JP2006281203A - Catalyst composition comprising metal vanadate apatite and method for forming carbon-carbon bond using it - Google Patents
Catalyst composition comprising metal vanadate apatite and method for forming carbon-carbon bond using it Download PDFInfo
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- JP2006281203A JP2006281203A JP2006064968A JP2006064968A JP2006281203A JP 2006281203 A JP2006281203 A JP 2006281203A JP 2006064968 A JP2006064968 A JP 2006064968A JP 2006064968 A JP2006064968 A JP 2006064968A JP 2006281203 A JP2006281203 A JP 2006281203A
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000002184 metal Substances 0.000 title claims abstract description 54
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052586 apatite Inorganic materials 0.000 title claims abstract description 38
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 18
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims description 15
- 238000006957 Michael reaction Methods 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 16
- 238000006842 Henry reaction Methods 0.000 claims abstract description 14
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 11
- 238000005575 aldol reaction Methods 0.000 claims abstract description 11
- 238000010485 C−C bond formation reaction Methods 0.000 claims abstract description 8
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 18
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 100
- 150000001875 compounds Chemical class 0.000 abstract description 43
- 230000000694 effects Effects 0.000 abstract description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 abstract description 3
- 229910052805 deuterium Inorganic materials 0.000 abstract description 3
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- -1 alkali metal salts Chemical class 0.000 description 46
- 150000001728 carbonyl compounds Chemical class 0.000 description 35
- 238000004817 gas chromatography Methods 0.000 description 30
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 22
- 238000010813 internal standard method Methods 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 229910052755 nonmetal Inorganic materials 0.000 description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 14
- 150000002843 nonmetals Chemical group 0.000 description 14
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 11
- 150000001721 carbon Chemical group 0.000 description 11
- 150000002576 ketones Chemical class 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 125000006575 electron-withdrawing group Chemical group 0.000 description 10
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 10
- 150000002828 nitro derivatives Chemical class 0.000 description 10
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 6
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- JHZPNBKZPAWCJD-UHFFFAOYSA-N ethyl 2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCCC1=O JHZPNBKZPAWCJD-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexediene Natural products C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 5
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 5
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 5
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 5
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 4
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 4
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 4
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- GKKZMYDNDDMXSE-UHFFFAOYSA-N Ethyl 3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=CC=C1 GKKZMYDNDDMXSE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- FGSGHBPKHFDJOP-UHFFFAOYSA-N ethyl 2-oxocyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CCCCC1=O FGSGHBPKHFDJOP-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 3
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 3
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000004149 thio group Chemical group *S* 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- 0 *C(C#N)=C[C@]1CC=CCC1 Chemical compound *C(C#N)=C[C@]1CC=CCC1 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 2
- GSOHKPVFCOWKPU-UHFFFAOYSA-N 3-methylpentane-2,4-dione Chemical compound CC(=O)C(C)C(C)=O GSOHKPVFCOWKPU-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical class OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 150000003997 cyclic ketones Chemical class 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
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- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 239000010847 non-recyclable waste Substances 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Chemical group C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000003551 oxepanyl group Chemical group 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- VNXUJPCYZSNXDG-UHFFFAOYSA-N thiopyran-4-one Chemical group O=C1C=CSC=C1 VNXUJPCYZSNXDG-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、例えば、マイケル（Michael）反応、クネベナーゲル（Knoevenagel）反応、ヘンリー（Henry）反応、アルドール（Aldol）反応、ディールスアルダー（Diels-Alder）反応などの炭素−炭素結合形成反応、重水素化反応等の触媒として有用な金属バナジン酸アパタイトを含む触媒用組成物、および該触媒用組成物を用いた炭素−炭素結合形成方法及び重水素化方法に関する。 The present invention includes, for example, carbon-carbon bond forming reactions such as Michael reaction, Knoevenagel reaction, Henry reaction, Aldol reaction, Diels-Alder reaction, and deuteration. The present invention relates to a catalyst composition containing metal vanadate apatite useful as a catalyst for reaction and the like, and a carbon-carbon bond forming method and a deuteration method using the catalyst composition.
炭素−炭素結合の選択的な形成は、ファインケミカルズ合成の基幹となる反応プロセスであり、有機合成化学において重要な位置を占める。マイケル（Michael）反応、アルドール（Aldol）反応などでは、古くから酸塩基触媒として硫酸や塩酸などのブレンステッド酸、塩化アルミニウムやフッ化ホウ素などのルイス酸、又は水酸化ナトリウム、アルカリ金属アルコラート、アミン類に代表される均一系塩基が化学量論又は量論量近く使用されている。これらの試剤は反応性が高いものの、生成物との分離操作が煩雑で、回収・再使用が困難であり、反応器も耐腐食性の高いものを使用する必要がある。また、反応後の中和処理によって、多量の無機塩を再生不可能な廃棄物として生成することが多いため、反応のグリーン度が低いという問題がある。 The selective formation of carbon-carbon bonds is a reaction process that forms the basis of fine chemicals synthesis and occupies an important position in organic synthetic chemistry. In the Michael and Aldol reactions, acid-base catalysts such as Bronsted acids such as sulfuric acid and hydrochloric acid, Lewis acids such as aluminum chloride and boron fluoride, sodium hydroxide, alkali metal alcoholates, and amines have long been used. A homogeneous base typified by the class is used in a stoichiometric or near stoichiometric amount. Although these reagents have high reactivity, the separation operation from the product is complicated, recovery and reuse are difficult, and it is necessary to use a reactor having high corrosion resistance. In addition, since neutralization after the reaction often produces a large amount of inorganic salt as non-recyclable waste, there is a problem that the greenness of the reaction is low.
近年、中性条件下での均一系反応を可能とする有機金属錯体を用いた触媒反応も活発に研究されている（J. Am. Chem. Soc., 111, 5954(1989)など）。パラジウムやルテニウムなどの貴金属錯体やチタンなどの前周期遷移金属錯体を用いると、温和な条件下で炭素−炭素結合形成反応が進行するが、厳密な脱水条件を必要とすることや、反応後の生成物の分離、触媒の再使用が困難という実用上の問題がある。 In recent years, catalytic reactions using organometallic complexes that enable homogeneous reactions under neutral conditions have also been actively studied (J. Am. Chem. Soc., 111, 5954 (1989), etc.). When using a noble metal complex such as palladium or ruthenium or a transition metal complex such as titanium, the carbon-carbon bond formation reaction proceeds under mild conditions. However, strict dehydration conditions are required, There is a practical problem that it is difficult to separate the product and reuse the catalyst.
Mat. Res. Bull. Vol. 14, pp. 1479-1483, 1979には、硫酸カルシウム等の金属硫酸塩とバナジン酸ナトリウム等とをアルカリの存在下で反応させて種々のヒドロキシアパタイトを調製する方法が開示されている。しかし、こうして得られるヒドロキシアパタイトの触媒作用については全く記載がない。
本発明の目的は、安価で、且つ炭素−炭素結合形成反応や重水素化反応等に対して高い活性を示す固体触媒として有用な触媒用組成物を提供することにある。
本発明の他の目的は、反応に有機溶媒を必要とせず、目的化合物を簡易な手段で大量に製造でき、しかも生成物との分離及び再利用が容易な触媒組成物を提供することにある。
本発明の他の目的は、温和な反応条件下で反応が進行し、有機溶媒を必要とせず、目的化合物を簡易な手段で大量に製造でき、しかも生成物と触媒とを容易に分離できる炭素−炭素結合形成方法及び重水素化方法を提供することにある。
An object of the present invention is to provide a catalyst composition that is inexpensive and useful as a solid catalyst exhibiting high activity for carbon-carbon bond forming reaction, deuteration reaction, and the like.
Another object of the present invention is to provide a catalyst composition which does not require an organic solvent for the reaction, can produce the target compound in a large amount by a simple means, and can be easily separated from the product and reused. .
Another object of the present invention is carbon that allows the reaction to proceed under mild reaction conditions, does not require an organic solvent, can be produced in large quantities by a simple means, and can easily separate a product and a catalyst. -To provide a carbon bond formation method and a deuteration method.
本発明者らは、前記目的を達成するため鋭意検討した結果、バナジン酸塩（Ａ）と金属塩（Ｂ）との反応により容易に調製できる金属バナジン酸アパタイトが、マイケル（Michael）反応、クネベナーゲル（Knoevenagel）反応、ヘンリー（Henry）反応、アルドール（Aldol）反応、ディールスアルダー（Diels-Alder）反応などの炭素−炭素結合形成反応、及び重水素化反応等に極めて高い活性を示すことを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have found that a metal vanadate apatite that can be easily prepared by a reaction between a vanadate (A) and a metal salt (B) has a Michael reaction, a kunebener gel. (Knoevenagel) reaction, Henry (Henry) reaction, Aldol (Aldol) reaction, Diels-Alder reaction and other carbon-carbon bond formation reaction, deuteration reaction, etc. The present invention has been completed.
すなわち、本発明は、バナジン酸塩（Ａ）と金属塩（Ｂ）とを反応して得られる金属バナジン酸アパタイトを含む触媒用組成物を提供する。金属バナジン酸アパタイトには、下記の組成式（Ｉ）
Ｍ10-z（ＨＶＯ4）z（ＶＯ4）6-z（ＯＨ）2-z （Ｉ）
（式中、Ｍは金属原子を示し、０≦ｚ≦１である）
で表される化合物が含まれる。金属バナジン酸アパタイトとして、例えばカルシウムバナジン酸アパタイトが挙げられる。
That is, this invention provides the composition for catalysts containing the metal vanadate apatite obtained by reacting vanadate (A) and a metal salt (B). The metal vanadate apatite has the following composition formula (I)
M 10-z (HVO 4 ) z (VO 4 ) 6-z (OH) 2-z (I)
(In the formula, M represents a metal atom, and 0 ≦ z ≦ 1)
The compound represented by these is included. An example of the metal vanadate apatite is calcium vanadate apatite.
本発明は、また、上記の触媒用組成物の存在下、有機化合物を反応させて炭素−炭素結合を形成することを特徴とする炭素−炭素結合形成方法を提供する。この方法において、例えば、マイケル（Michael）反応、クネベナーゲル（Knoevenagel）反応、ヘンリー（Henry）反応、アルドール（Aldol）反応又はディールスアルダー（Diels-Alder）反応により炭素−炭素結合を形成してもよい。 The present invention also provides a carbon-carbon bond forming method characterized in that an organic compound is reacted in the presence of the above catalyst composition to form a carbon-carbon bond. In this method, a carbon-carbon bond may be formed by, for example, a Michael reaction, a Knoevenagel reaction, a Henry reaction, an Aldol reaction, or a Diels-Alder reaction.
本発明は、さらに、上記の触媒用組成物の存在下、有機化合物を重水と反応させて重水素化することを特徴とする重水素化方法を提供する。 The present invention further provides a deuteration method comprising deuterating an organic compound by reacting with deuterated water in the presence of the above catalyst composition.
本発明の触媒用組成物は、安価であり、且つ不均一系触媒として炭素−炭素結合形成反応、重水素化反応等に対して極めて高い活性及び選択性を示す。また、この触媒は、高い活性・選択性を保持したまま再利用が可能である。さらに、反応に有機溶媒を必要とせず、取扱性、反応の操作性に優れている。本発明の炭素−炭素結合形成方法及び重水素化方法によれば、温和な条件下で反応が進行し、有機溶媒を必要とせず、目的化合物を簡易な手段で且つ高い収率で得ることができ、しかも生成物と触媒とを容易に分離することができる。従って、目的物の大量生産に適しており、またグリーンケミストリー上、非常に有用である。 The catalyst composition of the present invention is inexpensive and exhibits extremely high activity and selectivity as a heterogeneous catalyst for carbon-carbon bond formation reaction, deuteration reaction, and the like. This catalyst can be reused while maintaining high activity and selectivity. Furthermore, an organic solvent is not required for the reaction, and the handling property and the operability of the reaction are excellent. According to the carbon-carbon bond forming method and the deuteration method of the present invention, the reaction proceeds under mild conditions, an organic solvent is not required, and the target compound can be obtained by a simple means and in a high yield. In addition, the product and the catalyst can be easily separated. Therefore, it is suitable for mass production of the object and is very useful in terms of green chemistry.
［触媒用組成物］
本発明の触媒用組成物は、バナジウム酸塩（＝バナジン酸塩）（Ａ）と金属塩（Ｂ）との反応により得られる金属バナジン酸アパタイトを含む。本発明の触媒用組成物は前記金属バナジン酸アパタイトのみで構成されていてもよく、金属バナジン酸アパタイトとともに他の成分を含んでいてもよい。バナジウム酸塩（Ａ）としては、オルトバナジウム酸塩（＝オルトバナジン酸塩）［Ｍ′I 3ＶＯ4（Ｍ′は金属原子を表す）］を使用できる。バナジウム酸塩（Ａ）の代表的な例として、バナジウム酸ナトリウム、バナジウム酸カリウム、バナジウム酸カルシウム、バナジウム酸ストロンチウムなどが挙げられる。
[Composition for catalyst]
The catalyst composition of the present invention contains metal vanadate apatite obtained by reaction of vanadate (= vanadate) (A) and metal salt (B). The catalyst composition of the present invention may be composed only of the metal vanadate apatite, and may contain other components together with the metal vanadate apatite. As the vanadate (A), orthovanadate (= orthovanadate) [M ′ I 3 VO 4 (M ′ represents a metal atom)] can be used. Typical examples of the vanadate (A) include sodium vanadate, potassium vanadate, calcium vanadate, strontium vanadate, and the like.
金属塩（Ｂ）には無機酸又は有機酸の金属塩が含まれる。該無機酸としては、硫酸、塩酸、硝酸、リン酸、ホウ酸、炭酸などが挙げられる。また、有機酸としては、酢酸などのカルボン酸、メタンスルホン酸などのスルホン酸が挙げられる。金属塩としては、例えば、ナトリウム塩、カリウム塩等のアルカリ金属塩；マグネシウム塩、カルシウム塩、ストロンチウム塩、バリウム塩等のアルカリ土類金属塩；亜鉛塩、ニッケル塩、カドミウム塩等の遷移金属塩などが挙げられる。好ましい金属塩（Ｂ）として、硫酸マグネシウム、硫酸カルシウム、硝酸カルシウム、塩化カルシウム、硫酸バリウム、硫酸ストロンチウムなどのアルカリ金属の無機酸塩が挙げられる。そのなかでも、カルシウムの無機酸塩、特に硫酸カルシウムが好ましい。 The metal salt (B) includes a metal salt of an inorganic acid or an organic acid. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, carbonic acid and the like. Examples of the organic acid include carboxylic acids such as acetic acid and sulfonic acids such as methanesulfonic acid. Examples of the metal salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt, calcium salt, strontium salt and barium salt; transition metal salts such as zinc salt, nickel salt and cadmium salt Etc. Preferred metal salts (B) include inorganic salts of alkali metals such as magnesium sulfate, calcium sulfate, calcium nitrate, calcium chloride, barium sulfate, and strontium sulfate. Of these, inorganic salts of calcium, particularly calcium sulfate, are preferred.
金属バナジン酸アパタイトには前記式（Ｉ）で表される組成式を有する化合物が含まれる。式（Ｉ）中、Ｍは金属原子を示し、０≦ｚ≦１である。Ｍは前記金属塩（Ｂ）に対応する金属である。従って、Ｍとして、アルカリ金属、アルカリ土類金属、遷移金属等が挙げられる。好ましい金属バナジン酸アパタイトは、Ｍがアルカリ土類金属であるアルカリ土類金属バナジン酸アパタイトである。特にＭがカルシウムであるカルシウムバナジン酸アパタイトが好ましい。ｚは、好ましくは０〜０．５の範囲であり、特に０であるのが好ましい。 The metal vanadate apatite includes a compound having the composition formula represented by the formula (I). In formula (I), M represents a metal atom and 0 ≦ z ≦ 1. M is a metal corresponding to the metal salt (B). Accordingly, examples of M include alkali metals, alkaline earth metals, and transition metals. A preferred metal vanadate apatite is an alkaline earth metal vanadate apatite where M is an alkaline earth metal. In particular, calcium vanadate apatite where M is calcium is preferable. z is preferably in the range of 0 to 0.5, particularly preferably 0.
金属バナジン酸アパタイトは、バナジウム酸塩（Ａ）と金属塩（Ｂ）とを、例えば水性溶媒中で反応させることにより製造することができる。水性溶媒としては、水、水と水溶性有機溶媒（メタノール、エタノール、エチレングリコール等のアルコール；アセトン等のケトン；テトラヒドロフラン、ジオキサン、ジメトキシエタン等のエーテル類；Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン性有機溶媒など）との混合液が挙げられる。これらの中でも水が好ましい。 The metal vanadate apatite can be produced by reacting the vanadate (A) with the metal salt (B), for example, in an aqueous solvent. Examples of aqueous solvents include water, water and water-soluble organic solvents (alcohols such as methanol, ethanol and ethylene glycol; ketones such as acetone; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; N, N-dimethylformamide, dimethyl sulfoxide and the like. And an aprotic organic solvent). Among these, water is preferable.
バナジウム酸塩（Ａ）の使用量は、金属塩（Ｂ）１モルに対して、例えば０．３〜１モル、好ましくは０．５〜０．７モル、さらに好ましくは約０．６モルである。 The amount of vanadate (A) used is, for example, 0.3-1 mol, preferably 0.5-0.7 mol, more preferably about 0.6 mol, per 1 mol of metal salt (B). is there.
バナジウム酸塩（Ａ）と金属塩（Ｂ）との反応は、通常、アルカリ存在下で行われる。アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；炭酸マグネシウム等のアルカリ土類金属炭酸塩；ナトリウムメトキシド、ナトリウムエトキシド等のアルカリ金属アルコキシドなどが挙げられる。アルカリの使用量は、金属塩（Ｂ）１モルに対して、例えば０．２〜１０モル、好ましくは０．５〜５モル、さらに好ましくは１〜３モル程度である。 The reaction between the vanadate (A) and the metal salt (B) is usually performed in the presence of an alkali. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Examples include alkaline earth metal carbonates such as magnesium carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide. The usage-amount of an alkali is 0.2-10 mol with respect to 1 mol of metal salts (B), Preferably it is 0.5-5 mol, More preferably, it is about 1-3 mol.
反応温度は、バナジウム酸塩（Ａ）の種類や金属塩（Ｂ）の種類によっても異なるが、通常１０〜２００℃、好ましくは５０〜１５０℃、さらに好ましくは７０〜１３０℃程度である。 Although reaction temperature changes also with the kind of vanadate (A) and the kind of metal salt (B), it is 10-200 degreeC normally, Preferably it is 50-150 degreeC, More preferably, it is about 70-130 degreeC.
バナジウム酸塩（Ａ）と金属塩（Ｂ）との反応により生成した固体を濾過、遠心分離等によって分離し、必要に応じて、水、アセトン等の水溶性有機溶媒で洗浄し、乾燥した後、焼成することにより目的の金属バナジン酸アパタイトを得ることができる。焼成温度は、例えば３００℃以上、好ましくは５００℃以上、さらに好ましくは７００℃以上である。焼成温度の上限は、溶融しない範囲であればよいが、操作性や比表面積の大きさ等を考慮すると、例えば１０００℃、好ましくは９００℃程度である。焼成して得られた金属バナジン酸アパタイトは、適当な大きさに粉砕して粒状、粉末状等の形態で、或いは粉末状のものを打錠、成形することにより使用に供される。 The solid produced by the reaction of vanadate (A) and metal salt (B) is separated by filtration, centrifugation, etc., washed with a water-soluble organic solvent such as water or acetone as necessary, and dried. The desired metal vanadate apatite can be obtained by firing. The firing temperature is, for example, 300 ° C. or higher, preferably 500 ° C. or higher, more preferably 700 ° C. or higher. The upper limit of the firing temperature may be within the range where it does not melt, but considering operability, the size of the specific surface area, and the like, it is, for example, about 1000 ° C, preferably about 900 ° C. The metal vanadate apatite obtained by firing is pulverized to an appropriate size and used in the form of granules, powders, etc., or by tableting and molding powders.
こうして得られる金属バナジン酸アパタイトは、酸−塩基の両機能を表面に持っており、例えば有機合成反応における固体触媒、不均一系触媒として有用である。金属バナジン酸アパタイトの比表面積は、一般に１０ｍ2／ｇ以上（例えば１０〜３００ｍ2／ｇ程度）、好ましくは１５ｍ2／ｇ以上（例えば１５〜１００ｍ2／ｇ程度）である。 The metal vanadate apatite thus obtained has both acid-base functions on the surface, and is useful as, for example, a solid catalyst or a heterogeneous catalyst in an organic synthesis reaction. The specific surface area of the metal vanadate apatite is generally 10 m 2 / g or more (e.g. 10~300m about 2 / g), preferably 15 m 2 / g or more (e.g. 15~100m about 2 / g).
［炭素−炭素結合形成方法］
本発明の炭素−炭素結合形成方法では、上記金属バナジン酸アパタイトを含む触媒用組成物の存在下、有機化合物を反応させて炭素−炭素結合を形成する。炭素−炭素結合を形成する反応の種類としては、特に限定されず、例えば、酸又は塩基を触媒として進行する広範囲の反応が挙げられる。なかでも、極めて有利に適用できる炭素−炭素結合形成反応として、マイケル（Michael）反応、クネベナーゲル（Knoevenagel）反応、アルドール（Aldol）反応、ディールスアルダー（Diels-Alder）反応、及びヘンリー反応が挙げられる。
[Method for forming carbon-carbon bond]
In the carbon-carbon bond forming method of the present invention, a carbon-carbon bond is formed by reacting an organic compound in the presence of the catalyst composition containing the metal vanadate apatite. The type of reaction that forms a carbon-carbon bond is not particularly limited, and examples thereof include a wide range of reactions that proceed using an acid or a base as a catalyst. Among them, examples of the carbon-carbon bond forming reaction that can be applied very advantageously include the Michael reaction, the Knoevenagel reaction, the Aldol reaction, the Diels-Alder reaction, and the Henry reaction.
［マイケル（Michael）反応］
マイケル反応（マイケル付加反応）は一般に下記反応式で表される。
The Michael reaction (Michael addition reaction) is generally represented by the following reaction formula.
この反応では、活性メチレン又は活性メチンを有する化合物（１）と、二重結合を構成する炭素原子に電子吸引基Ｚ2が結合したオレフィン化合物（２）とが反応して、化合物（１）における活性メチレン又は活性メチンを構成する炭素原子が化合物（２）における電子吸引基Ｚ2のβ位の炭素原子に結合した付加生成物（３）が生成する。なお、この反応は分子内でも起こりうる。 In this reaction, the compound (1) having active methylene or active methine reacts with the olefin compound (2) in which the electron-withdrawing group Z 2 is bonded to the carbon atom constituting the double bond, and in the compound (1) An addition product (3) is produced in which the carbon atoms constituting the active methylene or active methine are bonded to the β-position carbon atom of the electron withdrawing group Z 2 in the compound (2). This reaction can occur in the molecule.
前記Ｚ1、Ｚ2における電子吸引基としては、例えば、アシル基（例えば、ホルミル基、アセチル基、プロピオニル基、ブチリル基、バレリル基、ヘキサノイル基、アクリロイル基、メタクリロイル基、アセトアセチル基等のＣ1-10脂肪族アシル基；シクロヘキサンカルボニル基等のＣ3-15脂環式アシル基；ベンゾイル基等のＣ6-14芳香族アシル基；ピリジンカルボニル基等の複素環式アシル基など）、置換オキシカルボニル基（エステル基）（例えば、メトキシカルボニル基、エトキシカルボニル基、プロピルオキシカルボニル基、イソプロピルオキシカルボニル基、ブチルオキシカルボニル基、ｔ−ブチルオキシカルボニル基等のＣ1-10アルコキシ−カルボニル基；ビニルオキシカルボニル基等のＣ2-10アルケニルオキシカルボニル基；シクロヘキシルオキシ−カルボニル基等のＣ3-15シクロアルキルオキシカルボニル基；フェニルオキシカルボニル基等のＣ6-14アリールオキシ−カルボニル基；Ｃ7-15ベンジルオキシカルボニル基等のアラルキルオキシカルボニル基など）、置換若しくは無置換カルバモイル基（例えば、カルバモイル基、メチルカルバモイル基、ジメチルカルバモイル基など）、カルボキシル基、シアノ基、ニトロ基、アルキルスルフィニル基、硫黄酸基、硫黄酸エステル基（例えば、メタンスルホニル基、ｐ−トルエンスルホニル基など）、芳香族性環式基（例えば、フェニル基など）などが挙げられる。 Examples of the electron withdrawing group in Z 1 and Z 2 include, for example, acyl groups (eg, formyl group, acetyl group, propionyl group, butyryl group, valeryl group, hexanoyl group, acryloyl group, methacryloyl group, acetoacetyl group, etc.) 1-10 aliphatic acyl group; C 3-15 alicyclic acyl group such as cyclohexanecarbonyl group; C 6-14 aromatic acyl group such as benzoyl group; heterocyclic acyl group such as pyridinecarbonyl group), substitution Oxycarbonyl group (ester group) (for example, C 1-10 alkoxy-carbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, t-butyloxycarbonyl group; C 2-10 alkenyloxy group such as a vinyl oxycarbonyl group; Sik Such as C 7-15 aralkyloxycarbonyl group such as benzyloxycarbonyl group); carbonyl group - C 6-14 aryloxy such as phenyloxy carbonyl group; - hexyloxy C 3-15 cycloalkyloxy group such as a carbonyl group A substituted or unsubstituted carbamoyl group (for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, etc.), carboxyl group, cyano group, nitro group, alkylsulfinyl group, sulfur acid group, sulfur acid ester group (for example, methanesulfonyl group, p-toluenesulfonyl group and the like) and aromatic cyclic groups (for example, phenyl group and the like).
Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5における非金属原子含有基としては、例えば、ハロゲン原子、炭化水素基、複素環式基、カルボキシル基、置換オキシカルボニル基、置換若しくは無置換カルバモイル基、シアノ基、アシル基、ニトロ基、アルキルスルフィニル基、硫黄酸基、硫黄酸エステル基、ヒドロキシル基、置換オキシ基、メルカプト基、置換チオ基、置換若しくは無置換アミノ基、これらが複数個結合した基などが挙げられる。前記カルボキシル基、硫黄酸基、ヒドロキシル基、メルカプト基は保護基で保護されていてもよい。保護基としては、有機合成の分野で慣用の保護基を使用できる。 Examples of the nonmetal atom-containing group in R 1 , R 2 , R 3 , R 4 and R 5 include a halogen atom, a hydrocarbon group, a heterocyclic group, a carboxyl group, a substituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group. Group, cyano group, acyl group, nitro group, alkylsulfinyl group, sulfuric acid group, sulfuric acid ester group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, substituted or unsubstituted amino group And the like. The carboxyl group, sulfur acid group, hydroxyl group, and mercapto group may be protected with a protecting group. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.
前記ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素原子が挙げられる。炭化水素基としては、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらが複数結合した基が挙げられる。脂肪族炭化水素基として、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル、ヘキシル、デシル、ドデシル、テトラデシル、ヘキサデシル、ビニル、アリル、エチニル、１−プロピニル基などの炭素数１〜２０（好ましくは１〜１０、さらに好ましくは１〜８）程度の直鎖状又は分岐鎖状の脂肪族炭化水素基（アルキル基、アルケニル基、アルキニル基）などが挙げられる。脂環式炭化水素基としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘキセニル、シクロオクチル、シクロデシル、シクロドデシル、ノルボルニル、アダマンチル基などの炭素数３〜２０（好ましくは３〜１５）程度の脂環式炭化水素基（シクロアルキル基、シクロアルケニル基、橋架け炭素環式基等）などが挙げられる。芳香族炭化水素基としては、例えば、フェニル、ナフチル基などの炭素数６〜１４程度の芳香族炭化水素基などが挙げられる。 Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which a plurality of these are bonded. Examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, decyl, dodecyl, tetradecyl, hexadecyl, vinyl, allyl, ethynyl, 1-propynyl group, and the like. And a linear or branched aliphatic hydrocarbon group (alkyl group, alkenyl group, alkynyl group) having about 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 8). Examples of the alicyclic hydrocarbon group include about 3 to 20 (preferably 3 to 15) carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclooctyl, cyclodecyl, cyclododecyl, norbornyl, and adamantyl groups. And alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkenyl groups, bridged carbocyclic groups, etc.). Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 carbon atoms such as phenyl and naphthyl groups.
脂肪族炭化水素基と脂環式炭化水素基とが結合した基として、例えば、シクロペンチルメチル、シクロヘキシルメチル、シクロヘキシルエチル基などが挙げられる。また、脂肪族炭化水素基と芳香族炭化水素基とが結合した基として、例えば、ベンジル、２−フェニルエチル、１−フェニルエチル、３−フェニルプロピル等のアラルキル基；２−メチルフェニル、３−メチルフェニル、４−メチルフェニル基などが挙げられる。 Examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include a cyclopentylmethyl, cyclohexylmethyl, and cyclohexylethyl groups. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include, for example, an aralkyl group such as benzyl, 2-phenylethyl, 1-phenylethyl, 3-phenylpropyl; 2-methylphenyl, 3-phenyl Examples include methylphenyl and 4-methylphenyl groups.
Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5における非金属原子含有基としての複素環式基を構成する複素環には、芳香族性複素環及び非芳香族性複素環が含まれる。このような複素環としては、例えば、ヘテロ原子として酸素原子を含む複素環（例えば、フラン、テトラヒドロフラン、オキサゾール、イソオキサゾールなどの５員環、４−オキソ−４Ｈ−ピラン、テトラヒドロピラン、モルホリンなどの６員環、ベンゾフラン、イソベンゾフラン、４−オキソ−４Ｈ−クロメン、クロマン、イソクロマンなどの縮合環など）、ヘテロ原子としてイオウ原子を含む複素環（例えば、チオフェン、チアゾール、イソチアゾール、チアジアゾールなどの５員環、４−オキソ−４Ｈ−チオピランなどの６員環、ベンゾチオフェンなどの縮合環など）、ヘテロ原子として窒素原子を含む複素環（例えば、ピロール、ピロリジン、ピラゾール、イミダゾール、トリアゾールなどの５員環、ピリジン、ピリダジン、ピリミジン、ピラジン、ピペリジン、ピペラジンなどの６員環、インドール、インドリン、キノリン、アクリジン、ナフチリジン、キナゾリン、プリンなどの縮合環など）などが挙げられる。 The heterocyclic ring constituting the heterocyclic group as the non-metal atom-containing group in R 1 , R 2 , R 3 , R 4 , and R 5 includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. As such a heterocyclic ring, for example, a heterocyclic ring containing an oxygen atom as a hetero atom (for example, 5-membered ring such as furan, tetrahydrofuran, oxazole, isoxazole, 4-oxo-4H-pyran, tetrahydropyran, morpholine, etc. 6-membered ring, condensed ring such as benzofuran, isobenzofuran, 4-oxo-4H-chromene, chromane, isochroman, etc.), heterocycle containing a sulfur atom as a hetero atom (for example, 5 such as thiophene, thiazole, isothiazole, thiadiazole) 5-membered rings, 6-membered rings such as 4-oxo-4H-thiopyran, condensed rings such as benzothiophene, etc.), heterocycles containing nitrogen atoms as heteroatoms (eg, pyrrole, pyrrolidine, pyrazole, imidazole, triazole, etc.) Ring, pyridine, pyridazine, pyrimi Emissions, pyrazine, piperidine, 6-membered ring such as piperazine, indole, indoline, quinoline, acridine, naphthyridine, quinazoline, other condensed rings purine) and the like.
Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5における非金属原子含有基としての置換オキシカルボニル基、置換若しくは無置換カルバモイル基、アシル基、アルキルスルフィニル基、硫黄酸エステル基としては、前記電子吸引基として例示したものと同様の基が挙げられる。置換オキシ基としては、例えば、メトキシ、エトキシ、イソプロピルオキシ、ブトキシ基等のＣ1-6アルコキシ基；シクロヘキシルオキシ基等のシクロアルキルオキシ基；フェノキシ基等のアリールオキシ基；アセチルオキシ、プロピオニルオキシ基等のアシルオキシ基などが挙げられる。置換チオ基としては、例えば、メチルチオ、エチルチオ基等のＣ1-6アルキルチオ基；シクロヘキシルチオ基等のシクロアルキルチオ基；フェニルチオ基等のアリールチオ基；アセチルチオ基等のアシルチオ基などが挙げられる。置換若しくは無置換アミノ基としては、例えば、アミノ基；メチルアミノ、ジメチルアミノ、エチルアミノ、ジエチルアミノ基等のモノ又はジＣ1-6アルキルアミノ基などが挙げられる。 A substituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, an acyl group, an alkylsulfinyl group, and a sulfur acid ester group as a non-metal atom-containing group in R 1 , R 2 , R 3 , R 4 , and R 5 Examples thereof include the same groups as those exemplified as the suction group. Examples of the substituted oxy group include C 1-6 alkoxy groups such as methoxy, ethoxy, isopropyloxy, and butoxy groups; cycloalkyloxy groups such as cyclohexyloxy groups; aryloxy groups such as phenoxy groups; acetyloxy, propionyloxy groups And acyloxy groups such as Examples of the substituted thio group include C 1-6 alkylthio groups such as methylthio and ethylthio groups; cycloalkylthio groups such as cyclohexylthio groups; arylthio groups such as phenylthio groups; acylthio groups such as acetylthio groups. Examples of the substituted or unsubstituted amino group include an amino group; a mono- or di-C 1-6 alkylamino group such as methylamino, dimethylamino, ethylamino, and diethylamino group.
Ｚ1、Ｒ1、Ｒ2のうち少なくとも２つが結合して隣接する炭素原子とともに形成する環、Ｚ2、Ｒ3、Ｒ4、Ｒ5のうち少なくとも２つが結合して隣接する炭素原子又は炭素−炭素二重結合とともに形成する環としては、例えば、シクロプロパン環、シクロブタン環、シクロペンタン環、シクロペンテン環、シクロヘキサン環、シクロヘキセン環、シクロオクタン環、シクロデカン環、シクロドデカン環、デカリン環、ノルボルナン環、ノルボルネン環、アダマンタン環などの３〜２０員（好ましくは３〜１５員）程度の非芳香族性炭素環（シクロアルカン環、シクロアルケン環、橋かけ炭素環）；ピロリジン環、ピペリジン環、ピペラジン環、モルホリン環、オキシラン環、オキセタン環、オキソラン環、オキサン環、オキセパン環、チオラン環、チアン環などの窒素原子、酸素原子及び硫黄原子からなる群より選択された少なくとも１種のヘテロ原子を有する非芳香族性複素環が挙げられる。これらの環は、置換基を有していてもよく、また他の環（非芳香族性環又は芳香族性環）が縮合していてもよい。 A ring formed by bonding at least two of Z 1 , R 1 and R 2 together with an adjacent carbon atom, an adjacent carbon atom or carbon formed by bonding at least two of Z 2 , R 3 , R 4 and R 5 Examples of the ring formed together with the carbon double bond include, for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, cyclooctane ring, cyclodecane ring, cyclododecane ring, decalin ring, norbornane ring , Norbornene ring, adamantane ring and the like non-aromatic carbocyclic ring (cycloalkane ring, cycloalkene ring, bridged carbocyclic ring) of about 3 to 20 members (preferably 3 to 15 members); pyrrolidine ring, piperidine ring, piperazine Ring, morpholine ring, oxirane ring, oxetane ring, oxolane ring, oxane ring, oxepane ring, thio Non-aromatic heterocycles having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, such as a lan ring and a thian ring. These rings may have a substituent, and other rings (non-aromatic ring or aromatic ring) may be condensed.
Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5としては、特に、水素原子、置換基を有していてもよい炭化水素基であるのが好ましい。また、Ｚ1、Ｒ1、Ｒ2のうち少なくとも２つが結合して隣接する炭素原子とともに非芳香族性炭素環を構成するのも好ましい。また、式（１）において、Ｒ1、Ｒ2のうち少なくとも１つは電子吸引基であるのが好ましい。 R 1 , R 2 , R 3 , R 4 and R 5 are particularly preferably a hydrogen atom or a hydrocarbon group which may have a substituent. It is also preferred that at least two of Z 1 , R 1 and R 2 are bonded to form a non-aromatic carbocycle together with adjacent carbon atoms. In formula (1), at least one of R 1 and R 2 is preferably an electron withdrawing group.
活性メチレン又は活性メチンを有する化合物（１）の代表的な例として、マロン酸ジメチル、マロン酸ジエチル等のマロン酸エステル；シアノ酢酸メチル、シアノ酢酸エチル等のシアノ酢酸エステル；アセト酢酸メチル、アセト酢酸エチル、３−オキソペンタン酸メチル、３−オキソペンタン酸エチル、２−メチル−３−オキソブタン酸メチル、２−メチル−３−オキソブタン酸エチル、ベンゾイル酢酸メチル、ベンゾイル酢酸エチル、２−オキソシクロペンタンカルボン酸メチル、２−オキソシクロペンタンカルボン酸エチル、２−オキソシクロヘキサンカルボン酸メチル、２−オキソシクロヘキサンカルボン酸エチルなどのβ−ケトエステル；アセチルアセトン、３−メチル−２，４−ペンタンジオン、２−アセチルシクロヘキサン−１−オン、２−アセチルシクロペンタン−１−オンなどのβ−ジケトン；酢酸エチル、酢酸プロピル等のカルボン酸エステル；アセトン、アセトフェノン、ベンゾフェノン等のケトン及び対応するケタール；アセトアルデヒド、プロピオンアルデヒド等のアルデヒド及び対応するアセタール；アセトニトリル、プロピオニトリル等のニトリル；ニトロメタン等のニトロ化合物；スルホン類；インデン、フルオレンなどの芳香環と非芳香族性炭素環との縮合化合物などが挙げられる。 Representative examples of the compound (1) having active methylene or active methine include malonic acid esters such as dimethyl malonate and diethyl malonate; cyanoacetic acid esters such as methyl cyanoacetate and ethyl cyanoacetate; methyl acetoacetate and acetoacetic acid Ethyl, methyl 3-oxopentanoate, ethyl 3-oxopentanoate, methyl 2-methyl-3-oxobutanoate, ethyl 2-methyl-3-oxobutanoate, methyl benzoyl acetate, ethyl benzoyl acetate, 2-oxocyclopentanecarboxylic Β-ketoesters such as methyl acetate, ethyl 2-oxocyclopentanecarboxylate, methyl 2-oxocyclohexanecarboxylate, ethyl 2-oxocyclohexanecarboxylate; acetylacetone, 3-methyl-2,4-pentanedione, 2-acetylcyclohexane -1 Β-diketones such as ON and 2-acetylcyclopentan-1-one; carboxylic acid esters such as ethyl acetate and propyl acetate; ketones such as acetone, acetophenone, and benzophenone and corresponding ketals; aldehydes such as acetaldehyde and propionaldehyde, and corresponding Acetals; nitriles such as acetonitrile and propionitrile; nitro compounds such as nitromethane; sulfones; and condensed compounds of aromatic rings such as indene and fluorene and non-aromatic carbocycles.
二重結合を構成する炭素原子に電子吸引基Ｚ2が結合したオレフィン化合物（２）の代表的な例として、アクリル酸メチル、アクリル酸エチル等のα，β−不飽和カルボン酸エステル；メチルビニルケトン、２−シクロヘキセン−１−オン等のα，β−不飽和ケトン；アクロレイン等のα，β−不飽和アルデヒド；アクリロニトリル等のα，β−不飽和ニトリル；α，β−不飽和ニトロ化合物；α，β−不飽和スルホン化合物などが挙げられる。 As typical examples of the olefin compound (2) in which the electron withdrawing group Z 2 is bonded to the carbon atom constituting the double bond, α, β-unsaturated carboxylic acid ester such as methyl acrylate and ethyl acrylate; methyl vinyl Α, β-unsaturated ketones such as ketone and 2-cyclohexen-1-one; α, β-unsaturated aldehydes such as acrolein; α, β-unsaturated nitriles such as acrylonitrile; α, β-unsaturated nitro compounds; Examples include α, β-unsaturated sulfone compounds.
反応は、溶媒の存在下又は非存在下で行われる。溶媒としては、水、有機溶媒、これらの混合溶媒の何れであってもよいが、特に水が好ましい。 The reaction is carried out in the presence or absence of a solvent. The solvent may be water, an organic solvent, or a mixed solvent thereof, but water is particularly preferable.
化合物（１）と化合物（２）との比率は適宜選択できるが、一般に、化合物（２）の使用量は、化合物（１）１モルに対して、０．５〜３モル、好ましくは０．８〜１．８程度である。金属バナジン酸アパタイト触媒の使用量は原料成分の種類によっても異なるが、バナジウム（Ｖ）として、化合物（１）に対して、例えば０．０００１〜１０モル％、好ましくは０．０００５〜５モル％程度の範囲で適宜選択できる。反応温度は原料成分の種類等に応じて適宜選択でき、例えば０〜１５０℃、好ましくは２０〜１００℃程度である。反応は、回分式、半回分式、連続式等の慣用の方式で行うことができる。反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、吸着、カラムクロマトグラフィーなどの分離手段やこれらを組み合わせた分離手段により分離精製できる。 The ratio of the compound (1) to the compound (2) can be selected as appropriate. In general, the amount of the compound (2) used is 0.5 to 3 mol, preferably 0. It is about 8 to 1.8. Although the usage-amount of a metal vanadate apatite catalyst changes also with the kind of raw material component, 0.0001-10 mol% with respect to a compound (1) as vanadium (V), Preferably it is 0.0005-5 mol%. It can select suitably in the range of a grade. The reaction temperature can be appropriately selected according to the type of raw material components, and is, for example, about 0 to 150 ° C., preferably about 20 to 100 ° C. The reaction can be carried out in a conventional manner such as batch, semi-batch, or continuous. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, etc., or a separation means combining these.
なお、前記活性メチレン又は活性メチンを有する化合物（１）に代えて、アミン等の他の活性水素を有する化合物を用いることもできる。この場合も、同様の付加反応が進行し、対応する付加生成物を得ることができる。 In addition, it can replace with the compound (1) which has the said active methylene or active methine, and can also use the compound which has other active hydrogens, such as an amine. In this case as well, the same addition reaction proceeds and the corresponding addition product can be obtained.
［クネベナーゲル（Knoevenagel）反応］
クネベナーゲル反応は一般に下記反応式で表される。
The Kunebenergel reaction is generally represented by the following reaction formula.
この反応では、活性メチレンを有する化合物（４）と、カルボニル化合物（５）とが反応して、脱水縮合したオレフィン化合物（６）が生成する。なお、この反応は分子内でも起こりうる。 In this reaction, the compound (4) having active methylene reacts with the carbonyl compound (5) to produce a dehydrated condensed olefin compound (6). This reaction can occur in the molecule.
Ｚ3、Ｚ4における電子吸引基としては、前記Ｚ1、Ｚ2における電子吸引基と同様のものが挙げられる。Ｒ6、Ｒ7における非金属原子含有基としては、前記Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5における非金属原子含有基と同様のものが挙げられる。Ｚ3、Ｚ4が互いに結合して隣接する炭素原子とともに形成する環、Ｒ6、Ｒ7が互いに結合して隣接する炭素原子とともに形成する環としては、前記Ｚ1、Ｒ1、Ｒ2のうち少なくとも２つが結合して隣接する炭素原子とともに形成する環と同様の環が挙げられる。Ｒ6、Ｒ7としては、特に、水素原子、置換基を有していてもよい炭化水素基であるのが好ましい。また、Ｒ6、Ｒ7のうち一方は水素原子であるのが好ましい。 Examples of the electron withdrawing group in Z 3 and Z 4 include the same electron withdrawing groups in Z 1 and Z 2 . Examples of the non-metal atom-containing group in R 6 and R 7 include the same non-metal atom-containing groups in R 1 , R 2 , R 3 , R 4 and R 5 . The ring formed by Z 3 and Z 4 bonded together and adjacent carbon atoms, and the ring formed by R 6 and R 7 bonded together and adjacent carbon atoms include Z 1 , R 1 and R 2 . The ring similar to the ring which at least 2 couple | bonds together and it forms with the adjacent carbon atom is mentioned. R 6 and R 7 are particularly preferably a hydrogen atom or a hydrocarbon group which may have a substituent. One of R 6 and R 7 is preferably a hydrogen atom.
活性メチレンを有する化合物（４）の代表的な例として、マロン酸ジメチル、マロン酸ジエチル等のマロン酸エステル；シアノ酢酸メチル、シアノ酢酸エチル等のシアノ酢酸エステル；アセト酢酸メチル、アセト酢酸エチル、３−オキソペンタン酸メチル、３−オキソペンタン酸エチル、ベンゾイル酢酸メチル、ベンゾイル酢酸エチルなどのβ−ケトエステル；アセチルアセトンなどのβ−ジケトンなどが挙げられる。 Representative examples of the compound (4) having active methylene include malonic acid esters such as dimethyl malonate and diethyl malonate; cyanoacetic acid esters such as methyl cyanoacetate and ethyl cyanoacetate; methyl acetoacetate, ethyl acetoacetate, 3 -Β-ketoesters such as methyl oxopentanoate, ethyl 3-oxopentanoate, methyl benzoylacetate and ethyl benzoylacetate; and β-diketones such as acetylacetone.
カルボニル化合物（５）の代表的な例として、アセトアルデヒド、プロピオンアルデヒド、ヘキサナール、フェニルアセトアルデヒド、シクロヘキサンカルボアルデヒド、３−シクロヘキセニルアルデヒド、ベンズアルデヒド、ｐ−メトキシベンズアルデヒド、ｐ−クロロベンズアルデヒド、シンナムアルデヒド、ピリジンカルボアルデヒドなどのアルデヒド（脂肪族アルデヒド、脂環式アルデヒド、芳香族アルデヒド、複素環アルデヒド等）；アセトン、メチルエチルケトン、３−ペンタノン、アセトフェノン、ベンゾフェノン、アセチルピリジン、シクロペンタノン、シクロヘキサノン、１−インダノンなどのケトン（鎖状ケトン、環状ケトン）が挙げられる。 Representative examples of the carbonyl compound (5) include acetaldehyde, propionaldehyde, hexanal, phenylacetaldehyde, cyclohexanecarbaldehyde, 3-cyclohexenylaldehyde, benzaldehyde, p-methoxybenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, pyridinecarbaldehyde. Aldehydes (aliphatic aldehydes, alicyclic aldehydes, aromatic aldehydes, heterocyclic aldehydes, etc.); ketones such as acetone, methyl ethyl ketone, 3-pentanone, acetophenone, benzophenone, acetylpyridine, cyclopentanone, cyclohexanone, 1-indanone (Chain ketone, cyclic ketone).
反応は、溶媒の存在下又は非存在下で行われる。溶媒としては、水、有機溶媒、これらの混合溶媒の何れであってもよいが、なかでも水、エタノール等のアルコール、ジメチルスルホキシド等の非プロトン性極性溶媒、又はこれらの混合溶媒が好ましく、とりわけ水が好ましい。 The reaction is carried out in the presence or absence of a solvent. The solvent may be any of water, an organic solvent, and a mixed solvent thereof. Among them, water, an alcohol such as ethanol, an aprotic polar solvent such as dimethyl sulfoxide, or a mixed solvent thereof is preferable. Water is preferred.
化合物（４）と化合物（５）との比率は適宜選択できるが、一般に、化合物（５）の使用量は、化合物（４）１モルに対して、０．５〜２モル、好ましくは０．８〜１．５程度である。金属バナジン酸アパタイト触媒の使用量は原料成分の種類によっても異なるが、バナジウム（Ｖ）として、化合物（４）に対して、例えば０．０００１〜１０モル％、好ましくは０．０００５〜５モル％程度の範囲で適宜選択できる。反応温度は原料成分の種類等に応じて適宜選択でき、例えば０〜１２０℃、好ましくは１０〜６０℃程度である。反応は、回分式、半回分式、連続式等の慣用の方式で行うことができる。反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、吸着、カラムクロマトグラフィーなどの分離手段やこれらを組み合わせた分離手段により分離精製できる。 Although the ratio of the compound (4) to the compound (5) can be appropriately selected, the amount of the compound (5) used is generally 0.5 to 2 mol, preferably 0. It is about 8 to 1.5. Although the usage-amount of a metal vanadate apatite catalyst changes also with the kind of raw material component, 0.0001-10 mol% with respect to a compound (4) as vanadium (V), Preferably it is 0.0005-5 mol%. It can select suitably in the range of a grade. The reaction temperature can be appropriately selected according to the type of raw material components, and is, for example, about 0 to 120 ° C., preferably about 10 to 60 ° C. The reaction can be carried out in a conventional manner such as batch, semi-batch, or continuous. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, etc., or a separation means combining these.
［アルドール（Aldol）反応］
アルドール反応は一般に下記反応式で表される。
The aldol reaction is generally represented by the following reaction formula.
この反応では、カルボニル化合物（７）と、カルボニル基の隣接位にメチレン基を有するカルボニル化合物（８）とが反応して、対応するアルドール化合物（β−ヒドロキシカルボニル化合物）（９）が生成し、条件によっては、さらに脱水反応が進行して対応するα，β−不飽和カルボニル化合物（１０）が生成する。なお、分子内に２つのカルボニル基（一方のカルボニル基の隣接位にはメチレン基が存在する）を有する化合物は分子内でアルドール反応が進行して、対応するアルドール化合物及び／又はα，β−不飽和カルボニル化合物が生成する。 In this reaction, the carbonyl compound (7) and the carbonyl compound (8) having a methylene group adjacent to the carbonyl group react to produce the corresponding aldol compound (β-hydroxycarbonyl compound) (9), Depending on the conditions, the dehydration reaction further proceeds to produce the corresponding α, β-unsaturated carbonyl compound (10). A compound having two carbonyl groups in the molecule (a methylene group is adjacent to one of the carbonyl groups) undergoes an aldol reaction in the molecule, and the corresponding aldol compound and / or α, β- An unsaturated carbonyl compound is formed.
Ｒ8、Ｒ9、Ｒ10、Ｒ11における非金属原子含有基としては、前記Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5における非金属原子含有基と同様のものが挙げられる。Ｒ8、Ｒ9が互いに結合して隣接する炭素原子とともに形成する環、Ｒ10、Ｒ11が互いに結合して隣接する炭素鎖とともに形成する環としては、前記Ｚ1、Ｒ1、Ｒ2のうち少なくとも２つが結合して隣接する炭素原子とともに形成する環と同様の環が挙げられる。Ｒ8、Ｒ9、Ｒ11としては、特に、置換基を有していてもよい炭化水素基であるのが好ましい。Ｒ10としては、特に、水素原子、又は置換基を有していてもよい炭化水素基であるのが好ましい。 Examples of the non-metal atom-containing group in R 8 , R 9 , R 10 , and R 11 include the same non-metal atom-containing groups in R 1 , R 2 , R 3 , R 4 , and R 5 . Examples of the ring formed by R 8 and R 9 being bonded together and adjacent carbon atoms, and the ring formed by R 10 and R 11 being bonded together and adjacent carbon chains are Z 1 , R 1 and R 2 . The ring similar to the ring which at least 2 couple | bonds together and it forms with the adjacent carbon atom is mentioned. R 8 , R 9 and R 11 are particularly preferably a hydrocarbon group which may have a substituent. R 10 is particularly preferably a hydrogen atom or a hydrocarbon group which may have a substituent.
カルボニル化合物（７）の代表的な例としては、前記カルボニル化合物（５）の代表的な例と同様の化合物が挙げられる。カルボニル基の隣接位にメチレン基を有するカルボニル化合物（８）の代表的な例として、アセトアルデヒド、プロピオンアルデヒド、ヘキサナール、フェニルアセトアルデヒドなどのアルデヒド；アセトン、アセトフェノン、アセチルピリジン、シクロペンタノン、シクロヘキサノンなどのケトン（鎖状ケトン、環状ケトン）が挙げられる。また、分子内に２つのカルボニル基（一方のカルボニル基の隣接位にはメチレン基が存在する）を有する化合物として、例えば、２，５−ヘキサンジオンなどが挙げられる。 Typical examples of the carbonyl compound (7) include the same compounds as the representative examples of the carbonyl compound (5). Representative examples of the carbonyl compound (8) having a methylene group adjacent to the carbonyl group include aldehydes such as acetaldehyde, propionaldehyde, hexanal, and phenylacetaldehyde; ketones such as acetone, acetophenone, acetylpyridine, cyclopentanone, and cyclohexanone. (Chain ketone, cyclic ketone). In addition, examples of the compound having two carbonyl groups in the molecule (a methylene group is present adjacent to one carbonyl group) include 2,5-hexanedione.
反応は、溶媒の存在下又は非存在下で行われる。溶媒としては、水、有機溶媒、これらの混合溶媒の何れであってもよいが、なかでも水、エタノール等のアルコール、ジメチルスルホキシド等の非プロトン性極性溶媒、又はこれらの混合溶媒が好ましく、とりわけ水が好ましい。 The reaction is carried out in the presence or absence of a solvent. The solvent may be any of water, an organic solvent, and a mixed solvent thereof. Among them, water, an alcohol such as ethanol, an aprotic polar solvent such as dimethyl sulfoxide, or a mixed solvent thereof is preferable. Water is preferred.
化合物（７）と化合物（８）との比率は適宜選択できるが、一般に、化合物（８）の使用量は、化合物（７）１モルに対して、０．５〜２モル、好ましくは０．８〜１．５程度である。金属バナジン酸アパタイト触媒の使用量は原料成分の種類によっても異なるが、バナジウム（Ｖ）として、化合物（７）に対して、例えば０．０００１〜１０モル％、好ましくは０．０００５〜５モル％程度の範囲で適宜選択できる。反応温度は原料成分の種類等に応じて適宜選択でき、例えば０〜１２０℃、好ましくは１０〜６０℃程度である。反応は、回分式、半回分式、連続式等の慣用の方式で行うことができる。反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、吸着、カラムクロマトグラフィーなどの分離手段やこれらを組み合わせた分離手段により分離精製できる。 The ratio of the compound (7) to the compound (8) can be appropriately selected. Generally, the amount of the compound (8) used is 0.5 to 2 mol, preferably 0. It is about 8 to 1.5. Although the usage-amount of a metal vanadate apatite catalyst changes also with the kind of raw material component, 0.0001-10 mol% with respect to a compound (7) as vanadium (V), Preferably it is 0.0005-5 mol%. It can select suitably in the range of a grade. The reaction temperature can be appropriately selected according to the type of raw material components, and is, for example, about 0 to 120 ° C., preferably about 10 to 60 ° C. The reaction can be carried out in a conventional manner such as batch, semi-batch, or continuous. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, etc., or a separation means combining these.
［ディールスアルダー（Diels-Alder）反応］
ディールスアルダー反応は一般に下記反応式で表される。
The Diels-Alder reaction is generally represented by the following reaction formula.
この反応では、ジエン（１１）と、ジエノフィル［アルケン（１２ａ）又はアルキン（１２ｂ）］とが反応（付加）して、対応する環化生成物［シクロヘキセン化合物（１３ａ）又はシクロヘキサジエン化合物（１３ｂ）］が生成する。なお、この反応は分子内でも起こりうる。 In this reaction, diene (11) and dienophile [alkene (12a) or alkyne (12b)] react (add), and the corresponding cyclized product [cyclohexene compound (13a) or cyclohexadiene compound (13b) ] Is generated. This reaction can occur in the molecule.
Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16、Ｒ17、Ｒ18、Ｒ19、Ｒ20、Ｒ21、Ｒ22、Ｒ23における非金属原子含有基としては、前記Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5における非金属原子含有基と同様のものが挙げられる。Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16、Ｒ17のうち少なくとも２つが互いに結合して形成する環、Ｒ18、Ｒ19、Ｒ20、Ｒ21のうち少なくとも２つが互いに結合して形成する環としては、前記Ｚ1、Ｒ1、Ｒ2のうち少なくとも２つが結合して隣接する炭素原子とともに形成する環と同様の環が挙げられる。Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16、Ｒ17としては、特に、水素原子又は置換基を有していてもよい炭化水素基であるのが好ましい。Ｒ19、Ｒ21の少なくとも一方、Ｒ22、Ｒ23の少なくとも一方は電子吸引基であるのが好ましい。 Non-metal atom-containing groups in R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 are the above R 1 , R 2 , R 3 , R 4 and R 5 are the same as the non-metal atom-containing groups. A ring formed by bonding at least two of R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 , and at least two of R 18 , R 19 , R 20 , and R 21 are bonded to each other; Examples of the ring to be formed include the same ring as the ring formed by combining at least two of Z 1 , R 1 and R 2 together with the adjacent carbon atom. R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are particularly preferably a hydrogen atom or a hydrocarbon group which may have a substituent. At least one of R 19 and R 21 and at least one of R 22 and R 23 are preferably an electron withdrawing group.
ジエン（１１）の代表的な例として、１，３−シクロヘキサジエン、シクロペンタジエン、１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエンなどが挙げられる。ジエノフィル［アルケン（１２ａ）又はアルキン（１２ｂ）］の代表的な例として、アクロレイン等のα，β−不飽和アルデヒド；メチルビニルケトン、キノン等のα，β−不飽和ケトン；アクリル酸メチル、アクリル酸エチル等のα，β−不飽和カルボン酸エステル；無水マレイン酸等のα，β−不飽和酸無水物などが挙げられる。 Representative examples of the diene (11) include 1,3-cyclohexadiene, cyclopentadiene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene and the like. As typical examples of dienophile [alkene (12a) or alkyne (12b)], α, β-unsaturated aldehydes such as acrolein; α, β-unsaturated ketones such as methyl vinyl ketone and quinone; methyl acrylate, acrylic Examples include α, β-unsaturated carboxylic acid esters such as ethyl acid; α, β-unsaturated acid anhydrides such as maleic anhydride.
反応は、溶媒の存在下又は非存在下で行われる。溶媒としては、水、有機溶媒、これらの混合溶媒の何れであってもよい。好ましい溶媒にはニトロメタン等のニトロ化合物が含まれる。 The reaction is carried out in the presence or absence of a solvent. As a solvent, any of water, an organic solvent, and these mixed solvents may be sufficient. Preferred solvents include nitro compounds such as nitromethane.
化合物（１１）と化合物（１２ａ）又は（１２ｂ）との比率は適宜選択できるが、一般に、化合物（１２ａ）又は（１２ｂ）の使用量は、化合物（１１）１モルに対して、０．５〜２モル、好ましくは０．８〜１．５程度である。金属バナジン酸アパタイト触媒の使用量は原料成分の種類によっても異なるが、バナジウム（Ｖ）として、化合物（１１）に対して、例えば０．０００１〜１０モル％、好ましくは０．０００５〜５モル％程度の範囲で適宜選択できる。反応温度は原料成分の種類等に応じて適宜選択でき、例えば０〜１２０℃、好ましくは１０〜６０℃程度である。反応は、回分式、半回分式、連続式等の慣用の方式で行うことができる。反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、吸着、カラムクロマトグラフィーなどの分離手段やこれらを組み合わせた分離手段により分離精製できる。 The ratio of the compound (11) and the compound (12a) or (12b) can be selected as appropriate. Generally, the amount of the compound (12a) or (12b) used is 0.5 with respect to 1 mol of the compound (11). ˜2 mol, preferably about 0.8 to 1.5. Although the usage-amount of a metal vanadate apatite catalyst changes also with the kind of raw material component, 0.0001-10 mol% with respect to a compound (11) as vanadium (V), Preferably it is 0.0005-5 mol%. It can select suitably in the range of a grade. The reaction temperature can be appropriately selected according to the type of raw material components, and is, for example, about 0 to 120 ° C., preferably about 10 to 60 ° C. The reaction can be carried out in a conventional manner such as batch, semi-batch, or continuous. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, etc., or a separation means combining these.
［ヘンリー（Henry）反応］
ヘンリー反応は一般に下記反応式で表される。
The Henry reaction is generally represented by the following reaction formula.
この反応では、カルボニル化合物（１４）と、ニトロ基の隣接位にメチレン基を有するニトロ化合物（１５）とが反応して、対応するβ−ヒドロキシニトロ化合物（１６ａ）及び／又は１，３−ジニトロ化合物（１６ｂ）が生成する。なお、分子内にカルボニル基とニトロ基（ニトロ基の隣接位にはメチレン基が存在する）を有する化合物は分子内でヘンリー反応が進行する場合がある。 In this reaction, the carbonyl compound (14) reacts with the nitro compound (15) having a methylene group at the position adjacent to the nitro group, and the corresponding β-hydroxynitro compound (16a) and / or 1,3-dinitro Compound (16b) is produced. A compound having a carbonyl group and a nitro group in the molecule (a methylene group is present adjacent to the nitro group) may undergo a Henry reaction in the molecule.
Ｒ24、Ｒ25、Ｒ26における非金属原子含有基としては、前記Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5における非金属原子含有基と同様のものが挙げられる。Ｒ24、Ｒ25が互いに結合して隣接する炭素原子とともに形成する環としては、前記Ｚ1、Ｒ1、Ｒ2のうち少なくとも２つが結合して隣接する炭素原子とともに形成する環と同様の環が挙げられる。Ｒ24、Ｒ25、Ｒ26としては、特に、水素原子、又は置換基を有していてもよい炭化水素基であるのが好ましい。 Examples of the non-metal atom-containing group in R 24 , R 25 , and R 26 include the same non-metal atom-containing groups in R 1 , R 2 , R 3 , R 4 , and R 5 . The ring formed by R 24 and R 25 bonded together and adjacent carbon atoms is the same ring as the ring formed by bonding at least two of Z 1 , R 1 and R 2 together with adjacent carbon atoms. Is mentioned. R 24 , R 25 , and R 26 are particularly preferably a hydrogen atom or a hydrocarbon group that may have a substituent.
カルボニル化合物（１４）の代表的な例としては、前記カルボニル化合物（５）の代表的な例と同様の化合物（アルデヒド又はケトン）が挙げられる。ニトロ基の隣接位にメチレン基を有するニトロ化合物（１５）の代表的な例として、ニトロメタン、ニトロエタン、ニトロプロパン、ニトロブタン等のニトロアルカンなどが挙げられる。 Representative examples of the carbonyl compound (14) include the same compounds (aldehyde or ketone) as the representative examples of the carbonyl compound (5). Representative examples of the nitro compound (15) having a methylene group adjacent to the nitro group include nitroalkanes such as nitromethane, nitroethane, nitropropane and nitrobutane.
反応は、溶媒の存在下又は非存在下で行われる。溶媒としては、水、有機溶媒、これらの混合溶媒の何れであってもよいが、なかでも水、エタノール等のアルコール、ジメチルスルホキシド、テトラヒドロフラン等の非プロトン性極性溶媒、又はこれらの混合溶媒が好ましく、とりわけ水が好ましい。 The reaction is carried out in the presence or absence of a solvent. The solvent may be any of water, an organic solvent, and a mixed solvent thereof. Among them, water, an alcohol such as ethanol, an aprotic polar solvent such as dimethyl sulfoxide and tetrahydrofuran, or a mixed solvent thereof is preferable. In particular, water is preferred.
化合物（１４）と化合物（１５）との比率は適宜選択でき、一般に、化合物（１５）の使用量は、化合物（１４）１モルに対して、０．５〜１０モル程度であるが、大過剰量用いてもよい。金属バナジン酸アパタイト触媒の使用量は原料成分の種類によっても異なるが、バナジウム（Ｖ）として、化合物（１４）に対して、例えば０．０００１〜１０モル％、好ましくは０．０００５〜５モル％程度の範囲で適宜選択できる。反応温度は原料成分の種類等に応じて適宜選択でき、例えば０〜２００℃、好ましくは５０〜１５０℃程度である。反応は加圧下で行ってもよい。反応は、回分式、半回分式、連続式等の慣用の方式で行うことができる。反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、吸着、カラムクロマトグラフィーなどの分離手段やこれらを組み合わせた分離手段により分離精製できる。 The ratio of the compound (14) and the compound (15) can be appropriately selected. Generally, the amount of the compound (15) used is about 0.5 to 10 mol with respect to 1 mol of the compound (14). An excessive amount may be used. Although the usage-amount of a metal vanadate apatite catalyst changes also with the kind of raw material component, it is 0.0001-10 mol% with respect to a compound (14) as vanadium (V), Preferably it is 0.0005-5 mol%. It can select suitably in the range of a grade. The reaction temperature can be appropriately selected according to the type of raw material components, and is, for example, about 0 to 200 ° C, preferably about 50 to 150 ° C. The reaction may be performed under pressure. The reaction can be carried out in a conventional manner such as batch, semi-batch, or continuous. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, etc., or a separation means combining these.
［重水素化方法］
本発明の重水素化方法では、上記金属バナジン酸アパタイトを含む触媒用組成物の存在下、有機化合物を重水と反応させて重水素化する。
[Deuteration method]
In the deuteration method of the present invention, an organic compound is reacted with deuterium to deuterate in the presence of the catalyst composition containing the metal vanadate apatite.
基質となる有機化合物としては、例えば、α位に水素原子を有するカルボニル化合物などが挙げられる。このようなカルボニル化合物の代表的な例としては、前記カルボニル化合物（５）の代表的な例と同様の化合物（アルデヒド又はケトン）が例示される。 Examples of the organic compound serving as a substrate include a carbonyl compound having a hydrogen atom at the α-position. As a typical example of such a carbonyl compound, the same compound (aldehyde or ketone) as the typical example of the said carbonyl compound (5) is illustrated.
この反応では、カルボニル化合物のα位の水素原子が重水素化される。反応は、溶媒の存在下又は非存在下で行われる。溶媒としては、反応成分である重水を用いる場合が多い。基質の溶解性を高めるため、重水とともに、テトラヒドロフランなどの重水素化反応に不活性で且つ水と混和する有機溶媒を用いてもよい。基質である有機化合物と重水との比率は適宜選択できるが、一般に、重水を過剰量、好ましくは大過剰量使用する。金属バナジン酸アパタイト触媒の使用量は原料成分の種類によっても異なるが、バナジウム（Ｖ）として、基質である有機化合物に対して、例えば０．０００１〜１０モル％、好ましくは０．０００５〜５モル％程度の範囲で適宜選択できる。反応温度は原料成分の種類等に応じて適宜選択でき、例えば０〜１５０℃、好ましくは１０〜１００℃程度である。反応は加圧下で行ってもよい。反応は、回分式、半回分式、連続式等の慣用の方式で行うことができる。反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、吸着、カラムクロマトグラフィーなどの分離手段やこれらを組み合わせた分離手段により分離精製できる。 In this reaction, the α-position hydrogen atom of the carbonyl compound is deuterated. The reaction is carried out in the presence or absence of a solvent. As the solvent, heavy water as a reaction component is often used. In order to increase the solubility of the substrate, an organic solvent that is inert to the deuteration reaction such as tetrahydrofuran and miscible with water may be used together with heavy water. The ratio of the organic compound serving as a substrate and heavy water can be selected as appropriate, but generally an excessive amount, preferably a large excess amount of heavy water is used. Although the amount of the metal vanadate apatite catalyst used varies depending on the type of raw material component, the vanadium (V) is, for example, 0.0001 to 10 mol%, preferably 0.0005 to 5 mol, based on the organic compound as the substrate. It can select suitably in the range of about%. The reaction temperature can be appropriately selected according to the type of raw material components and the like, and is, for example, about 0 to 150 ° C., preferably about 10 to 100 ° C. The reaction may be performed under pressure. The reaction can be carried out in a conventional manner such as batch, semi-batch, or continuous. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, etc., or a separation means combining these.
以下、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。生成物の定量は、ガスクロマトグラフィー（ＧＣ）、ガスクロマトグラフィー−質量分析（ＧＣ−ＭＳ）で行った。化学式中、Ｍｅはメチル基、Ｅｔはエチル基、Ａｃはアセチル基を示す。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples. The product was quantified by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). In the chemical formula, Me represents a methyl group, Et represents an ethyl group, and Ac represents an acetyl group.
実施例１（カルシウムバナジン酸アパタイトの製造）
バナジン酸ナトリウム（Ｎａ3ＶＯ4）４０ｍｍｏｌを水２００ｍｌに溶解させ、水酸化ナトリウム１２５ｍｍｏｌ（５ｇ）を加えた。この水溶液に、硫酸カルシウム（ＣａＳＯ4・２Ｈ2Ｏ）６６．８ｍｍｏｌを加え、１０５℃にて２時間撹拌した。得られたスラリーを吸引ろ過し、水およびアセトンで洗浄した後、減圧にて乾燥させた。続いてマッフル炉により８００℃にて３時間焼成すると、白色のカルシウムバナジン酸アパタイト（ＶＡｐ；Ｃａ10（ＶＯ4）6（ＯＨ）2）粉末（Ｃａ：３５．０３重量％、Ｖ：６．５３重量％、ＢＥＴ比表面積２８．５０ｍ2／ｇ、Ｃａ／Ｖ＝１．６７、Ｖ含量５．２ｍｍｏｌ／ｇ）が得られた。
Example 1 (Production of calcium vanadate apatite)
40 mmol of sodium vanadate (Na 3 VO 4 ) was dissolved in 200 ml of water, and 125 mmol (5 g) of sodium hydroxide was added. To this aqueous solution, 66.8 mmol of calcium sulfate (CaSO 4 .2H 2 O) was added and stirred at 105 ° C. for 2 hours. The obtained slurry was suction filtered, washed with water and acetone, and then dried under reduced pressure. Subsequently, when calcined at 800 ° C. for 3 hours in a muffle furnace, white calcium vanadate apatite (VAp; Ca 10 (VO 4 ) 6 (OH) 2 ) powder (Ca: 35.03 wt%, V: 6.53) Weight%, BET specific surface area 28.50 m 2 / g, Ca / V = 1.67, V content 5.2 mmol / g).
実施例２（マイケル反応）
実施例３（マイケル反応）
なお、反応後の反応混合液から回収した触媒を用いて同様の反応を行ったところ、上記と同様の反応成績が得られた。また、反応後の反応混合液から触媒を除いた溶液（バナジウムは検出されなかった）を用いて同様の反応を試みたが、反応は進行しなかった。
Example 3 (Michael reaction)
In addition, when the same reaction was performed using the catalyst collect | recovered from the reaction liquid mixture after reaction, the same reaction result as the above was obtained. A similar reaction was attempted using a solution obtained by removing the catalyst from the reaction mixture after the reaction (no vanadium was detected), but the reaction did not proceed.
実施例４（マイケル反応）
実施例５（マイケル反応）
実施例６（マイケル反応）
実施例７（マイケル反応）
実施例８（マイケル反応）
実施例９（マイケル反応）
実施例１０（マイケル反応）
実施例１１（マイケル反応）
実施例１２（クネベナーゲル反応）
実施例１３（クネベナーゲル反応）
実施例１４（クネベナーゲル反応）
実施例１５（クネベナーゲル反応）
実施例１６（クネベナーゲル反応）
実施例１７（アルドール反応）
実施例１８（ディールスアルダー反応）
実施例１９（ディールスアルダー反応）
実施例２０（ディールスアルダー反応）
実施例２１（ディールスアルダー反応）
実施例２２（マイケル反応）
実施例２３（マイケル反応）
実施例２４（マイケル反応）
実施例２５（マイケル反応）
実施例２６（マイケル反応）
実施例２７（マイケル反応）
実施例２８（マイケル反応）
実施例２９（クネベナーゲル反応）
実施例３０（クネベナーゲル反応）
実施例３１（クネベナーゲル反応）
実施例３２（クネベナーゲル反応）
実施例３３（クネベナーゲル反応）
実施例３４（ヘンリー反応）
実施例３５（ヘンリー反応）
実施例３６（ヘンリー反応）
実施例３７（重水素化反応）
実施例３８（重水素化反応）
実施例３９（重水素化反応）
実施例４０（重水素化反応）
Example 40 (deuteration reaction)
Claims (6)
Ｍ10-z（ＨＶＯ4）z（ＶＯ4）6-z（ＯＨ）2-z （Ｉ）
（式中、Ｍは金属原子を示し、０≦ｚ≦１である）
で表される請求項１記載の触媒用組成物。 Metal vanadate apatite has the following composition formula (I)
M 10-z (HVO 4 ) z (VO 4 ) 6-z (OH) 2-z (I)
(In the formula, M represents a metal atom, and 0 ≦ z ≦ 1)
The composition for catalysts of Claim 1 represented by these.
A deuteration method, comprising deuterating an organic compound by reacting with deuterated water in the presence of the catalyst composition according to any one of claims 1 to 3.
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Cited By (5)
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| JP2007063158A (en) * | 2005-08-30 | 2007-03-15 | Nippon Soda Co Ltd | METHOD FOR PRODUCING DISUBSTITUTED beta-KETOESTERS |
| CN102070673A (en) * | 2010-12-27 | 2011-05-25 | 罗梅 | O-amino benzylamine nickel coordination compound |
| CN102304151A (en) * | 2011-05-25 | 2012-01-04 | 合肥工业大学 | Manganese complex and synthesis method thereof |
| CN103755551A (en) * | 2014-01-20 | 2014-04-30 | 黄山科宏生物香料股份有限公司 | 5-oxo-octadecanoic acid synthesis method |
| CN104016889A (en) * | 2014-06-08 | 2014-09-03 | 中国科学院上海有机化学研究所 | Isotope labeled sodium cyclamate and preparation method thereof |
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| JP2007063158A (en) * | 2005-08-30 | 2007-03-15 | Nippon Soda Co Ltd | METHOD FOR PRODUCING DISUBSTITUTED beta-KETOESTERS |
| CN102070673A (en) * | 2010-12-27 | 2011-05-25 | 罗梅 | O-amino benzylamine nickel coordination compound |
| CN102070673B (en) * | 2010-12-27 | 2013-04-17 | 罗梅 | O-amino benzylamine nickel coordination compound |
| CN102304151A (en) * | 2011-05-25 | 2012-01-04 | 合肥工业大学 | Manganese complex and synthesis method thereof |
| CN102304151B (en) * | 2011-05-25 | 2014-12-03 | 合肥工业大学 | Manganese complex and synthesis method thereof |
| CN103755551A (en) * | 2014-01-20 | 2014-04-30 | 黄山科宏生物香料股份有限公司 | 5-oxo-octadecanoic acid synthesis method |
| CN104016889A (en) * | 2014-06-08 | 2014-09-03 | 中国科学院上海有机化学研究所 | Isotope labeled sodium cyclamate and preparation method thereof |
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