JP5507525B2 - 水素化促進剤、水素化触媒及びアルケン化合物の製法 - Google Patents
水素化促進剤、水素化触媒及びアルケン化合物の製法 Download PDFInfo
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- JP5507525B2 JP5507525B2 JP2011243193A JP2011243193A JP5507525B2 JP 5507525 B2 JP5507525 B2 JP 5507525B2 JP 2011243193 A JP2011243193 A JP 2011243193A JP 2011243193 A JP2011243193 A JP 2011243193A JP 5507525 B2 JP5507525 B2 JP 5507525B2
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 295
- -1 alkene compound Chemical class 0.000 title claims description 162
- 239000003054 catalyst Substances 0.000 title claims description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 178
- 238000006243 chemical reaction Methods 0.000 claims description 92
- 239000003638 chemical reducing agent Substances 0.000 claims description 80
- 150000001875 compounds Chemical class 0.000 claims description 58
- 229910052763 palladium Inorganic materials 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 50
- 150000002941 palladium compounds Chemical class 0.000 claims description 42
- 239000002105 nanoparticle Substances 0.000 claims description 32
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000003446 ligand Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 11
- 230000002776 aggregation Effects 0.000 claims description 10
- 238000004220 aggregation Methods 0.000 claims description 10
- 239000003223 protective agent Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 230000007306 turnover Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 description 71
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- 101150003085 Pdcl gene Proteins 0.000 description 14
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
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- 239000012535 impurity Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
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- 150000002576 ketones Chemical class 0.000 description 8
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
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- 239000002184 metal Substances 0.000 description 7
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
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- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
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- 125000001424 substituent group Chemical group 0.000 description 5
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- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- FFFMSANAQQVUJA-UHFFFAOYSA-N but-1-ynylbenzene Chemical compound CCC#CC1=CC=CC=C1 FFFMSANAQQVUJA-UHFFFAOYSA-N 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- JYRIJBPELVXSTC-UHFFFAOYSA-N cycloprop-2-yn-1-one Chemical compound O=C1C#C1 JYRIJBPELVXSTC-UHFFFAOYSA-N 0.000 description 4
- 239000004210 ether based solvent Substances 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical class P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 4
- 238000011403 purification operation Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 229910010082 LiAlH Inorganic materials 0.000 description 3
- 229910004013 NO 2 Inorganic materials 0.000 description 3
- 241000556679 Pholis Species 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- NKTDTMONXHODTI-UHFFFAOYSA-N 2-pentyne Chemical compound CCC#CC NKTDTMONXHODTI-UHFFFAOYSA-N 0.000 description 2
- 241000349731 Afzelia bipindensis Species 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 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 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- BTDWSZJDLLLTMI-UHFFFAOYSA-N hex-2-yn-1-ol Chemical compound CCCC#CCO BTDWSZJDLLLTMI-UHFFFAOYSA-N 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 239000000543 intermediate Substances 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- DBYQHFPBWKKZAT-UHFFFAOYSA-N lithium;benzene Chemical compound [Li+].C1=CC=[C-]C=C1 DBYQHFPBWKKZAT-UHFFFAOYSA-N 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WWZZMSXCGDTJQS-UHFFFAOYSA-N oct-4-yne-1,6-diol Chemical compound CCC(O)C#CCCCO WWZZMSXCGDTJQS-UHFFFAOYSA-N 0.000 description 2
- YXSWPCZHVFJVJS-UHFFFAOYSA-N oct-4-yne-2,6-diol Chemical compound CCC(O)C#CCC(C)O YXSWPCZHVFJVJS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
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- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229960003986 tuaminoheptane Drugs 0.000 description 2
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 description 1
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 description 1
- ILPBINAXDRFYPL-HYXAFXHYSA-N (Z)-2-octene Chemical compound CCCCC\C=C/C ILPBINAXDRFYPL-HYXAFXHYSA-N 0.000 description 1
- 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 1
- IRUCBBFNLDIMIK-BQYQJAHWSA-N (e)-oct-4-ene Chemical compound CCC\C=C\CCC IRUCBBFNLDIMIK-BQYQJAHWSA-N 0.000 description 1
- IRUCBBFNLDIMIK-FPLPWBNLSA-N (z)-oct-4-ene Chemical compound CCC\C=C/CCC IRUCBBFNLDIMIK-FPLPWBNLSA-N 0.000 description 1
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- AQFZADYMAHLUSR-UHFFFAOYSA-N oct-6-yne-1,2-diol Chemical compound CC#CCCCC(O)CO AQFZADYMAHLUSR-UHFFFAOYSA-N 0.000 description 1
- SZUFPVYNRIGTJP-UHFFFAOYSA-N oct-6-yne-1,3-diol Chemical compound CC#CCCC(O)CCO SZUFPVYNRIGTJP-UHFFFAOYSA-N 0.000 description 1
- CLYLWKDGQAIPIP-UHFFFAOYSA-N oct-6-yne-1,5-diol Chemical compound CC#CC(O)CCCCO CLYLWKDGQAIPIP-UHFFFAOYSA-N 0.000 description 1
- JUTSQNHGIQHLRE-UHFFFAOYSA-N oct-6-yne-2,3-diol Chemical compound CC#CCCC(O)C(C)O JUTSQNHGIQHLRE-UHFFFAOYSA-N 0.000 description 1
- KDGYGMXDXJUQKA-UHFFFAOYSA-N oct-6-yne-2,4-diol Chemical compound CC#CCC(O)CC(C)O KDGYGMXDXJUQKA-UHFFFAOYSA-N 0.000 description 1
- WQIIBFKRUIIDHM-UHFFFAOYSA-N oct-6-yne-2,5-diol Chemical compound CC#CC(O)CCC(C)O WQIIBFKRUIIDHM-UHFFFAOYSA-N 0.000 description 1
- LKRPVEIGZOOCCA-UHFFFAOYSA-N oct-6-yne-3,4-diol Chemical compound CCC(O)C(O)CC#CC LKRPVEIGZOOCCA-UHFFFAOYSA-N 0.000 description 1
- IVTWTZGOZFWXMV-UHFFFAOYSA-N oct-6-yne-3,5-diol Chemical compound CCC(O)CC(O)C#CC IVTWTZGOZFWXMV-UHFFFAOYSA-N 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YNUJADNRNHJXDT-UHFFFAOYSA-N palladium;pentane-2,4-dione Chemical compound [Pd].CC(=O)CC(C)=O.CC(=O)CC(C)=O YNUJADNRNHJXDT-UHFFFAOYSA-N 0.000 description 1
- WLPYSOCRPHTIDZ-UHFFFAOYSA-N pent-2-yn-1-ol Chemical compound CCC#CCO WLPYSOCRPHTIDZ-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
- HJFRLXPEVRXBQZ-UHFFFAOYSA-N pent-3-yn-2-ol Chemical compound CC#CC(C)O HJFRLXPEVRXBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- FWLKYEAOOIPJRL-UHFFFAOYSA-N prop-1-yn-1-ol Chemical compound CC#CO FWLKYEAOOIPJRL-UHFFFAOYSA-N 0.000 description 1
- DGXZDQFYFRCMJB-UHFFFAOYSA-N prop-1-yne-1,3-diol Chemical compound OCC#CO DGXZDQFYFRCMJB-UHFFFAOYSA-N 0.000 description 1
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical group CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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Description
Pd(II)XjLk …(1)
(Pd(II)Xm)2-の塩 …(2)
(Pd(II)Ln)2+の塩 …(3)
(Pd(IV)Xp)2-の塩 …(4)
(一般式(1)〜(4)中、Lは含リン配位子を除く単座又は多座配位子(化合物中にLが2以上存在するときは各々独立して互いに同じであってもよいし異なっていてもよい)、Xはアニオン性基、jはXjが全体で−2価となるようにXの価数に応じて決まる値、kは0〜4のいずれかの整数、mはXmが全体で−4価となるようにXの価数に応じて決まる値、nは4〜6のいずれかの整数、pはXpが全体で−6価となるようにXの価数に応じて決まる値である)
DMF中でPdCl2とアルキンとして4−オクチンと塩基としてKOtBuとを反応させることにより得られる新規な水素化促進剤を、以下のようにして合成した。即ち、撹拌子を備えた20mlシュレンク型反応管に、パラジウム化合物としてPdCl2(32.4mg,0.183mmol)を量り取り、アルゴン雰囲気下でDMF(18.3ml)、4−オクチン(0.268ml,1.83mmol)を加えて攪拌した。続いてKOtBu(41.0mg,0.366mmol,Pdに対して2.0当量)を加えて攪拌すると、反応が開始して溶液の色調が濃茶色に変化すると共に、DMFに不溶だったPdCl2が少しずつ溶解して消失していった。この様子は、水素化促進剤が生成していることを示すものと考えられる。その後、室温で3時間攪拌し、目的とする水素化促進剤(1)を含むDMF溶液を得た。
得られた水素化促進剤(1)のX線回折測定を行ったところ、2θ=39.4(deg)にPd(111)に由来する回折と、70(deg)にPd(220)に由来する回折が認められ、水素化促進剤が0価のパラジウムであると同定された。また、回折ピークの半値幅から、結晶径の平均値は1.6nmと計算された。この結果、実施例1の水素化促進剤は結晶径平均が1.6nmのパラジウムナノ粒子であると同定された。なお、実施例1の結果については表1に示した。
表1に、実施例2〜17,A〜Gの結果を示す。実施例2〜17,A〜Gは、各種パラジウム化合物、各種の塩基又は還元剤、各種のアルキン化合物を用いて調製した水素化促進剤の合成例である。反応条件は、実施例1の場合と同様にして行った。ただし、実施例5は塩基をPdに対して8当量用いた。得られた水素化促進剤は、本明細書中では水素化促進剤(2)〜(17),(A)〜(G)と称することとした。
DMF中でPd(OAc)2と2−ブチン−1,4−ジオールとを塩基も還元剤もなしで反応させることにより得られる新規な水素化促進剤を、以下のようにして合成した。即ち、撹拌子を備えた20mlシュレンク型反応管に、パラジウム化合物としてPd(OAc)2(42.0mg,0.187mmol)、アルキンとして2−ブチン−1,4−ジオール(0.161g,1.87mmol)を量り取り、アルゴン雰囲気下でDMF(18.7ml)を加えて攪拌した。反応が開始して溶液の色調が濃茶色に変化した。室温で3時間攪拌し、目的とする水素化促進剤(18)を含むDMF溶液が得られた。この実施例18の結果については表2に示した。
表2に、実施例H〜Kの結果を示す。実施例H〜Kは、各種のアルキニルアルコールを用いて調製した水素化促進剤の合成例である。反応は、実施例18の場合と同様にして行った。得られた水素化促進剤は、本明細書中では水素化促進剤(H)〜(K)と称することとした。
水素化促進剤と還元剤とを含む水素化触媒を、以下のようにして調製した。即ち、撹拌子を備えた20mlシュレンク型反応管に、KBH4(80.9mg,1.5mmol)を加え、アルゴン雰囲気下にて実施例1で調製した水素化促進剤(1)を含むDMF溶液(Pd濃度=10μmol/ml)を3ml(Pd量=30μmol)、DMFを18ml加えて攪拌することにより、目的とする水素化触媒(1)を得た。この実施例19の結果については表3に示した。
表3に、実施例20〜23,Lの結果を示す。実施例20〜23,Lは、種々の水素化促進剤を用いて調製した水素化触媒の合成例である。得られた水素化触媒は、本明細書中では水素化触媒(2)〜(5),(L)と称することとした。なお、実施例20〜23,Lの実験手順は実施例19に準じて行った。
水素化促進剤と還元剤とを含む水素化触媒を用いて、アルキン化合物を部分水素化してアルケン化合物を製造する例を以下に示す。まず、周囲を30℃に保温した攪拌子を備えた100mlガラス製オートクレーブに、NaBH4を37.8mg(1.00mmol)仕込み、アルゴンガスで置換した。次に、このオートクレーブに、DMFを10ml、4−オクチンを1.47ml(10mmol)、実施例1で得た水素化促進剤(1)を1.00ml(Pd量=10μmol)アルゴン雰囲気下で加えた。この操作にてオートクレーブ内で、水素化促進剤(1)とNaBH4からなる水素化触媒(1)が調製された。ガス導入管を用いてオートクレーブと水素ボンベを接続し、導入管内の空気を2気圧の水素で3回置換した。続いて、8気圧の水素をオートクレーブに導入したのちに2気圧まで注意深く放出する操作を7回繰り返した後、水素圧を8気圧にして溶液を30℃で激しく攪拌した。これにより水素化反応が進行した。変換率及び生成物中のシス−4−オクテンの選択性は、GCにより決定した。副生成物として、トランス体(トランス−4−オクテン)、位置異性体(トランス−3−オクテン及びシス−2−オクテン等)、過剰水添体(オクタン)が生成した。本実施例の結果を表4に示す。なお、表4に記載した選択性は、生成した全てのアルケン(シス体、トランス体及び位置異性体)とアルカンの合算中におけるシス体の割合を表す。この点は表5以降も同様である。
表4に、実施例25〜42の結果を示す。実施例25〜42は、各種の水素化促進剤を用いて、水素化反応時に水素化触媒を系中で調製し4−オクチンの水素化を行なった反応例である。なお、これらの実施例の実験手順は実施例24に準じて行った。
表5に、実施例43〜47,M〜Xの結果を示す。これらの実施例は、いずれも4−オクチンの水素化反応例であり、実施例N以外はPd(OAc)2をパラジウム源として調製した水素化促進剤を用いた水素化反応例である。このうち実施例44,45,M,U〜Xは、塩基を用いずにアルキニルアルコールを加えることにより調製した水素化促進剤を用いた水素化反応例であり、実施例46は、Pd(OAc)2をそのまま用いた水素化反応例であり、実施例47は、塩基とアルキニルアルコールを加えることにより調製した水素化促進剤(17)を用いた水素化反応例である。なお、これらの実施例における水素化反応の操作は実施例24に準じて行った。
表6に、実施例26,28,P,48〜53,AAの結果を示す。実施例48〜53,AAは、実施例19〜23,Lの水素化触媒(1)〜(5),(L)を用いて4−オクチンの水素化を行った反応例である。水素化反応の操作は実施例24と同様にして行ったが、実施例48〜53,AAでは水素化触媒調製の時点で塩基又は還元剤を加えてあるため、水素化反応の際に塩基又は還元剤を加えていない。
表7に、実施例28,54〜61の結果を示す。実施例54〜61は、2価のパラジウム化合物と塩基又は還元剤とを含む水素化触媒を用いて4−オクチンの水素化を行った反応例である。なお、これらの実施例における水素化反応の操作は実施例24に準じて行った。
表8は、実施例62〜66の結果を示す。実施例62〜66は、塩化パラジウム(II)と塩基とを含む水素化触媒を用いて4−オクチンの水素化を行った反応例である。なお、反応基質は4−オクチン、S/Cは1000とした。また、これらの実施例における水素化反応の操作は実施例24に準じて行った。
表9に、実施例26〜29,67〜70の結果を示す。実施例67〜70は、種々の反応条件で4−オクチンの水素化を行った例である。なお、これらの実施例における水素化反応の操作は実施例24に準じて行った。
表10に、実施例71〜79の結果を示す。実施例71〜79は、種々の反応基質の水素化反応例である。使用した水素化促進剤は水素化促進剤(1)であり、水素化反応の際に還元剤を加えて水素化触媒を系中で調製した。これらの実施例における水素化反応の操作は実施例24に準じて行った。なお、反応基質は、塩基とBu4NBH4を用いた精製操作により、酸性物質、ケトン等を除去したものを用いた。典型的な精製方法を実施例80に示す。
不純物としてアセチレンケトンが0.46%含まれている4−オクチンを以下のようにして精製した。まず、分液漏斗に4−オクチンを40ml(273mmol)入れ、1%Na2CO3水溶液で洗浄(10ml×5回)することにより、酸性成分を中和した。水洗、飽和NaCl水洗を行った後、1.5gの無水Na2SO4で乾燥した。処理した4−オクチンを100mlナスフラスコへ移し、Bu4NBH4を1.40g(5.46mmol)加えて攪拌した。Bu4NBH4は4−オクチンに対する溶解性は低く、攪拌してもBu4NBH4は白色粉末のまま懸濁するが、数分で発熱や色調の変化が観察され、アセチレンケトンとBu4NBH4の反応が開始する。50℃で1時間攪拌保持すると、アセチレンケトンとBu4NBH4の反応物が粘稠体として得られる。4−オクチンと粘稠体とを分離し、4−オクチンへ再度Bu4NBH4を1.40g(5.46mmol)加えて50℃、1時間攪拌保持する。ろ過してBu4NBH4を除去した後、水洗して4−オクチンに溶解した微量のBu4NBH4を除去した。飽和NaClで水洗した後、減圧蒸留を行って4−オクチンを得た。本操作によって精製された4−オクチンのGC分析では、アセチレンケトンは検出されなかった。
表11に、実施例AB〜AI,AJ〜AP,AQ〜AVの結果を示す。これらの実施例は各種の水素化促進剤による内部アルキンの水素化反応の例であり、実施例AB〜AIでは反応基質として4−オクチンを用い、実施例AJ〜APでは反応基質として1−フェニル−1−ブチンを用い、実施例AQ〜AVは反応基質としてジフェニルアセチレンを用いた。これらの実施例における水素化反応の操作は実施例24に準じて行った。また、比較例A,B,Cはリンドラー触媒による水素化反応の例であり、それぞれ、反応基質として4−オクチン、1−フェニル−1−ブチン、ジフェニルアセチレンを用いた。これらの比較例では、Bu4NBH4を添加せずキノリンを添加した。これらの実施例における水素化反応の操作は実施例24に準じて行った。
表13に、実施例81,82の結果を示す。実施例82は、水素化触媒を水素ガスで前処理したあと水素化反応を行った例である。用いた水素化促進剤は水素化促進剤(1)であり、水素化反応の際に還元剤を加えて水素化触媒を調製した。水素化反応はS/C=20000の条件で実施した。なお、これらの実施例における水素化反応の操作は実施例24に準じて行った。
表14に、実施例67,48,83〜85及び比較例1,2の結果を示す。実施例83〜85は高S/C条件下にて4−オクチンの水素化を実施した例である。なお、これらの実施例における水素化反応の操作は実施例24に準じて行った。
Claims (9)
- 有機溶媒中、アルキニルアルコール化合物又はアルケニルアルコール化合物と、一般式(1)〜(4)からなるパラジウム化合物群から選ばれた1種又は2種以上のパラジウム化合物又はその多量体とを反応させることにより得られる、前記アルキニルアルコール化合物又は前記アルケニルアルコール化合物を凝集保護剤として有するパラジウムナノ粒子である、水素化促進剤。
Pd(II)XjLk …(1)
(Pd(II)Xm)2-の塩 …(2)
(Pd(II)Ln)2+の塩 …(3)
(Pd(IV)Xp)2-の塩 …(4)
(一般式(1)〜(4)中、Lは含リン配位子を除く単座又は多座配位子(化合物中にLが2以上存在するときは各々独立して互いに同じであってもよいし異なっていてもよい)、Xはアニオン性基、jはXjが全体で−2価となるようにXの価数に応じて決まる値、kは0〜4のいずれかの整数、mはXmが全体で−4価となるようにXの価数に応じて決まる値、nは4〜6のいずれかの整数、pはXpが全体で−6価となるようにXの価数に応じて決まる値である) - 請求項1に記載の水素化促進剤を水素化触媒又は水素化触媒の構成要素として用いた場合に、4−オクチンの水素化反応においてターン・オーバー・ナンバー(TON)が100万以上であるか該水素化反応が完結した時点でのターン・オーバー・フリクエンシー(TOF)が100sec-1以上である、水素化促進剤。
- 請求項1又は2に記載の水素化促進剤を含む、水素化触媒。
- 請求項1又は2に記載の水素化促進剤と塩基及び/又は還元剤とを含む、水素化触媒。
- 前記還元剤がボロヒドリド化合物である、請求項4に記載の水素化触媒。
- 有機溶媒中、アルキニルアルコール化合物又はアルケニルアルコール化合物と、一般式(1)〜(4)からなるパラジウム化合物群から選ばれた1種又は2種以上のパラジウム化合物又はその多量体とを反応させることにより、前記アルキニルアルコール化合物又は前記アルケニルアルコール化合物を凝集保護剤として有するパラジウムナノ粒子である、水素化促進剤を得る、水素化促進剤の製法。
Pd(II)XjLk …(1)
(Pd(II)Xm)2-の塩 …(2)
(Pd(II)Ln)2+の塩 …(3)
(Pd(IV)Xp)2-の塩 …(4)
(一般式(1)〜(4)中、Lは含リン配位子を除く単座又は多座配位子(化合物中にLが2以上存在するときは各々独立して互いに同じであってもよいし異なっていてもよい)、Xはアニオン性基、jはXjが全体で−2価となるようにXの価数に応じて決まる値、kは0〜4のいずれかの整数、mはXmが全体で−4価となるようにXの価数に応じて決まる値、nは4〜6のいずれかの整数、pはXpが全体で−6価となるようにXの価数に応じて決まる値である) - 請求項3〜5のいずれかに記載の水素化触媒を用いて、反応溶媒中、水素又は水素を供与する化合物の存在下、反応基質であるアルキン化合物を部分水素化することによりアルケン化合物を得る、アルケン化合物の製法。
- 請求項4又は5に記載の水素化触媒を用いて、反応溶媒中、水素又は水素を供与する化合物の存在下、反応基質である内部アルキン化合物を部分水素化することにより、高選択的にシスアルケン化合物を得る、アルケン化合物の製法。
- 請求項7又は8に記載のアルケン化合物の製法であって、水素化触媒を水素ガスで前処理したのちアルキン化合物の水素化反応を行うことを特徴とする、アルケン化合物の製法。
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