JP2005206549A - Production method for carrying out organic synthesis under multistage, variable and supercritical condition - Google Patents
Production method for carrying out organic synthesis under multistage, variable and supercritical condition Download PDFInfo
- Publication number
- JP2005206549A JP2005206549A JP2004016368A JP2004016368A JP2005206549A JP 2005206549 A JP2005206549 A JP 2005206549A JP 2004016368 A JP2004016368 A JP 2004016368A JP 2004016368 A JP2004016368 A JP 2004016368A JP 2005206549 A JP2005206549 A JP 2005206549A
- Authority
- JP
- Japan
- Prior art keywords
- organic compound
- reaction
- ketones
- producing
- carbon dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 title abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000006243 chemical reaction Methods 0.000 claims abstract description 134
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 69
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 68
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- -1 ammonium cations Chemical class 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 18
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical group CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 150000002576 ketones Chemical class 0.000 claims description 12
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims description 7
- ZIXLDMFVRPABBX-UHFFFAOYSA-N 2-methylcyclopentan-1-one Chemical compound CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- 150000003431 steroids Chemical class 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 5
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 claims description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 4
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- FDMAFOTXGNYBFG-UHFFFAOYSA-N 2-methylcycloheptan-1-one Chemical compound CC1CCCCCC1=O FDMAFOTXGNYBFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000003609 aryl vinyl group Chemical group 0.000 claims description 3
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- PTUXNCQDACBMKP-UHFFFAOYSA-N 1-phenylbut-3-en-2-one Chemical compound C=CC(=O)CC1=CC=CC=C1 PTUXNCQDACBMKP-UHFFFAOYSA-N 0.000 claims description 2
- BVEVFHZKAPQDJV-UHFFFAOYSA-N 1-phenylpent-3-en-2-one Chemical compound CC=CC(=O)CC1=CC=CC=C1 BVEVFHZKAPQDJV-UHFFFAOYSA-N 0.000 claims description 2
- LPCWMYHBLXLJJQ-UHFFFAOYSA-N 3-hexen-2-one Chemical compound CCC=CC(C)=O LPCWMYHBLXLJJQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexanedione Natural products CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 150000003673 urethanes Chemical class 0.000 claims description 2
- SLOCIJOTBVAMAJ-UHFFFAOYSA-N cycloheptane-1,2-dione Chemical compound O=C1CCCCCC1=O SLOCIJOTBVAMAJ-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 18
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 15
- VSGJHHIAMHUZKF-UHFFFAOYSA-N 2-methylcyclohexane-1,3-dione Chemical compound CC1C(=O)CCCC1=O VSGJHHIAMHUZKF-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 description 3
- 125000005594 diketone group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- KLTVSWGXIAYTHO-UHFFFAOYSA-N 1-Octen-3-one Chemical compound CCCCCC(=O)C=C KLTVSWGXIAYTHO-UHFFFAOYSA-N 0.000 description 2
- HMJJEFPBARGSAT-UHFFFAOYSA-N 2,3,4,7,8,8a-hexahydronaphthalene-1,6-dione Chemical compound O=C1CCCC2=CC(=O)CCC21 HMJJEFPBARGSAT-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- UJBOOUHRTQVGRU-UHFFFAOYSA-N 3-methylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1 UJBOOUHRTQVGRU-UHFFFAOYSA-N 0.000 description 2
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- FEWIGMWODIRUJM-UHFFFAOYSA-N 4-hexen-3-one Chemical compound CCC(=O)C=CC FEWIGMWODIRUJM-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000003997 cyclic ketones Chemical group 0.000 description 2
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 2
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 2
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 2
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- ZPGYUDWZVQOWNY-UHFFFAOYSA-N hept-4-en-3-one Chemical compound CCC=CC(=O)CC ZPGYUDWZVQOWNY-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- JTHNLKXLWOXOQK-UHFFFAOYSA-N hex-1-en-3-one Chemical compound CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 2
- 229940051960 magnesium oxide 50 mg Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- DNHDRUMZDHWHKG-UHFFFAOYSA-N wieland–miescher ketone Chemical compound C1CC(=O)C=C2CCCC(=O)C21C DNHDRUMZDHWHKG-UHFFFAOYSA-N 0.000 description 2
- DVSZKTAMJJTWFG-SKCDLICFSA-N (2e,4e,6e,8e,10e,12e)-docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCC\C=C\C=C\C=C\C=C\C=C\C=C\C(O)=O DVSZKTAMJJTWFG-SKCDLICFSA-N 0.000 description 1
- LABTWGUMFABVFG-ONEGZZNKSA-N (3E)-pent-3-en-2-one Chemical compound C\C=C\C(C)=O LABTWGUMFABVFG-ONEGZZNKSA-N 0.000 description 1
- FEWIGMWODIRUJM-HWKANZROSA-N (E)-4-hexen-3-one Chemical compound CCC(=O)\C=C\C FEWIGMWODIRUJM-HWKANZROSA-N 0.000 description 1
- 239000001764 (E)-oct-3-en-2-one Substances 0.000 description 1
- ULPMRIXXHGUZFA-UHFFFAOYSA-N (R)-4-Methyl-3-hexanone Natural products CCC(C)C(=O)CC ULPMRIXXHGUZFA-UHFFFAOYSA-N 0.000 description 1
- VAIFYHGFLAPCON-UHFFFAOYSA-N 1,3-Diacetylpropane Chemical compound CC(=O)CCCC(C)=O VAIFYHGFLAPCON-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 1
- LVGUHATVVHIJET-UHFFFAOYSA-N 1-phenylpent-1-en-3-one Chemical compound CCC(=O)C=CC1=CC=CC=C1 LVGUHATVVHIJET-UHFFFAOYSA-N 0.000 description 1
- CIISROPQPGGRTG-UHFFFAOYSA-N 2,5-diethylcyclopentan-1-one Chemical compound CCC1CCC(CC)C1=O CIISROPQPGGRTG-UHFFFAOYSA-N 0.000 description 1
- MKLARKDYEBNZFK-UHFFFAOYSA-N 2,5-dimethylcyclopentan-1-one Chemical compound CC1CCC(C)C1=O MKLARKDYEBNZFK-UHFFFAOYSA-N 0.000 description 1
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 1
- CATGMLRVPMQRJQ-UHFFFAOYSA-N 2,6-diethylcyclohexan-1-one Chemical compound CCC1CCCC(CC)C1=O CATGMLRVPMQRJQ-UHFFFAOYSA-N 0.000 description 1
- AILVYPLQKCQNJC-UHFFFAOYSA-N 2,6-dimethylcyclohexan-1-one Chemical compound CC1CCCC(C)C1=O AILVYPLQKCQNJC-UHFFFAOYSA-N 0.000 description 1
- BZIBDUSNXGEVLS-UHFFFAOYSA-N 2,7-diethylcycloheptan-1-one Chemical compound C(C)C1C(C(CCCC1)CC)=O BZIBDUSNXGEVLS-UHFFFAOYSA-N 0.000 description 1
- AUFDKTSDMKFYAX-UHFFFAOYSA-N 2,7-dihydronaphthalene-1,6-dione Chemical compound O=C1CC=CC2=CC(=O)CC=C21 AUFDKTSDMKFYAX-UHFFFAOYSA-N 0.000 description 1
- JEEQHJDSYXNZDE-UHFFFAOYSA-N 2,7-dimethylcycloheptan-1-one Chemical compound CC1CCCCC(C)C1=O JEEQHJDSYXNZDE-UHFFFAOYSA-N 0.000 description 1
- SURCGQGDUADKBL-UHFFFAOYSA-N 2-(2-hydroxyethylamino)-5-nitrobenzo[de]isoquinoline-1,3-dione Chemical compound [O-][N+](=O)C1=CC(C(N(NCCO)C2=O)=O)=C3C2=CC=CC3=C1 SURCGQGDUADKBL-UHFFFAOYSA-N 0.000 description 1
- NAFAJFUPGSGMJP-UHFFFAOYSA-N 2-ethylcycloheptan-1-one Chemical compound CCC1CCCCCC1=O NAFAJFUPGSGMJP-UHFFFAOYSA-N 0.000 description 1
- WKYYYUWKFPFVEY-UHFFFAOYSA-N 2-ethylcyclohexan-1-one Chemical compound CCC1CCCCC1=O WKYYYUWKFPFVEY-UHFFFAOYSA-N 0.000 description 1
- HNFOYUZUPUVFDP-UHFFFAOYSA-N 2-ethylcyclooctan-1-one Chemical compound CCC1CCCCCCC1=O HNFOYUZUPUVFDP-UHFFFAOYSA-N 0.000 description 1
- PPTKUTYPOKHBTL-UHFFFAOYSA-N 2-ethylcyclopentan-1-one Chemical compound CCC1CCCC1=O PPTKUTYPOKHBTL-UHFFFAOYSA-N 0.000 description 1
- TXVAOITYBBWKMG-HWKANZROSA-N 2-hepten-4-one Chemical compound CCCC(=O)\C=C\C TXVAOITYBBWKMG-HWKANZROSA-N 0.000 description 1
- MJFJFHJQZCMMKL-UHFFFAOYSA-N 2-methylcyclooctan-1-one Chemical compound CC1CCCCCCC1=O MJFJFHJQZCMMKL-UHFFFAOYSA-N 0.000 description 1
- JHHZQADGLDKIPM-AATRIKPKSA-N 3-Hepten-2-one Chemical compound CCC\C=C\C(C)=O JHHZQADGLDKIPM-AATRIKPKSA-N 0.000 description 1
- ZCFOBLITZWHNNC-VOTSOKGWSA-N 3-Octen-2-one Chemical compound CCCC\C=C\C(C)=O ZCFOBLITZWHNNC-VOTSOKGWSA-N 0.000 description 1
- ZCFOBLITZWHNNC-UHFFFAOYSA-N 3-Octen-2-one Natural products CCCCC=CC(C)=O ZCFOBLITZWHNNC-UHFFFAOYSA-N 0.000 description 1
- IEVRHAUJJJBXFH-UHFFFAOYSA-N 3-ethylcyclohexan-1-one Chemical compound CCC1CCCC(=O)C1 IEVRHAUJJJBXFH-UHFFFAOYSA-N 0.000 description 1
- DAHXJQBIVWXDAZ-UHFFFAOYSA-N 3-ethylcyclooctan-1-one Chemical compound CCC1CCCCCC(=O)C1 DAHXJQBIVWXDAZ-UHFFFAOYSA-N 0.000 description 1
- XERALSLWOPMNRJ-UHFFFAOYSA-N 3-ethylcyclopentan-1-one Chemical compound CCC1CCC(=O)C1 XERALSLWOPMNRJ-UHFFFAOYSA-N 0.000 description 1
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 1
- GSYFDULLCGVSNJ-UHFFFAOYSA-N 3-methylcycloheptan-1-one Chemical compound CC1CCCCC(=O)C1 GSYFDULLCGVSNJ-UHFFFAOYSA-N 0.000 description 1
- HNEQUAAFVQKBFI-UHFFFAOYSA-N 3-methylcyclooctan-1-one Chemical compound CC1CCCCCC(=O)C1 HNEQUAAFVQKBFI-UHFFFAOYSA-N 0.000 description 1
- AOKRXIIIYJGNNU-UHFFFAOYSA-N 3-methylcyclopentan-1-one Chemical compound CC1CCC(=O)C1 AOKRXIIIYJGNNU-UHFFFAOYSA-N 0.000 description 1
- FOCKPZOFYCTNIA-UHFFFAOYSA-N 4,4a,5,6,7,8-hexahydro-3h-naphthalen-2-one Chemical compound C1CCCC2=CC(=O)CCC21 FOCKPZOFYCTNIA-UHFFFAOYSA-N 0.000 description 1
- JPTOCTSNXXKSSN-VOTSOKGWSA-N 4-Octen-3-one Chemical compound CCC\C=C\C(=O)CC JPTOCTSNXXKSSN-VOTSOKGWSA-N 0.000 description 1
- KURXRTNJIITRCV-UHFFFAOYSA-N 4-ethylcycloheptan-1-one Chemical compound CCC1CCCC(=O)CC1 KURXRTNJIITRCV-UHFFFAOYSA-N 0.000 description 1
- OKSDJGWHKXFVME-UHFFFAOYSA-N 4-ethylcyclohexan-1-one Chemical compound CCC1CCC(=O)CC1 OKSDJGWHKXFVME-UHFFFAOYSA-N 0.000 description 1
- UOUGRVQDOAJZRF-UHFFFAOYSA-N 4-ethylcyclooctan-1-one Chemical compound CCC1CCCCC(=O)CC1 UOUGRVQDOAJZRF-UHFFFAOYSA-N 0.000 description 1
- WXVNSHRGPVHBPD-UHFFFAOYSA-N 4-methylcycloheptan-1-one Chemical compound CC1CCCC(=O)CC1 WXVNSHRGPVHBPD-UHFFFAOYSA-N 0.000 description 1
- DIYVEGISSYQDLK-UHFFFAOYSA-N 4-methylcyclooct-2-en-1-one Chemical compound CC1CCCCC(=O)C=C1 DIYVEGISSYQDLK-UHFFFAOYSA-N 0.000 description 1
- OHERZLWVBJCXOF-UHFFFAOYSA-N 4a-methyl-3,4,5,6,7,8-hexahydronaphthalen-2-one Chemical compound C1CCCC2=CC(=O)CCC21C OHERZLWVBJCXOF-UHFFFAOYSA-N 0.000 description 1
- GZJLLYHBALOKEX-UHFFFAOYSA-N 6-Ketone, O18-Me-Ussuriedine Natural products CC=CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O GZJLLYHBALOKEX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001529742 Rosmarinus Species 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 1
- KAUVQQXNCKESLC-UHFFFAOYSA-N docosahexaenoic acid (DHA) Natural products COC(=O)C(C)NOCC1=CC=CC=C1 KAUVQQXNCKESLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical compound CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QVJOMQRREBIZOD-UHFFFAOYSA-N non-4-en-3-one Chemical compound CCCCC=CC(=O)CC QVJOMQRREBIZOD-UHFFFAOYSA-N 0.000 description 1
- SEVSRVAJBFYTEX-UHFFFAOYSA-N oct-5-en-4-one Chemical compound CCCC(=O)C=CCC SEVSRVAJBFYTEX-UHFFFAOYSA-N 0.000 description 1
- YWXLSHOWXZUMSR-UHFFFAOYSA-N octan-4-one Chemical compound CCCCC(=O)CCC YWXLSHOWXZUMSR-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
- JHHZQADGLDKIPM-UHFFFAOYSA-N trans-hept-3-en-2-one Natural products CCCC=CC(C)=O JHHZQADGLDKIPM-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、二酸化炭素の存在下に、反応基質を反応させて有機化合物を合成するにあたり、少なくとも反応圧力を変化させる反応条件で該有機化合物を合成する、新規な有機化合物の合成方法に関するものであり、更に詳しくは、二酸化炭素、即ち、超臨界二酸化炭素、亜臨界二酸化炭素ないし加圧二酸化炭素の存在下での反応において、圧力・温度を多段階に可変させることにより、各圧力・温度下における二酸化炭素の密度や、基質の二酸化炭素に対する溶解度等が連続的に変化することを利用して、従来の、単純な温度・圧力の制御だけでは、高収率、高選択率で製造することが難しかった有機化合物を、選択的・効率的に製造することを可能とする新規有機合成方法に関するものである。
本発明は、環境問題等を抜本的に解消することが可能な、次世代の化学合成技術としてその実用化が強く期待されている、超臨界流体、亜臨界流体等の加圧媒体を利用した有機化合物の合成技術の分野において、二酸化炭素の存在下に、少なくとも反応圧力を多段階に、及び連続的に可変させる反応条件下で反応基質を反応させることにより、化合物の選択的合成が可能であり、更に、従来のように、合成反応・分離操作を繰返すことなく、一段階で、収率良く目的化合物を合成することが可能な新しい有機合成技術を提供するものである。
本発明の多段階可変超臨界有機合成法は、反応基質を選ばず、短時間で、大量に、しかも、環境にやさしく、有機化合物を製造することができる、新規な有機合成方法として有用である。
The present invention relates to a novel organic compound synthesis method for synthesizing an organic compound under reaction conditions at least changing the reaction pressure when synthesizing an organic compound by reacting a reaction substrate in the presence of carbon dioxide. More specifically, in the reaction in the presence of carbon dioxide, that is, supercritical carbon dioxide, subcritical carbon dioxide or pressurized carbon dioxide, by varying the pressure and temperature in multiple stages, Manufacturing with high yield and high selectivity only by simple temperature / pressure control, using the continuous change of carbon dioxide density and solubility of carbon dioxide in the substrate. The present invention relates to a novel organic synthesis method that makes it possible to selectively and efficiently produce an organic compound that has been difficult to achieve.
The present invention utilizes a pressurized medium such as a supercritical fluid and a subcritical fluid, which is expected to be practically used as a next-generation chemical synthesis technology capable of drastically solving environmental problems and the like. In the field of organic compound synthesis technology, selective synthesis of a compound is possible in the presence of carbon dioxide by reacting a reaction substrate under reaction conditions in which reaction pressure is varied in multiple steps and continuously. Furthermore, the present invention provides a new organic synthesis technique capable of synthesizing a target compound with a high yield in one step without repeating the synthesis reaction / separation operation as in the prior art.
The multistage variable supercritical organic synthesis method of the present invention is useful as a novel organic synthesis method capable of producing an organic compound in a short time, in a large amount, and in an environmentally friendly manner, without selecting a reaction substrate. .
これまで、超臨界二酸化炭素、亜臨界二酸化炭素、あるいは二酸化炭素を反応溶媒として用いた反応は、圧力一定、温度一定ないしは、圧力一定、温度可変で検討が行なわれている。特に、超臨界二酸化炭素を用いた有機物の抽出に関しては、温度可変精留塔等による段階的抽出が行なわれている。従来、先行技術文献において、例えば、温度勾配を付した超臨界流体抽出塔を新規に制作し、エイコサペンタエン酸（ＥＰＡ）、ドコサヘキサエン酸（ＤＨＡ）を半回分的操作により、効率的に抽出精製する方法が提案されている（非特許文献１）。また、同様に、温度勾配を付した超臨界抽出装置を製作し、ローズマリーからのカルバゾールを効率よく抽出する方法が提案されている（特許文献1）。これらは、全て、超臨界二酸化炭素及びその温度勾配を利用した抽出方法に関するものであり、従来、抽出に多く用いられる超臨界二酸化炭素の利用技術として、圧力は一定のままで、温度勾配を利用した事例はある。しかし、超臨界二酸化炭素及びその圧力変化あるいは圧力勾配を利用した抽出ないし反応例は、非常に稀である。 So far, reactions using supercritical carbon dioxide, subcritical carbon dioxide, or carbon dioxide as a reaction solvent have been studied under constant pressure, constant temperature, constant pressure, and variable temperature. In particular, for extraction of organic substances using supercritical carbon dioxide, stepwise extraction using a temperature variable rectification column or the like is performed. Conventionally, in prior art documents, for example, a supercritical fluid extraction tower with a temperature gradient is newly produced, and eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are efficiently extracted and purified by semi-batch operations. A method has been proposed (Non-Patent Document 1). Similarly, a method for producing a supercritical extraction apparatus with a temperature gradient and efficiently extracting carbazole from rosemary has been proposed (Patent Document 1). These are all related to the extraction method using supercritical carbon dioxide and its temperature gradient. Conventionally, as a technology for using supercritical carbon dioxide, which is often used for extraction, the pressure remains constant and the temperature gradient is used. There is a case. However, examples of extraction or reaction utilizing supercritical carbon dioxide and its pressure change or pressure gradient are very rare.
超臨界二酸化炭素を用いた反応は、近年、論文、特許出願件数ともに大幅に増大している。特に、二酸化炭素を超臨界状態で使用することで、反応時間、反応収率が大幅に改善されるため、その反応溶媒としての利用が非常に注目される。しかし、それらの反応では、依然として、圧力・温度一定の元で反応が行なわれており、結局、有機溶媒を用いた場合と比べて、超臨界二酸化炭素を用いた場合であっても、反応操作上の大幅な短縮にはならないのが現状である。 In recent years, the number of papers and patent applications has greatly increased in reactions using supercritical carbon dioxide. In particular, when carbon dioxide is used in a supercritical state, the reaction time and the reaction yield are greatly improved. However, in these reactions, the reaction is still performed under a constant pressure and temperature, and as a result, even when supercritical carbon dioxide is used compared to the case of using an organic solvent, the reaction operation is performed. The current situation is not a significant shortening of the above.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、簡単な合成プロセスで、有機化合物を、高い選択性で、収率良く合成することができ、しかも、環境問題を解決できる、新しい有機化合物の製造方法を開発することを目標として、鋭意研究を積み重ねた結果、超臨界二酸化炭素、亜臨界二酸化炭素又は加圧二酸化炭素を反応溶媒とし、二酸化炭素が、温度、圧力に応じて、容易に密度・溶解度・粘度等を可変できる点に着目し、多段階ないしは連続的に温度・圧力を変化させることで、従来、数段階の反応・分離操作を繰り返すことで合成していた工程を、反応容器内の化合物を、他の容器に移動させることなく、一段階で、効率的に行うことが可能になることを見出し、本発明を完成するに至った。
即ち、本発明の目的は、多段階ないしは連続的に温度・圧力を変化させることで、数段階の反応・分離操作を繰り返すことなく、一段階で、目的の有機化合物を合成することができる有機化合物の製造方法を提供することである。
また、本発明の目的は、高選択性、高収率の有機化合物の製造方法を提供することである。
また、本発明の目的は、従来、何段階もあった一連の有機反応で、各段階で様々な反応操作、分離操作、抽出操作等が必要であり、実際の反応時間は数時間〜十数時間でも、トータルでは、何日、何週間も必要であった製造工程を、一段階に短縮し、しかも反応時間数分〜２４時間以内、トータル1日以内という、極めて短時間で、複雑な化学反応を遂行することが可能な有機化合物の製造方法を提供することである。
また、本発明の目的は、有機溶媒、酸、アルカリ等を極力使用せずに反応を遂行し、有機化合物を効率良く製造する方法を提供することである。
また、本発明の目的は、廃水、廃物がほとんど発生しない製造方法であって、廃水、廃物の処理をほとんど必要としない、環境にやさしい、有機化合物の製造方法を提供することである。
Under such circumstances, the present inventors have been able to synthesize organic compounds with high selectivity and high yield by a simple synthesis process in view of the above-described prior art, and also have environmental problems. As a result of intensive research with the goal of developing a new method for producing organic compounds that can be solved, supercritical carbon dioxide, subcritical carbon dioxide or pressurized carbon dioxide is used as the reaction solvent, and carbon dioxide is the temperature, pressure. Focusing on the fact that the density, solubility, viscosity, etc. can be easily changed according to the conditions, and by changing the temperature and pressure in multiple steps or continuously, it has been synthesized by repeating several steps of reaction and separation. The present inventors have found that it is possible to efficiently carry out the above process in one step without moving the compound in the reaction vessel to another vessel, and have completed the present invention.
That is, an object of the present invention is to provide an organic compound capable of synthesizing a target organic compound in one step without repeating several steps of reaction / separation operation by changing the temperature and pressure in multiple steps or continuously. It is to provide a method for producing a compound.
Another object of the present invention is to provide a method for producing an organic compound with high selectivity and high yield.
In addition, the object of the present invention is a series of organic reactions that have conventionally been performed in a number of stages, and various reaction operations, separation operations, extraction operations, and the like are required at each stage. The actual reaction time is several hours to dozens. Even in terms of time, the manufacturing process, which required days or weeks in total, was shortened to one stage, and the reaction time was several minutes to 24 hours, and the total time was less than 1 day. It is to provide a method for producing an organic compound capable of performing a reaction.
Another object of the present invention is to provide a method for efficiently producing an organic compound by carrying out a reaction without using an organic solvent, acid, alkali or the like as much as possible.
Another object of the present invention is to provide an organic compound production method that is environmentally friendly and requires little treatment of waste water and waste, with little production of waste water and waste.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）二酸化炭素の存在下に、反応基質を反応させて有機化合物を合成するにあたり、少なくとも反応圧力を２段階以上の多段階又は連続的に可変させる反応条件下で、２段階以上の反応を含む一連の反応を１段階で、選択的に有機化合物を合成することを特徴とする、有機化合物の製造方法。
（２）二酸化炭素が、超臨界、亜臨界ないし加圧状態の二酸化炭素であることを特徴とする上記（１）に記載の有機化合物の製造方法。
（３）反応条件が、反応圧力又は反応圧力と反応温度を、段階的に多段階に、又は連続的に可変させることを特徴とする上記（１）又は（２）に記載の有機化合物の製造方法。
（４）反応容器に反応基質を収容し、バッチ方式で反応させることを特徴とする上記（１）から（３）のいずれかに記載の有機化合物の製造方法。
（５）連続方式により反応させることを特徴とする上記（１）から（３）のいずれかに記載の有機化合物の製造方法。
（６）反応条件が、反応圧力７．３ＭＰａ以上５０ＭＰａ以下、反応温度３１℃以上３００℃以下の少なくとも超臨界状態の範囲から選ばれることを特徴とする上記（１）から（５）のいずれかに記載の有機化合物の合成方法。
（７）反応基質が、炭素数１〜５０個の範囲で構成される有機化合物で、アルカン類、アルケン類、アルキン類、アリール類、アルコール類、エーテル類、チオール類、チオエーテル類、ケトン類、アルデヒド類、カルボン酸類、カルボン酸誘導体類、アミン類、ウレタン類、イミン類、ニトリル類、ニトロ類、有機ハロゲン類、カルボカチオン類、カルボアニオン類、アンモニウムカチオン類、ホスホニウムカチオン類、スルホニウムカチオン類から選ばれることを特徴とする上記（１）から（６）のいずれかに記載の有機化合物の製造方法。
（８）反応基質が、ケトン類であり、アルキルケトン類、シクロアルキルケトン類、アルキルジケトン類、シクロアルキルジケトン類、アルキルトリケトン類、シクロアルキルトリケトン類、アルキルテトラケトン類、シクロアルキルテトラケトン類、アリールケトン類、アリールアルキルケトン類、アリールシクロアルキルケトン類及びビニルケトン類、アルキルビニルケトン類、シクロアルキルビニルケトン類、アリールビニルケトン類、シクロアルキルビニルケトン類、アリールアルキルビニルケトン類、アリールシクロアルキルビニルケトン類及びそれらの誘導体から選ばれることを特徴とする上記（１）から（６）のいずれかに記載の有機化合物の製造方法。
（９）ケトン類が、シクロペンタノン、メチルシクロペンタノン、シクロペンタジオン、メチルシクロペンタジオン、シクロヘキサノン、メチルシクロヘキサノン、シクロヘキサジオン、メチルシクロヘキサジオン、シクロヘプタノン、メチルシクロヘプタノン、シクロヘプタジオン、メチルシクロヘプタジオン、アセトン、ブタノン、ペンタノン、ペンタジオン、ヘキサノン、ヘキサジオン、ヘプタノン、ヘプタジオン及びそれらの誘導体から選ばれることを特徴とする上記（８）に記載の有機化合物の製造方法。
（１０）ビニルケトン類が、ブテノン、ペンテノン、へキセノン、フェニルブテノン、フェニルペンテノン及びその誘導体から選ばれることを特徴とする上記（８）に記載の有機化合物の製造方法。
（１１）有機化合物がステロイド環化生成物であることを特徴とする上記（８）に記載の有機化合物の製造方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) In synthesizing an organic compound by reacting a reaction substrate in the presence of carbon dioxide, at least two stages of reaction are performed under reaction conditions in which the reaction pressure is varied in two or more stages or continuously. A method for producing an organic compound, which comprises selectively synthesizing an organic compound in a single step including a series of reactions.
(2) The method for producing an organic compound as described in (1) above, wherein the carbon dioxide is carbon dioxide in a supercritical, subcritical or pressurized state.
(3) The production of the organic compound as described in (1) or (2) above, wherein the reaction conditions are such that the reaction pressure or the reaction pressure and the reaction temperature are varied stepwise in multiple steps or continuously. Method.
(4) The method for producing an organic compound according to any one of (1) to (3) above, wherein a reaction substrate is accommodated in a reaction vessel and reacted in a batch system.
(5) The method for producing an organic compound as described in any one of (1) to (3) above, wherein the reaction is carried out in a continuous manner.
(6) Any one of (1) to (5) above, wherein the reaction conditions are selected from a range of at least a supercritical state of a reaction pressure of 7.3 MPa to 50 MPa and a reaction temperature of 31 ° C. to 300 ° C. A method for synthesizing the organic compound described in 1.
(7) The reaction substrate is an organic compound composed of 1 to 50 carbon atoms, alkanes, alkenes, alkynes, aryls, alcohols, ethers, thiols, thioethers, ketones, From aldehydes, carboxylic acids, carboxylic acid derivatives, amines, urethanes, imines, nitriles, nitros, organic halogens, carbocations, carbanions, ammonium cations, phosphonium cations, sulfonium cations The method for producing an organic compound according to any one of (1) to (6) above, which is selected.
(8) The reaction substrate is a ketone, and the alkyl ketone, cycloalkyl ketone, alkyl diketone, cycloalkyl diketone, alkyl triketone, cycloalkyl triketone, alkyl tetraketone, cycloalkyl tetraketone , Aryl ketones, aryl alkyl ketones, aryl cycloalkyl ketones and vinyl ketones, alkyl vinyl ketones, cycloalkyl vinyl ketones, aryl vinyl ketones, cycloalkyl vinyl ketones, arylalkyl vinyl ketones, arylcyclo The method for producing an organic compound according to any one of (1) to (6) above, which is selected from alkyl vinyl ketones and derivatives thereof.
(9) Ketones are cyclopentanone, methylcyclopentanone, cyclopentadione, methylcyclopentadione, cyclohexanone, methylcyclohexanone, cyclohexadione, methylcyclohexadione, cycloheptanone, methylcycloheptanone, cyclohepta The method for producing an organic compound as described in (8) above, which is selected from dione, methylcycloheptadione, acetone, butanone, pentanone, pentadione, hexanone, hexadione, heptanone, heptadione and derivatives thereof.
(10) The method for producing an organic compound as described in (8) above, wherein the vinyl ketone is selected from butenone, pentenone, hexenone, phenylbutenone, phenylpentenone and derivatives thereof.
(11) The method for producing an organic compound as described in (8) above, wherein the organic compound is a steroid cyclization product.
次に、本発明について更に詳細に説明する。
本発明は、二酸化炭素、即ち、超臨界二酸化炭素、亜臨界二酸化炭素ないし加圧二酸化炭素の存在下での反応において、少なくとも圧力を連続的に変化させることにより、各反応条件下における、基質の二酸化炭素に対する溶解度が変化することを利用し、単純な温度圧力制御だけでは難しかった有機化合物を、選択的・効率的に製造することを特徴とするものである。本発明を実施するに当たっては、反応圧力に加え、反応温度を適宜組み合わせて、両者を変化させることにより、更に、効率良く有機化合物を合成することができる。また、本発明の製造方法は、目的とする化合物を、高選択的、高収率で、迅速に合成できる特徴を有するものであるが、これらは、後述する実施例に示される実験結果によってはじめて実証されたものである。
Next, the present invention will be described in more detail.
In the reaction in the presence of carbon dioxide, that is, supercritical carbon dioxide, subcritical carbon dioxide, or pressurized carbon dioxide, the present invention provides a substrate under each reaction condition by continuously changing at least the pressure. Utilizing the change in solubility in carbon dioxide, it is characterized by selectively and efficiently producing an organic compound, which has been difficult only by simple temperature and pressure control. In practicing the present invention, an organic compound can be synthesized more efficiently by changing both of the reaction pressure and the reaction temperature as appropriate. In addition, the production method of the present invention has a feature that a target compound can be rapidly synthesized with high selectivity and high yield. However, these are only obtained from the experimental results shown in the examples described later. It has been proven.
本発明の合成反応に用いる、二酸化炭素としては、超臨界二酸化炭素、亜臨界二酸化炭素ないしは加圧二酸化炭素が挙げられ、通常、温度０℃〜５００℃、圧力０．１ＭＰａ〜１００ＭＰａのものが用いられるが、好ましくは、温度３１℃〜５００℃、圧力０．１ＭＰａ〜５０ＭＰａ、更に好ましくは、温度３１℃〜３００℃、圧力７．３ＭＰａ〜５０ＭＰａの二酸化炭素が用いられる。また、反応に用いる二酸化炭素は、必ずしも純二酸化炭素を用いる必要は無く、二酸化炭素とは別な気体ないし液体ないし固体と混合した二酸化炭素でも良い。例えば、二酸化炭素と水素、酸素、窒素、フッ素、塩素、臭素、アンモニア、アセチレン、メタン、エタン、プロパン、エチレン、プロピレン、ヘリウム、ネオン、アルゴン、クリプトン、キセノン等のガスとの混合ガスでも構わず、通常、例えば、１０％以上純度を持つ二酸化炭素を用いるが、好ましくは、５０％以上の純度を持つ二酸化炭素、更に好ましくは、８０％以上の純度を持つ二酸化炭素が用いられる。本発明は、反応基質が限定されることなく、いかなる化合物に対しても適用可能であるが、目的とする有機化合物、反応基質の種類、反応経路に応じて、最適な反応温度、反応圧力を適宜選定する。 Examples of carbon dioxide used in the synthesis reaction of the present invention include supercritical carbon dioxide, subcritical carbon dioxide, and pressurized carbon dioxide. Usually, those having a temperature of 0 ° C. to 500 ° C. and a pressure of 0.1 MPa to 100 MPa are used. However, carbon dioxide having a temperature of 31 ° C. to 500 ° C. and a pressure of 0.1 MPa to 50 MPa, and more preferably a temperature of 31 ° C. to 300 ° C. and a pressure of 7.3 MPa to 50 MPa is used. Carbon dioxide used in the reaction is not necessarily pure carbon dioxide, and may be carbon dioxide mixed with a gas, liquid, or solid other than carbon dioxide. For example, a mixed gas of carbon dioxide and hydrogen, oxygen, nitrogen, fluorine, chlorine, bromine, ammonia, acetylene, methane, ethane, propane, ethylene, propylene, helium, neon, argon, krypton, xenon, etc. Usually, for example, carbon dioxide having a purity of 10% or more is used, preferably carbon dioxide having a purity of 50% or more, more preferably carbon dioxide having a purity of 80% or more. The present invention can be applied to any compound without limitation on the reaction substrate, but the optimum reaction temperature and reaction pressure can be selected according to the target organic compound, the type of reaction substrate, and the reaction route. Select as appropriate.
本発明の方法で用いる反応基質及び反応経路は、特に限定されるものではないが、脂肪族ケトン、これらのジケトン、トリケトン、テトラケトン、脂肪族環状ケトン、これらのジケトン、トリケトン、テトラケトン等のケトン類、そして、それらのケトン類の誘導体、芳香族ケトン、これらのジケトン、トリケトン、テトラケトン等のケトン類、そして、それらのケトン類の誘導体、脂肪族アルデヒド、これらのジアルデヒド、トリアルデヒド、テトラアルデヒド、そしてそれらのアルデヒド類の誘導体、脂肪族環状アルデヒド、これらのジアルデヒド、トリアルデヒド、テトラアルデヒド、そしてそれらのアルデヒド類の誘導体と、ビニルケトン類、アルキルビニルケトン類、シクロアルキルビニルケトン類、アリールビニルケトン類、シクロアルキルビニルケトン類、アリールアルキルビニルケトン類、アリールシクロアルキルビニルケトン類、及びそれらの誘導体との反応による、環状ケトン構造を有する化合物の合成が、代表的な反応として挙げられる。これらの反応の基質の具体例としては、例えば、ケトン類としては、シクロペンタノン、２−メチルシクロペンタノン、３−メチルシクロペンタノン、２−エチルシクロペンタノン、３−エチルシクロペンタノン、２，５−ジメチルシクロペンタノン、２，５−ジエチルシクロペンタノン、シクロヘキサノン、２−メチルシクロヘキサノン、３−メチルシクロヘキサノン、４−メチルシクロヘキサノン、２−エチルシクロヘキサノン、３−エチルシクロヘキサノン、４−エチルシクロヘキサノン、２，６−ジメチルシクロヘキサノン、２，６−ジエチルシクロヘキサノン、シクロヘプタノン、２−メチルシクロヘプタノン、３−メチルシクロヘプタノン、４−メチルシクロヘプタノン、２−エチルシクロヘプタノン、３−エチルシクロヘプタノン、４−エチルシクロヘプタノン、２，７−ジメチルシクロヘプタノン、２，７−ジエチルシクロヘプタノン、シクロオクタノン、２−メチルシクロオクタノン、３−メチルシクロオクタノン、４−メチルシクロオクタノン、２−エチルシクロオクタノン、３−エチルシクロオクタノン、４−エチルシクロオクタノン、シクロペンタ−１，３−ジオン、２−メチルシクロペンタ−１，３−ジオン、４−メチルシクロペンタ−１，３−ジオン、シクロヘキサ−１，３−ジオン、２−メチルシクロヘキサ−１，３−ジオン、４−メチルシクロヘキサ−１，３−ジオン、シクロヘプタ−１，３−ジオン、２−メチルシクロヘプタ−１，３−ジオン、４−メチルシクロヘプタ−１，３−ジオン、シクロオクタ−１，３−ジオン、２−メチルシクロオクタ−１，３−ジオン、４−メチルシクロオクタ−１，３−ジオン、５−メチルシクロオクタ−１，３−ジオン、６−メチルシクロオクタ−１，３−ジオン、２−エチルシクロオクタ−１，３−ジオン、４−エチルシクロオクタ−１，３−ジオン、５−エチルシクロオクタ−１，３−ジオン、６−エチルシクロオクタ−１，３−ジオン、シクロヘキサ−１，３，５−トリオン、２−メチルシクロヘキサ−１，３，５−トリオン、２，４−ジメチルシクロヘキサ−１，３，５−トリオン、２，４，６−トリメチルシクロヘキサ−１，３，５−トリオン、シクロヘプタ−１，３，５，７−テトラオン、２−メチルシクロヘプタ−１，３，５，７−テトラオン、２，４−ジメチルシクロヘプタ−１，３，５，７−テトラオン、２，４，６−トリメチルシクロヘプタ−１，３，５，７−テトラオン、アセトン、２−ブタノン、２−ペンタノン、３−ペンタノン、２−ヘキサノン、３−ヘキサノン、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、２−オクタノン、３−オクタノン、４−オクタノン、２，４−ペンタジオン、２，４−ヘキサジオン、２，５−ヘキサジオン、２，４−ヘプタジオン、２，５−ヘプタジオン、２，６−ヘプタジオン、２，４−オクタジオン、２，５−オクタジオン、２，６−オクタジオン、２，７−オクタジオン等が挙げられる。また、ビニルケトンの具体例としては、例えば、３−ブテン−２−オン、３−ペンテン−２−オン、１−ペンテン−３−オン、メチル−３−ペンテン−２−オン、３−ヘキセン−２−オン、１−ヘキセン−３−オン、４−ヘキセン−３−オン、メチル−３−ヘキセン−２−オン、３−ヘプテン−２−オン、１−ヘプテン−３−オン、４−ヘプテン−３−オン、２−ヘプテン−４−オン、メチル−３−ヘプテン−２−オン、３−オクテン−２−オン、１−オクテン−３−オン、４−オクテン−３−オン、５−オクテン−４−オン、２−オクテン−３−オン、メチル−３−オクテン−２−オン、フェニルペンテン−３−オン等が挙げられる。本発明の合成方法は、ステロイド化合物等のこうした環状ケトン構造を有する化合物の合成反応以外にも、アルデヒド類、アルコール類、アミン類、ニトリル類、イミン類等を原料としてアクロレインの様なビニルアルデヒド構造を有する化合物等の合成や、キノン構造を有する化合物等の合成にも有用である。 The reaction substrate and reaction route used in the method of the present invention are not particularly limited, but ketones such as aliphatic ketones, these diketones, triketones, tetraketones, aliphatic cyclic ketones, these diketones, triketones, tetraketones and the like. , And derivatives of these ketones, aromatic ketones, ketones such as these diketones, triketones, tetraketones, and derivatives of these ketones, aliphatic aldehydes, these dialdehydes, trialdehydes, tetraaldehydes, And derivatives of these aldehydes, aliphatic cyclic aldehydes, these dialdehydes, trialdehydes, tetraaldehydes, and derivatives of these aldehydes, vinyl ketones, alkyl vinyl ketones, cycloalkyl vinyl ketones, aryl vinyl ketones Kind B alkyl vinyl ketones, arylalkyl vinyl ketones, arylcycloalkyl vinyl ketones, and by reaction with a derivative thereof, synthetic compounds having a cyclic ketone structure is mentioned as a typical reaction. Specific examples of substrates for these reactions include, for example, ketones such as cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2-ethylcyclopentanone, 3-ethylcyclopentanone, 2,5-dimethylcyclopentanone, 2,5-diethylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2-ethylcyclohexanone, 3-ethylcyclohexanone, 4-ethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,6-diethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone, 4-methylcycloheptanone, 2-ethylcycloheptanone, 3-ethylcyclo Hepta 4-ethylcycloheptanone, 2,7-dimethylcycloheptanone, 2,7-diethylcycloheptanone, cyclooctanone, 2-methylcyclooctanone, 3-methylcyclooctanone, 4-methylcyclooctane Non, 2-ethylcyclooctanone, 3-ethylcyclooctanone, 4-ethylcyclooctanone, cyclopenta-1,3-dione, 2-methylcyclopenta-1,3-dione, 4-methylcyclopenta-1 , 3-dione, cyclohexa-1,3-dione, 2-methylcyclohexa-1,3-dione, 4-methylcyclohexa-1,3-dione, cyclohepta-1,3-dione, 2-methylcyclohepta -1,3-dione, 4-methylcyclohepta-1,3-dione, cycloocta-1,3-dione, 2-methylcyclothio 1,3-dione, 4-methylcycloocta-1,3-dione, 5-methylcycloocta-1,3-dione, 6-methylcycloocta-1,3-dione, 2-ethylcycloocta- 1,3-dione, 4-ethylcycloocta-1,3-dione, 5-ethylcycloocta-1,3-dione, 6-ethylcycloocta-1,3-dione, cyclohexa-1,3,5- Trione, 2-methylcyclohexa-1,3,5-trione, 2,4-dimethylcyclohexa-1,3,5-trione, 2,4,6-trimethylcyclohexa-1,3,5-trione, Cyclohepta-1,3,5,7-tetraone, 2-methylcyclohepta-1,3,5,7-tetraone, 2,4-dimethylcyclohepta-1,3,5,7-tetraone, 2,4, 6-trimethyl Cyclohepta-1,3,5,7-tetraone, acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2,4-pentadione, 2,4-hexadione, 2,5-hexadione, 2,4-heptadione, 2,5-heptadione, 2,6-heptadione, 2,4-octadione, Examples include 2,5-octadione, 2,6-octadione, and 2,7-octadione. Specific examples of vinyl ketone include, for example, 3-buten-2-one, 3-penten-2-one, 1-penten-3-one, methyl-3-penten-2-one, and 3-hexene-2. -One, 1-hexen-3-one, 4-hexen-3-one, methyl-3-hexen-2-one, 3-hepten-2-one, 1-hepten-3-one, 4-heptene-3 -One, 2-hepten-4-one, methyl-3-hepten-2-one, 3-octen-2-one, 1-octen-3-one, 4-octen-3-one, 5-octene-4 -One, 2-octen-3-one, methyl-3-octen-2-one, phenylpenten-3-one and the like. The synthesis method of the present invention is not limited to the synthesis reaction of such a compound having a cyclic ketone structure such as a steroid compound, but a vinylaldehyde structure such as acrolein using aldehydes, alcohols, amines, nitriles, imines, etc. as raw materials. It is also useful for synthesizing compounds having a quinone structure and for synthesizing compounds having a quinone structure.
本発明は、多段階に反応圧力又は反応圧力及び反応温度を変化させることにより、各圧力・温度下における基質の二酸化炭素に対する溶解度が変化することを利用するものであるが、圧力、温度の変化は、連続的又は段階的のいずれの方式を採用しても良い。また、単一の容器内に反応基質を収容したままで、多段階に反応圧力、温度を変化させて反応を遂行するバッチ方式、及び反応圧力、温度が相違する複数の反応プロセスを連続して組み合わせて反応を遂行するセミバッチ方式及び連続方式等のいずれの反応方式でも本発明を実施できる。また、本発明では、多段階に反応圧力、温度を変化させるにあたり、反応基質、目的とする化合物、反応経路等により、その最適の条件は相違するので、生成物の状態を検討しながら反応条件は適宜決定できるが、通常の反応においては、段階的に反応条件を変化させる場合は、反応条件を、１回〜１０回の範囲で変化させることにより、目的の有機化合物を効率良く合成できる。本発明は、従来の製造工程のように、合成反応・分離操作の繰返しを必要としないため、目的の有機化合物を合成するに要する操作は簡単であり、また、合成反応は、超臨界状態の二酸化炭素を反応媒体として用いることから、各段階の反応時間を、極めて短縮することができるところから、トータルの製造時間は極めて短時間にすることが可能である。本発明による反応時間は、反応基質、目的とする化合物、反応経路、反応条件等により相違するが、通常、各段階の反応時間を、場合により１０００分の１にも短縮できることから、反応時間は５分〜１日程度で良い。 The present invention utilizes the fact that the solubility of the substrate in carbon dioxide under each pressure and temperature changes by changing the reaction pressure or reaction pressure and reaction temperature in multiple stages. Either a continuous method or a stepwise method may be adopted. In addition, a batch system in which reaction is performed by changing the reaction pressure and temperature in multiple stages while the reaction substrate is contained in a single container, and a plurality of reaction processes with different reaction pressure and temperature are continuously performed. The present invention can be carried out by any reaction system such as a semi-batch system and a continuous system in which the reaction is performed in combination. In the present invention, when changing the reaction pressure and temperature in multiple stages, the optimum conditions differ depending on the reaction substrate, target compound, reaction route, etc., so the reaction conditions are examined while examining the state of the product. In a normal reaction, when the reaction conditions are changed stepwise, the target organic compound can be efficiently synthesized by changing the reaction conditions in the range of 1 to 10 times. Since the present invention does not require repeated synthesis reaction / separation operation unlike the conventional production process, the operation required to synthesize the target organic compound is simple, and the synthesis reaction is in a supercritical state. Since carbon dioxide is used as a reaction medium, the reaction time at each stage can be extremely shortened, so that the total production time can be extremely short. The reaction time according to the present invention varies depending on the reaction substrate, target compound, reaction route, reaction conditions, etc., but usually the reaction time at each stage can be shortened to 1/1000 depending on the case, so the reaction time is It may be about 5 minutes to 1 day.
本発明の製造方法により、多段階で反応圧力・温度を変化させ、有機化合物を合成するには、例えば、耐圧容器内に、反応基質と二酸化炭素を導入して容器内の圧力を所定の値に調整した後、所定の反応温度の下で反応を遂行し、次いで、更に、容器内に二酸化炭素を導入して、容器内を、第二の圧力に調整するとともに、第二の反応温度の下で反応を遂行することにより有機化合物の合成が行われる。目的とする反応生成物に応じて、第三、第四等の反応条件が設定されても良い。後述する実施例において実証されるように、本発明によると、通常は、幾つもの反応を経て合成される有機化合物が、一段階で合成でき、しかも、その反応基質の転化率は１００％、目的とする化合物の収率９５％を得ることができることは、驚異的なことであり、このことは、本発明が、化合物の選択性が非常に高く、効率の良い合成方法であることを示すものである。 In order to synthesize an organic compound by changing the reaction pressure and temperature in multiple stages by the production method of the present invention, for example, a reaction substrate and carbon dioxide are introduced into a pressure resistant container, and the pressure in the container is set to a predetermined value. Then, the reaction is carried out under a predetermined reaction temperature, and then carbon dioxide is further introduced into the container to adjust the inside of the container to the second pressure, and at the second reaction temperature. The organic compound is synthesized by carrying out the reaction under. Third, fourth, etc. reaction conditions may be set depending on the target reaction product. As will be demonstrated in the examples described later, according to the present invention, an organic compound usually synthesized through several reactions can be synthesized in one step, and the conversion rate of the reaction substrate is 100%. It is surprising that a yield of 95% can be obtained, which indicates that the present invention is an efficient synthesis method with very high compound selectivity. It is.
本発明は、二酸化炭素の存在下に、反応基質を反応させて有機化合物を合成するにあたり、少なくとも反応圧力を多段階に可変させる反応条件下で該有機化合物を合成する、新規な有機化合物の製造方法に係るものであり、本発明により、（１）従来、数段階の反応・分離操作を繰り返すことで合成していた工程を、反応容器内の化合物を、他の容器に移動させることなく、一段階で効率的に行うことが可能である有機化合物の製造方法を提供できる、（２）反応に選択性があり、有機化合物を、高い選択性で、高収率で製造することができる、（３）一段階反応であり、反応時間が５分〜１日という、短時間で複雑な化学反応を遂行できる、（４）本発明の方法は、反応時間が短いため、短時間に大量の化合物を製造するのに適している、（５）操作が簡便である、（６）有機溶媒、酸、アルカリ等を極力使用せずに反応を遂行できるため、生成物に不純物が混入する恐れが少ない、（７）媒体の二酸化炭素は、常温で気体であるため、生成物との分離が容易である、（８）廃水、廃物がほとんど発生しない合成方法であって、廃水、廃物の処理を必要としない、環境にやさしい有機合成方法を提供できる、という効果が奏される。 The present invention provides a novel organic compound that synthesizes an organic compound under reaction conditions in which at least a reaction pressure is varied in multiple steps when synthesizing an organic compound by reacting a reaction substrate in the presence of carbon dioxide. According to the present invention, according to the present invention, (1) a process conventionally synthesized by repeating several steps of reaction / separation operation, without moving the compound in the reaction vessel to another vessel, An organic compound production method that can be efficiently performed in one step can be provided. (2) The reaction is selective, and the organic compound can be produced with high selectivity and high yield. (3) It is a one-step reaction and can perform a complex chemical reaction in a short time of 5 minutes to 1 day. (4) Since the method of the present invention has a short reaction time, Suitable for producing compounds, 5) The operation is simple. (6) Since the reaction can be performed without using organic solvents, acids, alkalis, etc. as much as possible, there is little risk of impurities being mixed into the product. (7) Carbon dioxide as the medium is Since it is a gas at normal temperature, it can be easily separated from the product. (8) A synthesis method that generates almost no waste water or waste, and does not require waste water or waste treatment. The effect that it can provide is produced.
次に、本発明の、多段階可変超臨界有機合成製造法を、実施例に基づいて具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 Next, although the multistage variable supercritical organic synthetic | combination manufacturing method of this invention is demonstrated concretely based on an Example, this invention is not limited at all by these Examples.
本実施例では、バッチ式で、２−メチルシクロヘキサン-1,3-ジオンから、ステロイド環化生成物と同様の構造を有する８ａ−メチル−３，４，８，８ａ−テトラヒドロ−２Ｈ，７Ｈ−ナフタレン−１，６−ジオンを、多段階圧力・温度可変法で製造した。２５ｍＬの耐圧容器に２−メチルシクロヘキサン−１，３−ジオン０．２ｇ（１．６ｍｍｏｌ）、３−ブテン−２−オン０．２ｍL（２．３ｍｍｏｌ、１．４当量）、酸化マグネシウム５０ｍｇを入れた。耐圧容器中に、室温（２５℃）において、二酸化炭素を導入し、１ＭＰａの圧力にした。その後、これを１００℃の油浴に入れた後、更に、二酸化炭素を導入して圧力を１０ＭＰａに調整した後、２時間反応させた。その後、耐圧容器の温度を速やかに１８０℃にした後、更に、二酸化炭素を導入して圧力を２０ＭＰａにして２時間反応させた。反応後、氷水で耐圧容器を急冷し、十分容器が冷却された後に開封した。得られた生成物は、フィルターで触媒を除去した後、そのままエーテルで薄めて、ＧＣ−ＭＳ／ＭＳを用いて分析した。その結果、２−メチルシクロヘキサン−１，３−ジオンの転化率は、１００％であり、目的物である８ａ−メチル−３，４，８，８ａ−テトラヒドロ−２Ｈ，７Ｈ−ナフタレン−１，６−ジオンの収率は、９５％であった。 In this example, 8a-methyl-3,4,8,8a-tetrahydro-2H, 7H- having a structure similar to that of a steroid cyclization product is obtained from 2-methylcyclohexane-1,3-dione in a batch system. Naphthalene-1,6-dione was produced by a multistage pressure / temperature variable method. In a 25 mL pressure vessel, 0.2 g (1.6 mmol) of 2-methylcyclohexane-1,3-dione, 0.2 mL (2.3 mmol, 1.4 eq) of 3-buten-2-one, and 50 mg of magnesium oxide are placed. It was. Carbon dioxide was introduced into the pressure vessel at room temperature (25 ° C.) to a pressure of 1 MPa. Then, after putting this in an oil bath at 100 ° C., carbon dioxide was further introduced to adjust the pressure to 10 MPa, followed by reaction for 2 hours. Thereafter, the temperature of the pressure vessel was quickly raised to 180 ° C., and further carbon dioxide was introduced to make the pressure 20 MPa and to react for 2 hours. After the reaction, the pressure vessel was quenched with ice water and opened after the vessel was sufficiently cooled. After removing the catalyst with a filter, the obtained product was directly diluted with ether and analyzed using GC-MS / MS. As a result, the conversion rate of 2-methylcyclohexane-1,3-dione was 100%, and the target product 8a-methyl-3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6 The yield of dione was 95%.
本実施例では、バッチ式で、シクロヘキサン−１，３−ジオンから、ステロイド環化生成物と同様の構造を有する３，４，８，８ａ−テトラヒドロ−２Ｈ，７Ｈ−ナフタレン−１，６−ジオンを多段階圧力・温度可変法で製造した。２５ｍＬの耐圧容器に、２−メチルシクロヘキサン−１，３−ジオン０．２ｇ（１．８ｍｍｏｌ）、３−ブテン−２−オン０．２ｍＬ（２．３ｍｍｏｌ、１．３当量）、酸化マグネシウム５０ｍｇを入れた。耐圧容器に、室温（２５℃）において、二酸化炭素を導入して圧力を１ＭＰａにした。その後、これを３５℃の油浴に入れた後、更に、二酸化炭素を導入して圧力を８ＭＰａに調整した後、２時間反応させた。その後、耐圧容器の温度を速やかに１８０℃にした後、更に、二酸化炭素を導入して圧力を１５ＭＰａにして２時間反応させた。反応後、耐圧容器を氷水で急冷し、十分容器が冷却された後に開封した。得られた生成物は、フィルターで触媒を除去して、そのままエーテルで薄めた後、ＧＣ−ＭＳ／ＭＳを用いて分析した。その結果、シクロヘキサン−１，３−ジオンの転化率は、１００％であり、目的物である３，４，８，８ａ−テトラヒドロ−２Ｈ，７Ｈ−ナフタレン−１，６−ジオンの収率は、９４％であった。 In this example, 3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione having a structure similar to that of a steroid cyclization product is obtained from cyclohexane-1,3-dione in a batch system. Was manufactured by a multi-stage pressure and temperature variable method. In a 25 mL pressure vessel, 0.2 g (1.8 mmol) of 2-methylcyclohexane-1,3-dione, 0.2 mL (2.3 mmol, 1.3 eq) of 3-buten-2-one, and 50 mg of magnesium oxide were added. I put it in. Carbon dioxide was introduced into the pressure vessel at room temperature (25 ° C.) to make the pressure 1 MPa. Then, after putting this in an oil bath at 35 ° C., carbon dioxide was further introduced to adjust the pressure to 8 MPa, followed by reaction for 2 hours. Thereafter, the temperature of the pressure vessel was quickly raised to 180 ° C., and further carbon dioxide was introduced to make the pressure 15 MPa and to react for 2 hours. After the reaction, the pressure vessel was quenched with ice water and opened after the vessel was sufficiently cooled. The obtained product was analyzed by GC-MS / MS after removing the catalyst with a filter and diluting with ether as it was. As a result, the conversion rate of cyclohexane-1,3-dione was 100%, and the yield of 3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione as the target product was 94%.
実施例１と同様の条件で、２−メチルシクロヘキサノン０．２ｇ（１．８ｍｍｏｌ）、３−ブテン−２−オン０．２ｍＬ（２．３ｍｍｏｌ、１．３当量）、酸化マグネシウム５０ｍｇを用いて実験を行なった。その結果、２−メチルシクロヘキサノンの転化率は、８０％であり、目的物である４ａ−メチル−４，４ａ，５，６，７，８−ヘキサヒドロ−３Ｈ−ナフタレン−２−オンの収率は、７１％であった。 Experiments were performed under the same conditions as in Example 1 using 2-methylcyclohexanone 0.2 g (1.8 mmol), 3-buten-2-one 0.2 mL (2.3 mmol, 1.3 eq), and magnesium oxide 50 mg. Was done. As a result, the conversion rate of 2-methylcyclohexanone was 80%, and the yield of the target 4a-methyl-4,4a, 5,6,7,8-hexahydro-3H-naphthalen-2-one was 71%.
実施例１と同様の条件で、シクロヘキサノン０．２ｇ（２．０ｍｍｏｌ）、３−ブテン−２−オン０．２ｍＬ（２．３ｍｍｏｌ、１．２当量）、酸化マグネシウム５０ｍｇを用いて実験を行なった。その結果、シクロヘキサノンの転化率は、８０％であり、目的物である４，４ａ，５，６，７，８−ヘキサヒドロ−３Ｈ−ナフタレン−２−オンの収率は、７６％であった。 Under the same conditions as in Example 1, 0.2 g (2.0 mmol) of cyclohexanone, 0.2 mL (2.3 mmol, 1.2 equivalents) of 3-buten-2-one, and 50 mg of magnesium oxide were used. . As a result, the conversion of cyclohexanone was 80%, and the yield of 4,4a, 5,6,7,8-hexahydro-3H-naphthalen-2-one as the target product was 76%.
シクロへキサノンとその他のビニルケトン化合物との反応についても、実施例１と同様の条件で実験した。その結果を下記の表１に示す。 The reaction between cyclohexanone and other vinyl ketone compounds was also conducted under the same conditions as in Example 1. The results are shown in Table 1 below.
各種ケトン類とブテノンとの反応についても、実施例１と同様の条件で実験した。その結果を下記の表２に示す。 The reaction between various ketones and butenone was also conducted under the same conditions as in Example 1. The results are shown in Table 2 below.
本実施例では、実施例１と同様の実験において、温度を変化させない場合について実験し、バッチ式で２−メチルシクロヘキサン−１，３−ジオンから、ステロイド環化生成物と同様の構造を有する８ａ−メチル−３，４，８，８ａ−テトラヒドロ−２Ｈ，７Ｈ−ナフタレン−１，６−ジオンを圧力・温度が一定の条件で製造した。２５ｍＬの耐圧容器に２−メチルシクロヘキサン−１，３−ジオン０．２ｇ（１．６ｍｍｏｌ）、３−ブテン−２−オン０．２ｍＬ（２．３ｍｍｏｌ、１．４当量）、酸化マグネシウム５０ｍｇを入れた。耐圧容器に、室温（２５℃）において、二酸化炭素を導入して圧力を１ＭＰａの圧力にした。その後、これを１００℃の油浴に入れ、更に、二酸化炭素を導入し、表３に記載の圧力に調整した後、２時間反応させた。反応後、耐圧容器を、氷水で急冷し、十分容器が冷却された後に開封した。得られた生成物は、フィルターで触媒を除去してそのままエーテルで薄めて、ＧＣ−ＭＳ／ＭＳを用いて分析した。２−メチルシクロヘキサン−１，３−ジオンの転化率、目的物である８ａ−メチル−３，４，８，８ａ−テトラヒドロ−２Ｈ，７Ｈ−ナフタレン−１，６−ジオンの収率を表３に示す。 In this example, a case where the temperature was not changed in the same experiment as in Example 1 was conducted, and batchwise, from 2-methylcyclohexane-1,3-dione, 8a having the same structure as the steroid cyclization product -Methyl-3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione was produced under constant pressure and temperature conditions. Put 2-methylcyclohexane-1,3-dione 0.2 g (1.6 mmol), 3-buten-2-one 0.2 mL (2.3 mmol, 1.4 eq) and magnesium oxide 50 mg in a 25 mL pressure vessel. It was. Carbon dioxide was introduced into the pressure vessel at room temperature (25 ° C.) to make the pressure 1 MPa. Thereafter, this was put in an oil bath at 100 ° C., carbon dioxide was further introduced, and the pressure was adjusted to the values shown in Table 3, followed by reaction for 2 hours. After the reaction, the pressure vessel was quenched with ice water and opened after the vessel was sufficiently cooled. The obtained product was removed by using a filter, diluted with ether as it was, and analyzed using GC-MS / MS. Table 3 shows the conversion rate of 2-methylcyclohexane-1,3-dione and the yield of the target product 8a-methyl-3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione. Show.
実施例７と同様の実験において、温度を１８０℃にして実験した。２−メチルシクロヘキサン−１，３−ジオンの転化率、目的物である８ａ−メチル−３，４，８，８ａ−テトラヒドロ−２Ｈ，７Ｈ−ナフタレン−１，６−ジオンの収率を表４に示す。 In the same experiment as in Example 7, the experiment was performed at a temperature of 180 ° C. Table 4 shows the conversion rate of 2-methylcyclohexane-1,3-dione and the yield of the target product 8a-methyl-3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione. Show.
以上詳述したように、本発明は、二酸化炭素の存在下に、反応基質を反応させて有機化合物を合成するにあたり、少なくとも反応圧力を変化させる反応条件で該有機化合物を合成する、新規な有機化合物の製造方法に係るものであり、本発明により、二酸化炭素、即ち、超臨界二酸化炭素、亜臨界二酸化炭素ないし加圧二酸化炭素の存在下での反応において、圧力・温度を連続的に変化させることにより、各圧力・温度下における基質の二酸化炭素に対する溶解度が変化すること、そして、二酸化炭素の粘度が変化すること等を利用し、単純な温度・圧力の制御だけでは難しかった有機化合物を選択的・効率的に製造する技術を提供することができる。本発明は、化合物の選択的合成が可能であり、従来のように、合成反応・分離操作を繰返すことなく、一段階で、選択性及び収率の高い合成を可能とするものである。また、本発明の多段階可変超臨界有機合成は、反応基質を選ばず、短時間で、大量に、しかも、環境にやさしく、有機化合物を製造することができる、新規な有機合成方法として有用である。
As described above in detail, the present invention is a novel organic compound that synthesizes an organic compound under reaction conditions that change at least the reaction pressure when synthesizing an organic compound by reacting a reaction substrate in the presence of carbon dioxide. According to the present invention, the pressure and temperature are continuously changed in the reaction in the presence of carbon dioxide, that is, supercritical carbon dioxide, subcritical carbon dioxide or pressurized carbon dioxide. This makes it possible to select organic compounds that were difficult to control by simple temperature and pressure control, utilizing the fact that the solubility of the substrate in carbon dioxide under each pressure and temperature changes and the viscosity of carbon dioxide changes. It is possible to provide technology for efficient and efficient manufacturing. The present invention enables selective synthesis of compounds, and enables synthesis with high selectivity and yield in one step without repeating the synthesis reaction / separation operation as in the prior art. In addition, the multistage variable supercritical organic synthesis of the present invention is useful as a novel organic synthesis method that can produce organic compounds in a short time, in large quantities, and in an environmentally friendly manner, regardless of the reaction substrate. is there.
Claims (11)
The method for producing an organic compound according to claim 8, wherein the organic compound is a steroid cyclization product.
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