた沈殿を吸引ろ過し、20 mLのアセトンで5回洗浄後、真空乾燥させ、触媒を得た(スルホキシド基含有Pd/SiO2)。
シュレンク管に、合成例3で得たスルホキシド基含有Pd/SiO2 0.050 g(Pd含量:2.3 μmol)を加え、ガスバック付き三方コックを装着した。反応器内を30分間ポンプにて真空引きした後、反応器内を水素で置換-脱気の繰り返しにより3回水素置換し、最後に水素を充填した。反応器内にn-ヘキサン5 mL、1-フェニル-1-プロピン 0.5 mmolを加え、30 oCにて反応時間を10〜120分に設定し、水素化反応を行った。ろ過により所定時間の反応物から触媒を除去し、ろ液をエバポレーターにより蒸発させて生成物を回収した。シリカゲルカラムクロマトグラフィー(WAKOGEL C-200、展開溶媒n-hexane:AcOEt)により、残留物から純粋な生成物を得た。生成物の同定はガスクロマトグラフィー(GC)、GC-MS、NMRを用い、定量は内部標準としてナフタレンを用いて、GCにて行った。その結果を図6に示す。尚、図中−◆−は、アルケンの収率を、−◇−は、アルカンの収率を表す。
Claims (4)
- スルホキシド基が、メチルスルフィニルメチレン基、メチルスルフィニルエチレン基、メチルスルフィニルプロピレン基、メチルスルフィニルブチレン基、メチルスルフィニルペンチレン基、メチルスルフィニルへキシレン基、エチルスルフィニルエチレン基、エチルスルフィニルプロピレン基、エチルスルフィニルブチレン基、エチルスルフィニルペンチレン基、エチルスルフィニルへキシレン基、プロピルスルフィニルエチレン基、プロピルスルフィニルプロピレン基、プロピルスルフィニルブチレン基、プロピルスルフィニルペンチレン基、プロピルスルフィニルへキシレン基、ブチルスルフィニルプロピレン基、ペンチルスルフィニルプロピレン基、又はヘキシルスルフィニルプロピレン基である、請求項1記載の製造方法。
- スルホキシド基が、メチルスルフィニルプロピレン基である、請求項1記載の製造方法。
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JP2007152199A (ja) * | 2005-12-02 | 2007-06-21 | Ne Chemcat Corp | 官能基選択的水素化触媒、及び官能基選択的水素化方法 |
WO2010020671A1 (en) * | 2008-08-20 | 2010-02-25 | Dsm Ip Assets B.V. | Novel selective hydrogenation catalyst comprising palladium on porous silica glass and the use thereof |
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JPS56120627A (en) * | 1980-02-27 | 1981-09-22 | Dainippon Ink & Chem Inc | Selective reduction of compound having acetylenic unsaturated bond |
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JPS57183725A (en) * | 1981-01-28 | 1982-11-12 | Exxon Research Engineering Co | Selective hydrogenation |
JPH08245432A (ja) * | 1995-01-20 | 1996-09-24 | Phillips Petroleum Co | アルキン含有供給物の選択的水素添加方法 |
JPH10168021A (ja) * | 1996-11-11 | 1998-06-23 | F Hoffmann La Roche Ag | 触媒的水素化 |
WO2006028146A1 (ja) * | 2004-09-07 | 2006-03-16 | Wako Pure Chemical Industries, Ltd. | パラジウム固定化イオン交換樹脂及びそれを用いた還元方法 |
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JP2007152199A (ja) * | 2005-12-02 | 2007-06-21 | Ne Chemcat Corp | 官能基選択的水素化触媒、及び官能基選択的水素化方法 |
WO2010020671A1 (en) * | 2008-08-20 | 2010-02-25 | Dsm Ip Assets B.V. | Novel selective hydrogenation catalyst comprising palladium on porous silica glass and the use thereof |
JP2014051447A (ja) * | 2012-09-06 | 2014-03-20 | Wako Pure Chem Ind Ltd | スルホキシド基含有パラジウム担持シリカの製造方法 |
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