JPH07206885A - Production of ruthenium-iodo-optically active phosphine complex and production of optically active 4-methyl-2-oxetanone using the same complex - Google Patents
Production of ruthenium-iodo-optically active phosphine complex and production of optically active 4-methyl-2-oxetanone using the same complexInfo
- Publication number
- JPH07206885A JPH07206885A JP6013115A JP1311594A JPH07206885A JP H07206885 A JPH07206885 A JP H07206885A JP 6013115 A JP6013115 A JP 6013115A JP 1311594 A JP1311594 A JP 1311594A JP H07206885 A JPH07206885 A JP H07206885A
- Authority
- JP
- Japan
- Prior art keywords
- group
- optically active
- methyl
- oxetanone
- ruthenium
- 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
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 42
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- 229910001505 inorganic iodide Inorganic materials 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 claims abstract description 4
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003277 amino group Chemical class 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000011914 asymmetric synthesis Methods 0.000 abstract description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 2
- 239000003814 drug Substances 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 38
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 24
- 239000000460 chlorine Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- GSCLMSFRWBPUSK-GSVOUGTGSA-N (4r)-4-methyloxetan-2-one Chemical compound C[C@@H]1CC(=O)O1 GSCLMSFRWBPUSK-GSVOUGTGSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- IOPQYDKQISFMJI-UHFFFAOYSA-N [1-[2-bis(4-methylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(4-methylphenyl)phosphane Chemical group C1=CC(C)=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 IOPQYDKQISFMJI-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 10
- 229910052740 iodine Inorganic materials 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- -1 3-hydroxybutyric acid ester Chemical class 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- 235000009518 sodium iodide Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- GTBPUYSGSDIIMM-UHFFFAOYSA-N phosphane;ruthenium Chemical compound P.[Ru] GTBPUYSGSDIIMM-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 150000003003 phosphines Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- ASNHGEVAWNWCRQ-UHFFFAOYSA-N 4-(hydroxymethyl)oxolane-2,3,4-triol Chemical compound OCC1(O)COC(O)C1O ASNHGEVAWNWCRQ-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- MXGXXBYVDMVJAO-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical group CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C=CC=CC3=CC=2)C=2C3=CC=CC=C3C=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 MXGXXBYVDMVJAO-UHFFFAOYSA-N 0.000 description 4
- WHLQQRGHOPIIMQ-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methylphenyl)-3-methylphenyl]-diphenylphosphane Chemical group CC=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(C)=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 WHLQQRGHOPIIMQ-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- GSCLMSFRWBPUSK-VKHMYHEASA-N (4s)-4-methyloxetan-2-one Chemical compound C[C@H]1CC(=O)O1 GSCLMSFRWBPUSK-VKHMYHEASA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- UHAUNWBFEUXSNO-UHFFFAOYSA-N (2,3,4-trimethylphenyl)azanium;iodide Chemical compound [I-].CC1=CC=C([NH3+])C(C)=C1C UHAUNWBFEUXSNO-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ABUFEAKDTQPJQZ-UHFFFAOYSA-N 2,2-diethylbutane-1,1,1-triol Chemical compound CCC(CC)(CC)C(O)(O)O ABUFEAKDTQPJQZ-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- YAQLSKVCTLCIIE-UHFFFAOYSA-N 2-bromobutyric acid Chemical compound CCC(Br)C(O)=O YAQLSKVCTLCIIE-UHFFFAOYSA-N 0.000 description 1
- RUJHATQMIMUYKD-UHFFFAOYSA-N 2-naphthalen-1-ylethanamine Chemical compound C1=CC=C2C(CCN)=CC=CC2=C1 RUJHATQMIMUYKD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NVLPDIRQWJSXLZ-UHFFFAOYSA-N 3-hydroxypyridine-4-carbaldehyde Chemical compound OC1=CN=CC=C1C=O NVLPDIRQWJSXLZ-UHFFFAOYSA-N 0.000 description 1
- NGPJMZBMZXQOTD-UHFFFAOYSA-N 4-[4-(dimethylamino)-2-diphenylphosphanyl-6-methylphenyl]-3-diphenylphosphanyl-n,n,5-trimethylaniline Chemical group C=1C(N(C)C)=CC(C)=C(C=2C(=CC(=CC=2C)N(C)C)P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1P(C=1C=CC=CC=1)C1=CC=CC=C1 NGPJMZBMZXQOTD-UHFFFAOYSA-N 0.000 description 1
- PJEUKNUOCWNERE-UHFFFAOYSA-N 6-methyl-1h-quinolin-4-one Chemical compound N1=CC=C(O)C2=CC(C)=CC=C21 PJEUKNUOCWNERE-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- LDLDJEAVRNAEBW-UHFFFAOYSA-N Methyl 3-hydroxybutyrate Chemical compound COC(=O)CC(C)O LDLDJEAVRNAEBW-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 102100026009 NF-kappa-B inhibitor zeta Human genes 0.000 description 1
- 101710115530 NF-kappa-B inhibitor zeta Proteins 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- ANSOKCGDSQQISA-UHFFFAOYSA-N [1-(2-diphenylphosphanyl-5,6,7,8-tetrahydronaphthalen-1-yl)-5,6,7,8-tetrahydronaphthalen-2-yl]-diphenylphosphane Chemical group C1CCCC(C=2C=3C(=CC=C4CCCCC4=3)P(C=3C=CC=CC=3)C=3C=CC=CC=3)=C1C=CC=2P(C=1C=CC=CC=1)C1=CC=CC=C1 ANSOKCGDSQQISA-UHFFFAOYSA-N 0.000 description 1
- CFGHBQVJUPCBQC-UHFFFAOYSA-N [1-[2-bis(3,5-ditert-butylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(3,5-ditert-butylphenyl)phosphane Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC(P(C=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)C=2C(=C3C=CC=CC3=CC=2)C=2C3=CC=CC=C3C=CC=2P(C=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)C=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)=C1 CFGHBQVJUPCBQC-UHFFFAOYSA-N 0.000 description 1
- MJRVUGAHDHEPEL-UHFFFAOYSA-N [1-[2-bis(3-methylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(3-methylphenyl)phosphane Chemical group CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C(=C3C=CC=CC3=CC=2)C=2C3=CC=CC=C3C=CC=2P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 MJRVUGAHDHEPEL-UHFFFAOYSA-N 0.000 description 1
- NHPSDZWBMKQHPV-UHFFFAOYSA-N [1-[2-bis(4-chlorophenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(4-chlorophenyl)phosphane Chemical group C1=CC(Cl)=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC(Cl)=CC=1)C=1C=CC(Cl)=CC=1)C1=CC=C(Cl)C=C1 NHPSDZWBMKQHPV-UHFFFAOYSA-N 0.000 description 1
- QWKBAJNZHNAEHD-UHFFFAOYSA-N [1-[2-bis(4-tert-butylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(4-tert-butylphenyl)phosphane Chemical group C1=CC(C(C)(C)C)=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC(=CC=1)C(C)(C)C)C=1C=CC(=CC=1)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1 QWKBAJNZHNAEHD-UHFFFAOYSA-N 0.000 description 1
- JQFWVWJCUZKNPZ-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-4,6-dimethylphenyl)-3,5-dimethylphenyl]-diphenylphosphane Chemical group C=1C(C)=CC(C)=C(C=2C(=CC(C)=CC=2C)P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1P(C=1C=CC=CC=1)C1=CC=CC=C1 JQFWVWJCUZKNPZ-UHFFFAOYSA-N 0.000 description 1
- KRJVQCZJJSUHHO-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methoxyphenyl)-3-methoxyphenyl]-diphenylphosphane Chemical group COC=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(OC)=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 KRJVQCZJJSUHHO-UHFFFAOYSA-N 0.000 description 1
- UNROUNAUCFDWAU-UHFFFAOYSA-N [2-(6-diphenylphosphanyl-2,3-dimethoxyphenyl)-3,4-dimethoxyphenyl]-diphenylphosphane Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)C=1C=CC(OC)=C(OC)C=1C1=C(OC)C(OC)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UNROUNAUCFDWAU-UHFFFAOYSA-N 0.000 description 1
- QXJARVSGJXWJQR-UHFFFAOYSA-N [2-(6-diphenylphosphanyl-3-methoxy-2,4-dimethylphenyl)-4-methoxy-3,5-dimethylphenyl]-diphenylphosphane Chemical group CC=1C(OC)=C(C)C=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C1=C(C)C(OC)=C(C)C=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QXJARVSGJXWJQR-UHFFFAOYSA-N 0.000 description 1
- GHUNCMLPKZAPJK-UHFFFAOYSA-N [2-[2-bis(4-methylphenyl)phosphanyl-6-methylphenyl]-3-methylphenyl]-bis(4-methylphenyl)phosphane Chemical group C1=CC(C)=CC=C1P(C=1C(=C(C)C=CC=1)C=1C(=CC=CC=1C)P(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 GHUNCMLPKZAPJK-UHFFFAOYSA-N 0.000 description 1
- SVFBCRWHOJQKAF-UHFFFAOYSA-N [2-[6-bis(4-methoxyphenyl)phosphanyl-3-methoxy-2,4-dimethylphenyl]-4-methoxy-3,5-dimethylphenyl]-bis(4-methoxyphenyl)phosphane Chemical group C1=CC(OC)=CC=C1P(C=1C(=C(C)C(OC)=C(C)C=1)C=1C(=CC(C)=C(OC)C=1C)P(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 SVFBCRWHOJQKAF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- LRRJQNMXIDXNIM-UHFFFAOYSA-M benzyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CC=C1 LRRJQNMXIDXNIM-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 244000309464 bull Species 0.000 description 1
- CALQKRVFTWDYDG-UHFFFAOYSA-N butan-1-amine;hydroiodide Chemical compound [I-].CCCC[NH3+] CALQKRVFTWDYDG-UHFFFAOYSA-N 0.000 description 1
- BEVHTMLFDWFAQF-UHFFFAOYSA-N butyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 BEVHTMLFDWFAQF-UHFFFAOYSA-N 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- VJVGVDCTJLFWMY-UHFFFAOYSA-N dicyclohexyl-[1-(2-dicyclohexylphosphanylnaphthalen-1-yl)naphthalen-2-yl]phosphane Chemical group C1CCCCC1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C1CCCCC1)C1CCCCC1)C1CCCCC1 VJVGVDCTJLFWMY-UHFFFAOYSA-N 0.000 description 1
- SKCMIKXIHUVXEG-UHFFFAOYSA-N dicyclohexyl-[2-(2-dicyclohexylphosphanyl-6-methylphenyl)-3-methylphenyl]phosphane Chemical group CC=1C=CC=C(P(C2CCCCC2)C2CCCCC2)C=1C=1C(C)=CC=CC=1P(C1CCCCC1)C1CCCCC1 SKCMIKXIHUVXEG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 1
- ZPEBBUBSCOELHI-UHFFFAOYSA-M ethyltrimethylammonium iodide Chemical compound [I-].CC[N+](C)(C)C ZPEBBUBSCOELHI-UHFFFAOYSA-M 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WCZSOHSGMBVYFW-UHFFFAOYSA-M heptyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCC)C1=CC=CC=C1 WCZSOHSGMBVYFW-UHFFFAOYSA-M 0.000 description 1
- UXMZNEHSMYESLH-UHFFFAOYSA-M hexadecyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCCCCCCC)C1=CC=CC=C1 UXMZNEHSMYESLH-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Natural products CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 125000000352 p-cymenyl group Chemical group C1(=C(C=C(C=C1)C)*)C(C)C 0.000 description 1
- VAUKWMSXUKODHR-UHFFFAOYSA-M pentyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC)C1=CC=CC=C1 VAUKWMSXUKODHR-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- SYZCZDCAEVUSPM-UHFFFAOYSA-M tetrahexylazanium;bromide Chemical compound [Br-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC SYZCZDCAEVUSPM-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- AEFPPQGZJFTXDR-UHFFFAOYSA-M tetraphenylphosphanium;iodide Chemical compound [I-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEFPPQGZJFTXDR-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DXJLCRNXYNRGRA-UHFFFAOYSA-M tributyl(methyl)azanium;iodide Chemical compound [I-].CCCC[N+](C)(CCCC)CCCC DXJLCRNXYNRGRA-UHFFFAOYSA-M 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- XMQSELBBYSAURN-UHFFFAOYSA-M triphenyl(propyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 XMQSELBBYSAURN-UHFFFAOYSA-M 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
- Epoxy Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なルテニウム−ヨ
ード−光学活性ホスフィン錯体の製法に関し、さらに詳
細には、各種の有機合成反応、特に不斉水素化反応等の
触媒として用いられる上記錯体の製法、およびこれを用
いる、ポリマー原料、医薬の合成原料あるいは液晶材料
等の有機合成化学工業における中間体として有用な光学
活性４−メチル−２−オキセタノンを製造する方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel ruthenium-iodo-optically active phosphine complex, and more specifically, the above complex used as a catalyst for various organic synthetic reactions, especially asymmetric hydrogenation reactions. And a method for producing optically active 4-methyl-2-oxetanone useful as an intermediate in an organic synthetic chemical industry such as a polymer raw material, a pharmaceutical synthetic raw material or a liquid crystal material using the same.
【０００２】[0002]
【従来の技術】従来、多くの遷移金属錯体が有機合成反
応の触媒として使用されている。 特にルテニウム金属
と光学活性な第三級ホスフィンによる金属錯体は、不斉
水素化反応の触媒として良く知られており、例えば、
２,２'−ビス（ジフェニルホスフィノ）−１,１'−ビナ
フチルや２,２'−ジメチル−６,６'−ビス（ジフェニル
ホスフィノ）−１,１'−ビフェニルのような光学活性な
第三級ホスフィンを配位子としたルテニウム−光学活性
ホスフィン錯体として、次のようなものが知られてい
る。2. Description of the Related Art Conventionally, many transition metal complexes have been used as catalysts for organic synthetic reactions. In particular, a metal complex of ruthenium metal and an optically active tertiary phosphine is well known as a catalyst for an asymmetric hydrogenation reaction.
Optically active compounds such as 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl and 2,2'-dimethyl-6,6'-bis (diphenylphosphino) -1,1'-biphenyl The following are known as ruthenium-optically active phosphine complexes having a tertiary phosphine as a ligand.
【０００３】 ＲｕxＨyＣｌz（第三級ホスフィン）2
（Ａ）p ［式中、Ａは第三級アミンを示し、ｙが０のとき、ｘは
２、ｚは４、ｐは１を示し、ｙが１のとき、ｘは１、ｚ
は１、ｐは０を示す］ （特開昭６１−６３６９０号公報、特開昭６３−１３５
３９７号公報） ［ＲｕＨr（第三級ホスフィン）m］Ｔn ［式中、ＴはＣｌＯ4、ＢＦ4、ＰＦ6を示し、ｒが０の
とき、ｍは１、ｎ は２を示し、ｒが１のとき、ｍは
２、ｎは１を示す］ （特開昭６３−４１４８７号公報、特開昭６３−１４５
４９２号公報）Ru x H y Cl z (tertiary phosphine) 2
(A) p [In the formula, A represents a tertiary amine, when y is 0, x is 2, z is 4, p is 1, and when y is 1, x is 1, z
Indicates 1 and p indicates 0] (JP-A 61-63690, JP-A 63-135)
397) [RuH r (tertiary phosphine) m ] T n [wherein T represents ClO 4 , BF 4 and PF 6, and when r is 0, m is 1 and n is 2; When r is 1, m is 2 and n is 1.] (JP-A-63-41487, JP-A-63-145)
No. 492 publication)
【０００４】 ［ＲｕＸa（Ｑ）b（第三級ホスフィ
ン）］Ｙc ［式中、Ｘはハロゲン原子を示し、Ｑは置換基を有して
いてもよいベンゼンまたはアセトニトリルを示し、Ｙは
ハロゲン原子、ＣｌＯ4、ＰＦ6、ＢＰｈ4（ここでＰｈ
はフェニル基を示す。以下同様）またはＢＦ4を示し、
Ｑが置換基を有していてもよいベンゼンの場合、ａ、ｂ
及びｃはいずれも１を示し、Ｑがアセトニトリルの場
合、ａが０のとき、ｂは４、ｃは２を示し、ａが１のと
き、ｂは２、ｃは１を示す。 尚、Ｑが置換基を有する
ベンゼンのうちｐ−シメンであり、Ｘ及びＬがヨウ素原
子である場合は、ａ、ｂ及びｃがいずれも１であるほ
か、ａが１、ｂが１、ｃが３であってもよい］ （特開平２−１９１２８９号公報、特開平５−１１１６
３９号公報）[RuX a (Q) b (tertiary phosphine)] Y c [wherein, X represents a halogen atom, Q represents benzene or acetonitrile which may have a substituent, and Y represents halogen. Atoms, ClO 4 , PF 6 , BPh 4 (where Ph
Represents a phenyl group. The same shall apply hereinafter) or BF 4 ,
When Q is benzene which may have a substituent, a, b
And c are both 1, and when Q is acetonitrile, when a is 0, b is 4 and c is 2, when a is 1, b is 2 and c is 1. In addition, when Q is p-cymene in benzene having a substituent and X and L are iodine atoms, a, b and c are all 1, a is 1, b is 1 and c May be 3] (JP-A-2-191289, JP-A-5-1116)
(Gazette No. 39)
【０００５】 （第三級ホスフィン）wＲｕ（ＯＣＯ
Ｒ’）（ＯＣＯＲ”） ［式中、Ｒ’およびＲ”は低級アルキル基、ハロゲン化
低級アルキル基、低級アルキル置換基を有してもよいフ
ェニル基、α−アミノアルキル基またはα−アミノフェ
ニルアルキル基を示すか、あるいはＲ’とＲ”が一緒に
なってアルキレン基を形成し、ｗは１または２を示す］ （特開昭６２−２６５２９３号公報、特開昭６３−１４
５２９１号公報）(Tertiary phosphine) w Ru (OCO
R ′) (OCOR ″) [wherein R ′ and R ″ are a lower alkyl group, a halogenated lower alkyl group, a phenyl group which may have a lower alkyl substituent, an α-aminoalkyl group or an α-aminophenyl group. It represents an alkyl group, or R'and R "together form an alkylene group, and w represents 1 or 2." (JP-A-62-265293, JP-A-63-14)
5291 publication)
【０００６】 ＲｕＪ2（第三級ホスフィン） ［式中、Ｊは塩素原子、臭素原子またはヨウ素原子を示
す］ （R.Noyori et al., J.Am.Chem.Soc., Vol.109, No.19,
pp.5856-5859 (1987)） ＲｕＧ2（第三級ホスフィ
ン） ［式中、Ｇはアリル基又はメタリル基を示す］ （J.P.Genet et al., Tetrahedron:Asymmetry, Vol.2,
No.7, pp.555-567(1991)）RuJ 2 (tertiary phosphine) [wherein J represents a chlorine atom, a bromine atom or an iodine atom] (R. Noyori et al., J. Am. Chem. Soc., Vol. 109, No. .19,
pp.5856-5859 (1987)) RuG 2 (tertiary phosphine) [wherein G represents an allyl group or a methallyl group] (JPGenet et al., Tetrahedron: Asymmetry, Vol. 2,
No.7, pp.555-567 (1991))
【０００７】しかし、これらのルテニウム−光学活性ホ
スフィン錯体を用いても、対象とする反応または反応基
質によっては、触媒活性や不斉収率が不十分である等、
実際の工業化に当たっては問題がある場合があった。However, even if these ruthenium-optically active phosphine complexes are used, the catalytic activity and asymmetric yield are insufficient depending on the target reaction or reaction substrate.
There were some problems in actual industrialization.
【０００８】一方、４−メチル−２−オキセタノン
（「β−ブチロラクトン」または「β−メチル−β−プ
ロピオラクトン」とも言う）は、従来より、ポリマー原
料等に用いられているが、近年になって、Ｎ.タナハシ
ら（N.Tanahashi et al., Macromolecules, Vol.24, p
p.5732-5733 (1991) ）が報告しているように、特にそ
の光学活性体が有用であるとして注目されている。On the other hand, 4-methyl-2-oxetanone (also referred to as "β-butyrolactone" or "β-methyl-β-propiolactone") has been conventionally used as a polymer raw material and the like. N. Tanahashi et al., Macromolecules, Vol.24, p.
As described in p.5732-5733 (1991)), the optically active substance has been particularly noted as being useful.
【０００９】光学活性な４−メチル−２−オキセタノン
の製法としては、次のような方法が報告されている。 （ａ） クロトン酸に臭化水素酸を付加して得られる３
−ブロモ酪酸を、光学活性なナフチルエチルアミンを用
いて光学分割し、次いで環化する方法（J.ReidShelton
et al., Polymer Letters, Vol.9, pp.173-178 (1971)
及び T.Satoet al., Tetrahedron Lett.,Vol.21, pp.33
77-3380 (1980)）。 （ｂ） 光学活性な３−ヒドロキシ酪酸にトリエチルオ
ルト酢酸を反応させて光学活性な２−エトキシ−２,６
−ジメチル−１,３−ジオキサン−４−オンを得、これ
を熱分解する方法（A.Griesbeck et al., Helv. Chim.
Acta, Vol.70, pp.1320-1325 (1987) 及び R.Breitschu
h et al., Chimia, Vol.44, pp.216-218 (1990)）。As a method for producing optically active 4-methyl-2-oxetanone, the following method has been reported. (A) 3 obtained by adding hydrobromic acid to crotonic acid
-Methods of optically resolving bromobutyric acid with optically active naphthylethylamine and then cyclizing (J. ReidShelton
et al., Polymer Letters, Vol.9, pp.173-178 (1971)
And T. Sato et al., Tetrahedron Lett., Vol. 21, pp. 33
77-3380 (1980)). (B) Optically active 2-hydroxy-2,6 is obtained by reacting optically active 3-hydroxybutyric acid with triethylorthoacetic acid.
-Dimethyl-1,3-dioxan-4-one is obtained and pyrolyzed (A. Griesbeck et al., Helv. Chim.
Acta, Vol.70, pp.1320-1325 (1987) and R. Breitschu
h et al., Chimia, Vol.44, pp.216-218 (1990)).
【００１０】（ｃ） 光学活性な３−ヒドロキシ酪酸エ
ステルをメタンスルホニルクロリドと反応させて水酸基
をメシル化した後、得られたエステルを加水分解し、次
いで炭酸水素ナトリウムで縮合環化する方法（Y.Zhang
et al., Macromolecules, Vol.23, pp.3206-3212 (199
0)）。更に、前記したルテニウム−光学活性ホスフィン
錯体を用いた例として次のような方法も報告されてい
る。(C) A method in which an optically active 3-hydroxybutyric acid ester is reacted with methanesulfonyl chloride to mesylate a hydroxyl group, the resulting ester is hydrolyzed, and then condensed and cyclized with sodium hydrogen carbonate (Y .Zhang
et al., Macromolecules, Vol.23, pp.3206-3212 (199
0)). Furthermore, the following method has been reported as an example using the above-mentioned ruthenium-optically active phosphine complex.
【００１１】（ｄ） ４−メチレン−２−オキセタノン
を、塩化メチレンまたはテトラヒドロフランのような非
プロトン性溶媒中で、［ＲｕＣｌ［（Ｓ）−もしくは
（Ｒ）−ＢＩＮＡＰ］（ベンゼン）］Ｃｌ、または、Ｒ
ｕ2Ｃｌ4［（Ｓ）−もしくは（Ｒ）−ＢＩＮＡＰ］
2（ＮＥｔ3）［ここで、ＢＩＮＡＰは２,２'−ビス（ジ
フェニルホスフィノ）−１,１'−ビナフチルを示し、Ｅ
ｔはエチル基を示す］を触媒として不斉水素化する方法
（T.Ohta et al., J. CHEM. SOC., CHEM. COMMUN., pp.
1725-1726 (1992)）。(D) 4-methylene-2-oxetanone in [RuCl [(S)-or (R) -BINAP] (benzene)] Cl in an aprotic solvent such as methylene chloride or tetrahydrofuran, or , R
u 2 Cl 4 [(S)-or (R) -BINAP]
2 (NEt 3 ) [where BINAP represents 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, E
t represents an ethyl group] as a catalyst for asymmetric hydrogenation (T. Ohta et al., J. CHEM. SOC., CHEM. COMMUN., pp.
1725-1726 (1992)).
【００１２】しかしながら、これらの方法はそれぞれ次
のような問題点を有していた。すなわち、（ａ）の方法
は、光学分割剤として特殊な光学活性アミンを原料化合
物と等モル必要とし、また、不要な鏡像体が目的物と等
モル副生するので、無駄が多く経済的に有利な方法では
ない。However, each of these methods has the following problems. That is, the method (a) requires a special optically active amine as an optical resolving agent in an equimolar amount with the starting compound, and an unnecessary enantiomer is by-produced in an equimolar amount with the target compound, which is wasteful and economical. Not an advantageous method.
【００１３】また、（ｂ）及び（ｃ）の方法は、原料化
合物である光学活性な３−ヒドロキシ酪酸またはそのエ
ステルの合成が容易ではない。 すなわち、微生物が産
生する光学活性なポリ−３−ヒドロキシ酪酸エステルを
熱分解するか、あるいは、ラセミ体の４−メチル−２−
オキセタノンをアルコーリシス反応によってアセト酢酸
エステルに導いた後不斉還元を行う必要があり、工程数
が多く操作が煩雑である。In the methods (b) and (c), it is not easy to synthesize the optically active 3-hydroxybutyric acid or its ester which is the starting compound. That is, the optically active poly-3-hydroxybutyric acid ester produced by a microorganism is thermally decomposed or racemic 4-methyl-2-
Since it is necessary to conduct asymmetric reduction after introducing oxetanone into acetoacetic acid ester by alcoholysis reaction, the number of steps is large and the operation is complicated.
【００１４】（ｄ）の方法は、上述した（ａ）〜（ｃ）
の方法の問題点の多くを解決してはいるが、まだいくつ
かの問題点を抱えている。 すなわち、触媒活性が低
く、反応時間が長い。さらに、得られる生成物の光学純
度が７０〜９２％ｅ.ｅ.と低く、工業的に十分満足のい
く方法ではなかった。The method (d) is the same as the above (a) to (c).
Although it solves many of the problems with this method, it still has some problems. That is, the catalytic activity is low and the reaction time is long. Further, the optical purity of the obtained product is as low as 70 to 92% ee, which is not a method which is industrially sufficiently satisfactory.
【００１５】[0015]
【発明が解決しようとする課題】従って、本発明の目的
は、触媒活性が高く、かつ、不斉反応における高い不斉
収率、すなわち、光学純度が高い生成物を得ることがで
きる触媒を提供し、さらに、この触媒を用いて、ポリマ
ー原料等として有用な光学活性４−メチル−２−オキセ
タノンを、短時間で効率よく、しかも高い光学純度のも
のを製造する方法を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a catalyst which has a high catalytic activity and a high asymmetric yield in an asymmetric reaction, that is, a product having a high optical purity. Further, it is still another object of the present invention to provide a method for producing optically active 4-methyl-2-oxetanone useful as a polymer raw material or the like in a short time efficiently and with high optical purity by using this catalyst.
【００１６】[0016]
【課題を解決するための手段】本発明者らは、前記課題
を解決するために鋭意研究を行なった結果、比較的簡単
な方法によって得られる新規なルテニウム−ヨード−光
学活性ホスフィン錯体は極めて高い触媒活性を有し、不
斉合成触媒として広く用いることができること、およ
び、特にこれを４−メチレン−２−オキセタノンの不斉
水素化反応の触媒に用いれば、短時間で効率よく、高い
光学純度の光学活性４−メチル−２−オキセタノンを製
造できることを見出し、本発明を完成した。As a result of intensive studies to solve the above problems, the present inventors have found that the novel ruthenium-iodo-optically active phosphine complex obtained by a relatively simple method is extremely high. It has catalytic activity and can be widely used as an asymmetric synthesis catalyst. Especially, if it is used as a catalyst for the asymmetric hydrogenation reaction of 4-methylene-2-oxetanone, it can be efficiently used in a short time with high optical purity. It was found that the optically active 4-methyl-2-oxetanone of can be produced, and the present invention has been completed.
【００１７】すなわち、本発明の目的は、次の式（１） Ｒｕ2Ｃｌ4（ＣＢＰ）2ＮＥｔ3 （１） ［式中、Ｅｔはエチル基を示し、ＣＢＰは式（２）That is, the object of the present invention is to provide the following formula (1) Ru 2 Cl 4 (CBP) 2 NEt 3 (1) [wherein Et represents an ethyl group and CBP represents the formula (2)
【化５】 （ここで、Ｒ1はアリール基または炭素数３〜８のシク
ロアルキル基を示す）または式（３）[Chemical 5] (Wherein R 1 represents an aryl group or a cycloalkyl group having 3 to 8 carbon atoms) or the formula (3).
【化６】 （ここで、Ｒ2はアリール基または炭素数３〜８のシク
ロアルキル基を、Ｒ3はメチル基またはメトキシ基を示
し、Ｒ4は水素原子、メチル基またはメトキシ基を、Ｒ5
は水素原子、メチル基、メトキシ基またはジ低級アルキ
ル置換アミノ基を示すか、Ｒ3とＲ4が一緒になって隣接
するフェニル基とともにテトラヒドロナフチル基を形成
する）で示される光学活性な第三級ホスフィンを示す］
で表されるルテニウム−光学活性ホスフィン錯体を、無
機ヨウ化物と反応させることを特徴とする新規なルテニ
ウム−ヨード−光学活性ホスフィン錯体の製法を提供す
ることである。また、本発明の別の目的は、上記ルテニ
ウム−ヨード−光学活性ホスフィン錯体を触媒として用
い、４−メチレン−２−オキセタノンを不斉水素化する
光学活性４−メチル−２−オキセタノンの製法を提供す
ることである。[Chemical 6] (Here, R 2 represents an aryl group or a cycloalkyl group having 3 to 8 carbon atoms, R 3 represents a methyl group or a methoxy group, R 4 represents a hydrogen atom, a methyl group or a methoxy group, R 5
Is a hydrogen atom, a methyl group, a methoxy group or a di-lower alkyl-substituted amino group, or R 3 and R 4 together form a tetrahydronaphthyl group with the adjacent phenyl group). Grade phosphine]
Another object of the present invention is to provide a method for producing a novel ruthenium-iodo-optically active phosphine complex, which comprises reacting a ruthenium-optically active phosphine complex represented by Another object of the present invention is to provide a method for producing optically active 4-methyl-2-oxetanone by asymmetric hydrogenation of 4-methylene-2-oxetanone using the above ruthenium-iodo-optically active phosphine complex as a catalyst. It is to be.
【００１８】本発明のルテニウム−ヨード−光学活性ホ
スフィン錯体（以下、「Ｒｕ−Ｉ−（ＣＢＰ）」と略記
する）は、窒素等の不活性ガスで置換を行った反応容器
中に、上記ルテニウム−ホスフィン錯体（１）、無機ヨ
ウ化物および相間移動触媒を入れ、疎水性有機溶媒およ
び水を加えて攪拌反応することによって、容易に得るこ
とができる。The ruthenium-iodo-optically active phosphine complex of the present invention (hereinafter abbreviated as "Ru-I- (CBP)") is prepared by replacing the above ruthenium in a reaction vessel in which an inert gas such as nitrogen is substituted. -A phosphine complex (1), an inorganic iodide and a phase transfer catalyst may be added, a hydrophobic organic solvent and water may be added, and a reaction of stirring may be performed to easily obtain the same.
【００１９】Ｒｕ−Ｉ−（ＣＢＰ）を製造するための原
料である、ルテニウム−光学活性ホスフィン錯体（１）
において、ＣＢＰが式（２）で表される配位子（以下、
「Ｒ1−ＢＩＮＡＰ」と略称する）である場合、Ｒ1で表
されるアリール基とは、フェニル基ならびにｐ−置換フ
ェニル基、ｍ−置換フェニル基およびｍ−ジ置換フェニ
ル基のような置換基を有するフェニル基を意味し、フェ
ニル基に置換してもよい置換基とは、メチル基、ｔｅｒ
ｔ−ブチル基のような低級アルキル基（「低級」とは炭
素数１〜４の直鎖または分岐鎖を意味する）、メトキシ
基および塩素原子を挙げることができる。 また、Ｒ1で
表される炭素数３〜８のアルキル基としては、特にシク
ロペンチル基およびシクロヘキシル基が好ましい。A ruthenium-optically active phosphine complex (1), which is a raw material for producing Ru-I- (CBP).
In, CBP is a ligand represented by the formula (2) (hereinafter,
In the case of “R 1 -BINAP”), the aryl group represented by R 1 is a phenyl group or a substituted group such as a p-substituted phenyl group, an m-substituted phenyl group and an m-disubstituted phenyl group. Means a phenyl group having a group, and the substituent which may be substituted on the phenyl group is a methyl group, ter
Examples thereof include a lower alkyl group such as t-butyl group (“lower” means a straight chain or branched chain having 1 to 4 carbon atoms), a methoxy group and a chlorine atom. Further, as the alkyl group having 3 to 8 carbon atoms represented by R 1 , a cyclopentyl group and a cyclohexyl group are particularly preferable.
【００２０】また、ルテニウム−光学活性ホスフィン錯
体（１）において、ＣＢＰが式（３）で表される配位子
（以下、「ＢＩＰＨＥＰ」と略称する）である場合、Ｒ
2で表されるアリール基とは、フェニル基並びにｐ−置
換フェニル基、ｍ−置換フェニル基及びｍ−ジ置換フェ
ニル基のような置換基を有するフェニル基を意味し、フ
ェニル基に置換してもよい置換基とは、メチル基、ｔｅ
ｒｔ−ブチル基のような低級アルキル基、メトキシ基及
び塩素原子を挙げることができる。 また、Ｒ1 で表され
る炭素数３〜８のアルキル基では、特にシクロヘキシル
基が好ましい。また、Ｒ5がジ低級アルキル置換アミノ
基である場合の、低級アルキル基とは、炭素数１〜４の
直鎖または分岐鎖のアルキル基を意味する。Further, a ruthenium-optically active phosphine complex
In the body (1), CBP is a ligand represented by the formula (3)
(Hereinafter, abbreviated as “BIPHEP”), R
2The aryl group represented by is a phenyl group and a p-position.
Phenyl group, m-substituted phenyl group and m-disubstituted phenyl group
A phenyl group having a substituent such as a nyl group,
The substituent which may be substituted on the phenyl group is a methyl group or te
lower alkyl group such as rt-butyl group, methoxy group and
And chlorine atom. Also, R1 Represented by
A C3-8 alkyl group, especially cyclohexyl
Groups are preferred. Also, RFiveIs di-lower alkyl substituted amino
When it is a group, the lower alkyl group has 1 to 4 carbon atoms.
It means a linear or branched alkyl group.
【００２１】このルテニウム−光学活性ホスフィン錯体
（１）において、Ｒ1−ＢＩＮＡＰで表される第三級ホ
スフィンの具体例としては、次のものを挙げることがで
きる。 （尚、いずれの第三級ホスフィンも（Ｒ）体及
び（Ｓ）体が存在するがその表記は省略した。 以下同
じ）In this ruthenium-optically active phosphine complex (1), the following can be mentioned as specific examples of the tertiary phosphine represented by R 1 -BINAP. (Note that any of the tertiary phosphines has an (R) form and an (S) form, but the description thereof is omitted. The same applies hereinafter.)
【００２２】（ア）２,２'−ビス（ジフェニルホスフィ
ノ）−１,１'−ビナフチル（以下、単に「ＢＩＮＡＰ」
と略記する） （イ）２,２'−ビス（ジ−ｐ−トリルホスフィノ）−
１,１'−ビナフチル（以下、「Ｔｏｌ−ＢＩＮＡＰ」と
略記する） （ウ）２,２'−ビス［ジ−（ｐ−ｔｅｒｔ−ブチルフェ
ニル）ホスフィノ］−１,１'−ビナフチル（以下、「ｔ
−Ｂｕ−ＢＩＮＡＰ」と略記する） （エ）２,２'−ビス（ジ−ｍ−トリルホスフィノ）−
１,１'−ビナフチル（以下、「ｍ−Ｔｏｌ−ＢＩＮＡ
Ｐ」と略記する）(A) 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (hereinafter simply referred to as "BINAP")
(A) 2,2'-bis (di-p-tolylphosphino)-
1,1′-binaphthyl (hereinafter abbreviated as “Tol-BINAP”) (C) 2,2′-bis [di- (p-tert-butylphenyl) phosphino] -1,1′-binaphthyl (hereinafter, "T
-Bu-BINAP ") (d) 2,2'-bis (di-m-tolylphosphino)-
1,1′-binaphthyl (hereinafter, “m-Tol-BINA
Abbreviated as "P")
【００２３】（オ）２,２'−ビス［ジ−（３,５−ジメ
チルフェニル）ホスフィノ］−１,１'−ビナフチル（以
下、「ＤＭ−ＢＩＮＡＰ」と略記する） （カ）２,２'−ビス［ジ−（３,５−ジ−ｔｅｒｔ−ブ
チルフェニル）ホスフィノ］−１,１'−ビナフチル（以
下、「ＤｔＢｕ−ＢＩＮＡＰ」と略記する） （キ）２,２'−ビス［ジ−（ｐ−メトキシフェニル）ホ
スフィノ］−１,１'−ビナフチル（以下、「Ｍｅｔｈｏ
ｘｙ−ＢＩＮＡＰ」と略記する） （ク）２,２'−ビス［ジ−（ｐ−クロロフェニル）ホス
フィノ］−１,１'−ビナフチル（以下、「ｐ−Ｃｌ−Ｂ
ＩＮＡＰ」と略記する） （ケ）２,２'−ビス（ジシクロペンチルホスフィノ）−
１,１'−ビナフチル（以下、「ＣｐＢＩＮＡＰ」と略記
する） （コ）２,２'−ビス（ジシクロヘキシルホスフィノ）−
１,１'−ビナフチル（以下、「ＣｙＢＩＮＡＰ」と略記
する）(E) 2,2'-bis [di- (3,5-dimethylphenyl) phosphino] -1,1'-binaphthyl (hereinafter abbreviated as "DM-BINAP") (f) 2,2 '-Bis [di- (3,5-di-tert-butylphenyl) phosphino] -1,1'-binaphthyl (hereinafter abbreviated as "DtBu-BINAP") (ki) 2,2'-bis [di -(P-Methoxyphenyl) phosphino] -1,1'-binaphthyl (hereinafter referred to as "Metho
abbreviated as "xy-BINAP") (h) 2,2'-bis [di- (p-chlorophenyl) phosphino] -1,1'-binaphthyl (hereinafter referred to as "p-Cl-B"
(KE) 2,2'-bis (dicyclopentylphosphino)-
1,1'-Binaphtyl (hereinafter abbreviated as "CpBINAP") (Co) 2,2'-bis (dicyclohexylphosphino)-
1,1'-binaphthyl (hereinafter abbreviated as "CyBINAP")
【００２４】これらの第三級ホスフィンは、特開昭６１
−６３６９０号公報、特開平３−２０２９０号公報、特
開平３−２５５０９０号公報、特開平１−６８３８６号
公報または特開平４−７４１９２号公報に記載されてい
る方法によって調製することができる。These tertiary phosphines are disclosed in JP-A-61 / 1986.
It can be prepared by the method described in JP-A-63690, JP-A-3-20290, JP-A-3-255090, JP-A-1-68386 or JP-A-4-74192.
【００２５】また、ＢＩＰＨＥＰで表される第三級ホス
フィンの具体例としては、次のものを挙げることができ
る。 （サ）２,２'−ジメチル−６,６'−ビス（ジフェニルホ
スフィノ）−１,１'−ビフェニル（以下、「ＢＩＰＨＥ
ＭＰ」と略記する） （シ）２,２'−ジメチル−６,６'−ビス（ジシクロヘキ
シルホスフィノ）−１,１'−ビフェニル（以下、「ＢＩ
ＣＨＥＰ」と略記する） （ス）２,２'−ビス（ジフェニルホスフィノ）−５,
５',６,６',７,７',８,８'−オクタヒドロ−１,１'−ビ
ナフチル（以下、「ＯｃＨＢＩＮＡＰ」と略記する）The following can be mentioned as specific examples of the tertiary phosphine represented by BIPHEP. (Sa) 2,2'-dimethyl-6,6'-bis (diphenylphosphino) -1,1'-biphenyl (hereinafter referred to as "BIPHE
Abbreviated as "MP") (si) 2,2'-dimethyl-6,6'-bis (dicyclohexylphosphino) -1,1'-biphenyl (hereinafter referred to as "BI
Abbreviated as “CHEP”) (s) 2,2′-bis (diphenylphosphino) -5,
5 ′, 6,6 ′, 7,7 ′, 8,8′-octahydro-1,1′-binaphthyl (hereinafter abbreviated as “OcHBINAP”)
【００２６】（セ）２,２'−ジメチル−４,４'−ビス
（ジメチルアミノ）−６,６'−ビス（ジフェニルホスフ
ィノ）−１,１'−ビフェニル （ソ）２,２',４,４'−テトラメチル−６,６'−ビス
（ジフェニルホスフィノ）−１,１'−ビフェニル （タ）２,２'−ジメトキシ−６,６'−ビス（ジフェニル
ホスフィノ）−１,１'−ビフェニル （チ）２,２',３,３'−テトラメトキシ−６,６'−ビス
（ジフェニルホスフィノ） −１,１'−ビフェニル(C) 2,2'-Dimethyl-4,4'-bis (dimethylamino) -6,6'-bis (diphenylphosphino) -1,1'-biphenyl (so) 2,2 ', 4,4'-tetramethyl-6,6'-bis (diphenylphosphino) -1,1'-biphenyl (ta) 2,2'-dimethoxy-6,6'-bis (diphenylphosphino) -1, 1'-biphenyl (thi) 2,2 ', 3,3'-tetramethoxy-6,6'-bis (diphenylphosphino) -1,1'-biphenyl
【００２７】（ツ）２,２',４,４'−テトラメチル−３,
３'−ジメトキシ−６,６'−ビス（ジフェニルホスフィ
ノ）−１,１'−ビフェニル （テ）２,２'−ジメチル−６,６'−ビス（ジ−ｐ−トリ
ルホスフィノ）−１,１'−ビフェニル （ト）２,２'−ジメチル−６,６'−ビス［ジ−（ｐ−ｔ
ｅｒｔ−ブチルフェニル）ホスフィノ］−１,１'−ビフ
ェニル （ナ）２,２',４,４'−テトラメチル−３,３'−ジメト
キシ−６,６'−ビス［ジ−（ｐ−メトキシフェニル）ホ
スフィノ］−１,１'−ビフェニル(T) 2,2 ', 4,4'-tetramethyl-3,
3'-dimethoxy-6,6'-bis (diphenylphosphino) -1,1'-biphenyl (te) 2,2'-dimethyl-6,6'-bis (di-p-tolylphosphino) -1,1 '-Biphenyl (to) 2,2'-dimethyl-6,6'-bis [di- (pt
ert-Butylphenyl) phosphino] -1,1′-biphenyl (na) 2,2 ′, 4,4′-tetramethyl-3,3′-dimethoxy-6,6′-bis [di- (p-methoxy Phenyl) phosphino] -1,1'-biphenyl
【００２８】これらの第三級ホスフィンは、特開昭６３
−１３５３９７号公報、特開平３−２７５６９１号公
報、特開平４−１３９１４０号公報、R.Schmid et al.,
Helv.Chim. Acta, Vol.74, pp.370-389(1991) 、R.Sch
mid et al., Helv.Chim.Acta,Vol.71, pp.897-929(198
8) またはN.Yamamoto et al., Chem.Pharm.Bull., Vol.
39 (4) pp.1085-1087(1991)に記載されている方法によ
って調製することができる。These tertiary phosphines are described in JP-A-63
-135397, JP-A-3-275691, JP-A-4-139140, R. Schmid et al.,
Helv.Chim.Acta, Vol.74, pp.370-389 (1991), R.Sch
mid et al., Helv.Chim.Acta, Vol.71, pp.897-929 (198
8) Or N. Yamamoto et al., Chem.Pharm.Bull., Vol.
39 (4) pp.1085-1087 (1991).
【００２９】ルテニウム−光学活性ホスフィン錯体
（１）において、ＣＢＰがＲ1−ＢＩＮＡＰで表される
化合物は、例えばＴ.イカリヤら（T.Ikariya et al.,
J.Chem.Soc.,Chem.Commun., pp.922-924 (1985)）また
は特開昭６１−６３６９０号公報に記載の方法により得
ることができる。In the ruthenium-optically active phosphine complex (1), the compound whose CBP is represented by R 1 -BINAP is, for example, T. Ikariya et al.
J.Chem.Soc., Chem.Commun., Pp.922-924 (1985)) or the method described in JP-A-61-63690.
【００３０】すなわち、塩化ルテニウムとシクロオクタ
−１,５−ジエン（以下、「ＣＯＤ」と略記する）とを
エタノール溶媒中で反応させて得られる［ＲｕＣｌ
2（ＣＯＤ）］q（ｑは自然数を示す）１モルを、更に、
トリエチルアミンの存在下、トルエンまたはエタノール
等の溶媒中で、Ｒ1−ＢＩＮＡＰ ０.９５〜１.２モルと
加熱反応させることにより製造される。[RuCl] obtained by reacting ruthenium chloride with cycloocta-1,5-diene (hereinafter abbreviated as "COD") in an ethanol solvent.
2 (COD)] q (q is a natural number) 1 mol,
It is produced by heating and reacting with 0.95 to 1.2 mol of R 1 -BINAP in a solvent such as toluene or ethanol in the presence of triethylamine.
【００３１】また、ルテニウム−光学活性ホスフィン錯
体（１）において、ＣＢＰがＢＩＰＨＥＰで表される化
合物は、特開昭６３−１３５３９７号公報に記載の方法
によって得ることができる。In the ruthenium-optically active phosphine complex (1), the compound in which CBP is represented by BIPHEP can be obtained by the method described in JP-A-63-135397.
【００３２】このようにして得られるルテニウム−ホス
フィン錯体（１）の具体例としては次のものを挙げるこ
とができる。The following can be mentioned as specific examples of the ruthenium-phosphine complex (1) thus obtained.
【００３３】Ｒｕ2Ｃｌ4（ＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（Ｔｏｌ−ＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ｔ−Ｂｕ−ＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ｍ−Ｔｏｌ−ＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ＤＭ−ＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ＤｔＢｕ−ＢＩＮＡＰ）2ＮＥｔ3 Ru 2 Cl 4 (BINAP) 2 NEt 3 Ru 2 Cl 4 (Tol-BINAP) 2 NEt 3 Ru 2 Cl 4 (t-Bu-BINAP) 2 NEt 3 Ru 2 Cl 4 (m-Tol-BINAP) 2 NEt 3 Ru 2 Cl 4 (DM-BINAP) 2 NEt 3 Ru 2 Cl 4 (DtBu-BINAP) 2 NEt 3
【００３４】Ｒｕ2Ｃｌ4（Ｍｅｔｈｏｘｙ−ＢＩＮＡ
Ｐ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ｐ−Ｃｌ−ＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ＣｐＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ＣｙＢＩＮＡＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ＢＩＰＨＥＭＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ＢＩＣＨＥＰ）2ＮＥｔ3 Ｒｕ2Ｃｌ4（ＯｃＨＢＩＮＡＰ）2ＮＥｔ3 Ru 2 Cl 4 (Method-BINA
P) 2 NEt 3 Ru 2 Cl 4 (p-Cl-BINAP) 2 NEt 3 Ru 2 Cl 4 (CpBINAP) 2 NEt 3 Ru 2 Cl 4 (CyBINAP) 2 NEt 3 Ru 2 Cl 4 (BIPHEMP) 2 NEt 3 Ru 2 Cl 4 (BICHEP) 2 NEt 3 Ru 2 Cl 4 (OcHBINAP) 2 NEt 3
【００３５】一方、Ｒｕ−Ｉ−（ＣＢＰ）を製造するた
めの原料である、無機ヨウ化物としては、例えば、ヨウ
化ナトリウム（以下、「ＮａＩ」と記載する）やヨウ化
カリウム（以下、「ＫＩ」と記載する）のようなアルカ
リ金属のヨウ化物、ヨウ化カルシウムのようなアルカリ
土類金属のヨウ化物、ヨウ化銀のようなその他の金属の
ヨウ化物等が挙げられるが、特にＮａＩおよびＫＩが好
ましい。On the other hand, examples of the inorganic iodide as a raw material for producing Ru-I- (CBP) include sodium iodide (hereinafter referred to as "NaI") and potassium iodide (hereinafter referred to as " Alkali metal iodide such as KI ”), alkaline earth metal iodide such as calcium iodide, other metal iodide such as silver iodide, and the like, particularly NaI and KI is preferred.
【００３６】この無機ヨウ化物の使用量は、ルテニウム
−ホスフィン錯体（１）に対しかなり過剰に用いること
が好ましい。 具体的には、ルテニウム−ホスフィン錯
体（１）１モルに対し、約４〜１００モルの範囲とする
のがよく、特に好ましくは約１０〜５０モルの範囲とす
るとよい。It is preferable that the amount of this inorganic iodide used is considerably excessive with respect to the ruthenium-phosphine complex (1). Specifically, the amount is preferably in the range of about 4 to 100 mol, and particularly preferably in the range of about 10 to 50 mol, per 1 mol of the ruthenium-phosphine complex (1).
【００３７】また、本発明方法によってＲｕ−Ｉ−（Ｃ
ＢＰ）を製造するためには、相間移動触媒を用いること
が好ましい。 この相間移動触媒としては、水相および
疎水性有機溶媒相の間を往復することによりヨウ素置換
反応を促進する触媒であれば特に限定されず、例えば、
次式（４） Ｒ6Ｒ7Ｒ8Ｒ9Ｘ+Ｙ- （４） （式中、Ｒ6、Ｒ7、Ｒ8およびＲ9は各々炭素数１〜２０
のアルキル基、アラルキル基またはアリール基を示し、
Ｘ+はアンモニウムイオンまたはホスホニウムイオンを
示し、Ｙ-はフッ素イオン、塩素イオン、臭素イオン、
ヨウ素イオン、ヒドロキシイオンまたは過塩素酸イオン
を示す）で表される触媒が使用される。Further, according to the method of the present invention, Ru-I- (C
For the production of BP) it is preferred to use a phase transfer catalyst. The phase transfer catalyst is not particularly limited as long as it is a catalyst that promotes the iodine substitution reaction by reciprocating between the aqueous phase and the hydrophobic organic solvent phase, for example,
Following formula (4) R 6 R 7 R 8 R 9 X + Y - (4) ( wherein, R 6, R 7, R 8 and R 9 each having 1 to 20 carbon atoms
Represents an alkyl group, an aralkyl group or an aryl group of
X + represents an ammonium ion or a phosphonium ion, Y − represents a fluorine ion, a chlorine ion, a bromine ion,
A catalyst represented by iodine ion, hydroxy ion or perchlorate ion) is used.
【００３８】具体的には、フッ化テトラメチルアンモニ
ウム、フッ化テトラエチルアンモニウム、フッ化テトラ
−ｎ−ブチルアンモニウム、塩化テトラメチルアンモニ
ウム、塩化テトラ−ｎ−プロピルアンモニウム、塩化テ
トラ−ｎ−ブチルアンモニウム、塩化トリ−ｎ−オクチ
ルメチルアンモニウム、塩化ラウリルトリメチルアンモ
ニウム、塩化ベンジルトリメチルアンモニウム、塩化ベ
ンジルトリ−ｎ−プロピルアンモニウム、塩化ベンジル
トリ−ｎ−ブチルアンモニウム、塩化フェニルトリメチ
ルアンモニウム、臭化テトラメチルアンモニウム、臭化
テトラエチルアンモニウム、臭化テトラ−ｎ−プロピル
アンモニウム、臭化テトラ−ｎ−ブチルアンモニウム、Specifically, tetramethylammonium fluoride, tetraethylammonium fluoride, tetra-n-butylammonium fluoride, tetramethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride, chloride Tri-n-octylmethylammonium, lauryltrimethylammonium chloride, benzyltrimethylammonium chloride, benzyltri-n-propylammonium chloride, benzyltri-n-butylammonium chloride, phenyltrimethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, Tetra-n-propylammonium bromide, tetra-n-butylammonium bromide,
【００３９】臭化テトラ−ｎ−ペンチルアンモニウム、
臭化テトラ−ｎ−ヘキシルアンモニウム、臭化テトラ−
ｎ−ヘプチルアンモニウム、臭化テトラ−ｎ−オクチル
アンモニウム、臭化ラウリルトリメチルアンモニウム、
臭化ミリスチルトリメチルアンモニウム、臭化セチルト
リメチルアンモニウム、臭化セチルジメチルエチルアン
モニウム、臭化ベンジルトリメチルアンモニウム、臭化
ベンジルトリエチルアンモニウム、ヨウ化テトラエチル
アンモニウム、ヨウ化テトラ−ｎ−プロピルアンモニウ
ム、ヨウ化テトラ−ｎ−ブチルアンモニウム、ヨウ化テ
トラ−ｎ−ヘキシルアンモニウム、ヨウ化エチルトリメ
チルアンモニウム、ヨウ化エチルトリ−ｎ−プロピルア
ンモニウム、ヨウ化メチルトリ−ｎ−ブチルアンモニウ
ム、ヨウ化ベンジルトリメチルアンモニウム、Tetra-n-pentylammonium bromide,
Tetra-n-hexyl ammonium bromide, tetra-bromide
n-heptyl ammonium, tetra-n-octyl ammonium bromide, lauryl trimethyl ammonium bromide,
Myristyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide, benzyl trimethyl ammonium bromide, benzyl triethyl ammonium bromide, tetraethyl ammonium iodide, tetra-n-propyl ammonium iodide, tetra-n iodide -Butylammonium, tetra-n-hexylammonium iodide, ethyltrimethylammonium iodide, ethyltri-n-propylammonium iodide, methyltri-n-butylammonium iodide, benzyltrimethylammonium iodide,
【００４０】ヨウ化フェニルトリメチルアンモニウム、
水酸化テトラ−ｎ−ブチルアンモニウム、過塩素酸テト
ラ−ｎ−ブチルアンモニウム、塩化ベンジルトリフェニ
ルホスホニウム、塩化テトラフェニルホスホニウム、臭
化テトラ−ｎ−ブチルホスホニウム、臭化エチルトリフ
ェニルホスホニウム、臭化ｎ−ブチルトリフェニルホス
ホニウム、臭化ｎ−プロピルトリフェニルホスホニウ
ム、臭化ｎ−ペンチルトリフェニルホスホニウム、臭化
ｎ−ヘプチルトリフェニルホスホニウム、臭化セチルト
リフェニルホスホニウム、臭化テトラフェニルホスホニ
ウム、ヨウ化メチルトリフェニルホスホニウム、ヨウ化
テトラフェニルホスホニウムなどを例示することができ
るが、特に、ヨウ化テトラ−ｎ−ブチルアンモニウム、
臭化テトラ−ｎ−ブチルアンモニウム（以下、「（Ｃ4
Ｈ9）4ＮＢｒ」と記載する）、臭化テトラ−ｎ−ブチル
ホスホニウムを使用するのが好ましい。Phenyltrimethylammonium iodide,
Tetra-n-butylammonium hydroxide, tetra-n-butylammonium perchlorate, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, tetra-n-butylphosphonium bromide, ethyltriphenylphosphonium bromide, n-bromide Butyltriphenylphosphonium, n-propyltriphenylphosphonium bromide, n-pentyltriphenylphosphonium bromide, n-heptyltriphenylphosphonium bromide, cetyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, methyltriphenyl iodide Examples thereof include phosphonium and tetraphenylphosphonium iodide, but especially tetra-n-butylammonium iodide,
Tetra-n-butylammonium bromide (hereinafter referred to as "(C 4
H 9 ) 4 NBr ”), tetra-n-butylphosphonium bromide is preferably used.
【００４１】相間移動触媒の使用量は、通常の触媒量で
あれば特に限定されることはなく、例えば、ルテニウム
−ホスフィン錯体（１）１モルに対し、約０.０００１
〜０.２モルの範囲とするのがよく、特に好ましくは約
０.０５〜０.１モルの範囲とするとよい。The amount of the phase transfer catalyst used is not particularly limited as long as it is a usual amount, and for example, about 0.0001 relative to 1 mol of the ruthenium-phosphine complex (1).
The amount is preferably in the range of about 0.2 to 0.2 mol, particularly preferably about 0.05 to 0.1 mol.
【００４２】ルテニウム−ホスフィン錯体（１）と無機
ヨウ素化合物の反応において用いられる溶媒としては、
疎水性有機溶媒と水の混合溶媒を挙げることができ、好
ましい疎水性有機溶媒としては、例えば、塩化メチレ
ン、臭化メチレン、トルエン、酢酸エチル等が挙げら
れ、特に塩化メチレンが好ましい。The solvent used in the reaction between the ruthenium-phosphine complex (1) and the inorganic iodine compound is
A mixed solvent of a hydrophobic organic solvent and water can be mentioned, and preferable hydrophobic organic solvents include, for example, methylene chloride, methylene bromide, toluene, ethyl acetate and the like, and methylene chloride is particularly preferable.
【００４３】本発明のＲｕ−Ｉ−（ＣＢＰ）を製造する
ための反応温度は、約０〜１１０℃、特に好ましくは室
温であり、また、反応時間は約３〜４８時間、特に好ま
しくは約２４時間とするとよい。The reaction temperature for producing the Ru-I- (CBP) of the present invention is about 0 to 110 ° C., particularly preferably room temperature, and the reaction time is about 3 to 48 hours, particularly preferably about. 24 hours is recommended.
【００４４】反応終了後、疎水性有機溶媒相を取り出
し、溶媒を留去、乾燥等の方法により精製すれば、目的
とするＲｕ−Ｉ−（ＣＢＰ）を得ることができる。After the completion of the reaction, the hydrophobic organic solvent phase is taken out, the solvent is distilled off and the residue is purified by a method such as drying to obtain the desired Ru-I- (CBP).
【００４５】このようにして得られるＲｕ−Ｉ−（ＣＢ
Ｐ）は、化合物（１）の塩素原子の一部または全部がヨ
ウ素原子に置き換わり、かつ、トリエチルアミンの大部
分が外れた構造を有する錯体であると推定される。すな
わち、本発明の錯体の最低限の構成要素であるルテニウ
ム、ヨウ素および光学活性第三級ホスフィンから成る式
で示せば、次のものを具体例として挙げることができ
る。 尚、上記Ｒｕ−Ｉ−（ＣＢＰ）は、用いるルテニ
ウム−光学活性ホスフィン錯体（１）の絶対配置によ
り、（Ｒ）体または（Ｓ）体のいずれかとして得られる
が、その表示は省略した。The Ru-I- (CB obtained in this way
It is presumed that P) is a complex having a structure in which a part or all of the chlorine atoms of the compound (1) are replaced with iodine atoms and most of triethylamine is removed. That is, the following can be mentioned as specific examples, as long as it is represented by the formula consisting of ruthenium, iodine and optically active tertiary phosphine which are the minimum constituents of the complex of the present invention. The Ru-I- (CBP) is obtained as either the (R) form or the (S) form depending on the absolute configuration of the ruthenium-optically active phosphine complex (1) used, but the display is omitted.
【００４６】Ｒｕ−Ｉ−（ＢＩＮＡＰ） Ｒｕ−Ｉ−（Ｔｏｌ−ＢＩＮＡＰ） Ｒｕ−Ｉ−（ｔ−Ｂｕ−ＢＩＮＡＰ） Ｒｕ−Ｉ−（ｍ−Ｔｏｌ−ＢＩＮＡＰ） Ｒｕ−Ｉ−（ＤＭ−ＢＩＮＡＰ） Ｒｕ−Ｉ−（ＤｔＢｕ−ＢＩＮＡＰ）Ru-I- (BINAP) Ru-I- (Tol-BINAP) Ru-I- (t-Bu-BINAP) Ru-I- (m-Tol-BINAP) Ru-I- (DM-BINAP) Ru-I- (DtBu-BINAP)
【００４７】Ｒｕ−Ｉ−（Ｍｅｔｈｏｘｙ−ＢＩＮＡ
Ｐ） Ｒｕ−Ｉ−（ｐ−Ｃｌ−ＢＩＮＡＰ） Ｒｕ−Ｉ−（ＣｐＢＩＮＡＰ） Ｒｕ−Ｉ−（ＣｙＢＩＮＡＰ） Ｒｕ−Ｉ−（ＢＩＰＨＥＭＰ） Ｒｕ−Ｉ−（ＢＩＣＨＥＰ） Ｒｕ−Ｉ−（ＯｃＨＢＩＮＡＰ）Ru-I- (Methodoxy-BINA
P) Ru-I- (p-Cl-BINAP) Ru-I- (CpBINAP) Ru-I- (CyBINAP) Ru-I- (BIPHEMP) Ru-I- (BICHEP) Ru-I- (OcHBINAP)
【００４８】斯くして得られる本発明のＲｕ−Ｉ−（Ｃ
ＢＰ）は、極めて高い触媒活性を有し、不斉合成用触媒
として広く用いることができる化合物である。特にこの
化合物を４−メチレン−２−オキセタノンの不斉水素化
反応の触媒に用いれば、短時間で効率よく、高い光学純
度の光学活性４−メチル−２−オキセタノンを製造でき
る。The Ru-I- (C of the present invention thus obtained
BP) is a compound that has extremely high catalytic activity and can be widely used as a catalyst for asymmetric synthesis. In particular, when this compound is used as a catalyst for the asymmetric hydrogenation reaction of 4-methylene-2-oxetanone, optically active 4-methyl-2-oxetanone of high optical purity can be produced efficiently in a short time.
【００４９】本発明のＲｕ−Ｉ−（ＣＢＰ）を用いて光
学活性４−メチル−２−オキセタノンを製造するには、
例えば、耐圧容器に窒素雰囲気下、上記したＲｕ−Ｉ−
（ＣＢＰ）、原料化合物である４−メチレン−２−オキ
セタノンおよび溶媒を加えて、水素雰囲気下で不斉水素
化を行えばよい。To produce optically active 4-methyl-2-oxetanone using Ru-I- (CBP) of the present invention,
For example, in a pressure vessel under a nitrogen atmosphere, the above Ru-I-
(CBP), 4-methylene-2-oxetanone as a raw material compound and a solvent may be added to carry out asymmetric hydrogenation in a hydrogen atmosphere.
【００５０】この方法において原料化合物として用いら
れる４−メチレン−２−オキセタノンは、例えば、Ｒ.
Ｊ.クレメンスらが報告した方法（R.J.Clemens et al.,
Chem.Rev., Vol.86, pp.241-318 (1986)）によって、
酢酸または無水酢酸を熱分解することによって容易に合
成により得ることができるものである。4-Methylene-2-oxetanone used as a starting compound in this method is, for example, R.M.
The method reported by J. Clemens et al. (RJClemens et al.,
Chem. Rev., Vol.86, pp.241-318 (1986)),
It can be easily obtained by synthesis by thermally decomposing acetic acid or acetic anhydride.
【００５１】不斉水素化触媒であるＲｕ−Ｉ−（ＣＢ
Ｐ）は、（Ｒ）体または（Ｓ）体のいずれかを選択する
ことにより、所望する絶対配置の４−メチル−２−オキ
セタノンを得ることができる。Ru-I- (CB which is an asymmetric hydrogenation catalyst
By selecting either the (R) form or the (S) form for P), 4-methyl-2-oxetanone having the desired absolute configuration can be obtained.
【００５２】また、光学活性４−メチル−２−オキセタ
ノンの製造を有利に実施するには、Ｒｕ−Ｉ−（ＣＢ
Ｐ）が、金属ルテニウムと光学活性ホスフィンのモル比
が１：１〜１：０.９５の割合で調製されたものを用い
るとよい。 通常の不斉反応では、ルテニウム１当量に
対し、光学活性ホスフィン配位子を約１.０５〜１.２当
量用いて得られる錯体を使用するが、光学活性４−メチ
ル−２−オキセタノンの製造ではこれを１当量以内に抑
えたものを用いることによって、副反応である４−メチ
レン−２−オキセタノンの重合反応を防ぐことができ
る。 尚、光学活性ホスフィン配位子が０.９５当量より
少ないと、金属ルテニウムが過剰になり、不経済とな
る。In order to advantageously carry out the production of optically active 4-methyl-2-oxetanone, Ru-I- (CB
It is preferable to use P) prepared in such a manner that the molar ratio of ruthenium metal to optically active phosphine is 1: 1 to 1: 0.95. In a usual asymmetric reaction, a complex obtained by using about 1.05 to 1.2 equivalents of an optically active phosphine ligand is used with respect to 1 equivalent of ruthenium, but the production of optically active 4-methyl-2-oxetanone is carried out. Then, by using the one in which this is suppressed within 1 equivalent, the polymerization reaction of 4-methylene-2-oxetanone, which is a side reaction, can be prevented. If the amount of the optically active phosphine ligand is less than 0.95 equivalent, the amount of ruthenium metal becomes excessive, which is uneconomical.
【００５３】触媒であるＲｕ−Ｉ−（ＣＢＰ）の使用量
は、原料化合物である４−メチレン−２−オキセタノン
１モルに対して約０.０００１モル〜０.０１モルの範
囲、特に好ましくは、約０.０００２モル〜０.００１モ
ルの範囲とするとよい。触媒が０.０００１モルより少
ない量では触媒としての効果を充分奏さず、また、０.
０１モルより多い量では不経済となる。The amount of Ru-I- (CBP) used as a catalyst is in the range of about 0.0001 mol to 0.01 mol, and particularly preferably 1 mol of 4-methylene-2-oxetanone used as a starting compound. , About 0.0002 mol to 0.001 mol. When the amount of the catalyst is less than 0.0001 mol, the effect as the catalyst is not sufficiently exerted, and the amount is less than 0.001 mol.
If the amount is more than 01 mol, it becomes uneconomical.
【００５４】溶媒としては、通常の不斉水素化に使用さ
れる溶媒であれば特に限定されないが、具体的には、ジ
エチルエーテル、テトラヒドロフラン、１,４−ジオキ
サン等の直鎖状または環状エーテル類、塩化メチレン、
臭化メチレン、ジクロロエタン等の有機ハロゲン化物、
アセトン、メチルエチルケトン、メチルブチルケトン等
のケトン類、酢酸、プロピオン酸等のカルボン酸類、酢
酸エチル、酢酸ブチル、３−ヒドロキシ酪酸メチル等の
エステル類、トルエン、ベンゼン等の芳香族化合物、メ
タノール、エタノール、イソプロパノール、ｔｅｒｔ−
ブチルアルコール、１,３−ブタンジオール等のアルコ
ール類及びこれらの混合溶媒を挙げることができる。The solvent is not particularly limited as long as it is a solvent used for ordinary asymmetric hydrogenation, and specifically, linear or cyclic ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane and the like. , Methylene chloride,
Organic halides such as methylene bromide and dichloroethane,
Acetone, methyl ethyl ketone, ketones such as methyl butyl ketone, acetic acid, carboxylic acids such as propionic acid, ethyl acetate, butyl acetate, esters such as methyl 3-hydroxybutyrate, aromatic compounds such as toluene and benzene, methanol, ethanol, Isopropanol, tert-
Examples thereof include butyl alcohol, alcohols such as 1,3-butanediol, and mixed solvents thereof.
【００５５】不斉水素化の反応温度、反応時間は、触媒
の種類やその他の反応条件により異なるが、通常、室温
〜１００℃、特に好ましくは約３０℃〜６０℃の温度
で、約０.５〜１５時間反応させるとよい。また、水素
圧は、約５〜１５０ｋｇ／ｃｍ2 、特に好ましくは約５
０〜１００ｋｇ／ｃｍ2とするとよい。The reaction temperature and reaction time for the asymmetric hydrogenation depend on the catalyst.
Depending on the type of reaction and other reaction conditions, it is usually room temperature
~ 100 ° C, particularly preferably about 30 ° C to 60 ° C
Then, it is advisable to carry out the reaction for about 0.5 to 15 hours. Also, hydrogen
Pressure is about 5 to 150 kg / cm2 , Particularly preferably about 5
0-100kg / cm2It is good to
【００５６】反応終了後、溶媒留去、蒸留等の方法によ
り反応生成物を精製することにより目的とする光学活性
４−メチル−２−オキセタノンを得ることができる。After completion of the reaction, the desired optically active 4-methyl-2-oxetanone can be obtained by purifying the reaction product by a method such as solvent removal and distillation.
【００５７】[0057]
【実施例】以下、実施例及び比較例を挙げて本発明を具
体的に説明するが、本発明はこれらになんら制約される
ものではない。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００５８】尚、以下の実施例において、得られた化合
物の物性の測定には、次の機器を用いた。 分 解 温 度： 熱重量測定装置（ＴＧＡ）／ＴＧＡ５０
（株式会社 島津製作所製） 元素分析値 ： ２４００ ＣＨＮ Ｅｌｅｍｅｎｔａｌ
Ａｎａｌｙｚｅｒ（パーキン エルマー社製）31 Ｐ−ＮＭＲスペクトル： ＡＭ−４００型装置（ブル
ッカー社製） 外部標準物質； ８５％リン酸 溶 媒 ； テトラヒドロフランｄ8 In the following examples, the following instruments were used to measure the physical properties of the obtained compounds. Decomposition temperature: Thermogravimetric analyzer (TGA) / TGA50
(Manufactured by Shimadzu Corporation) Elemental analysis value: 2400 CHN Elemental
Analyzer (manufactured by Perkin Elmer) 31 P-NMR spectrum: AM-400 apparatus (manufactured by Bruker) External standard material; 85% phosphoric acid solvent; tetrahydrofuran d 8
【００５９】実 施 例 １ Ｒｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］の製造：予
め窒素置換した３００ｍｌ容量の反応容器に、Ｒｕ2Ｃ
ｌ4［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］2ＮＥｔ3 ０.５７
ｇ（０.６３２ｍｍｏｌ）、ＮａＩ ０.９５ｇ（６.３４
ｍｍｏｌ）、（Ｃ4Ｈ9）4ＮＢｒ ２.０ｍｇ（０.００６
３ｍｍｏｌ）、塩化メチレン ５０ｍｌおよび蒸留水 ２
０ｍｌを入れ、室温で４４時間攪拌した。 反応後、塩
化メチレン層を注射器で採取し、塩化メチレンを減圧留
去した後、得られた錯体を５０℃で４時間減圧乾燥し
て、標題の黒紫色の錯体を０.６５ｇ（ヨウ素が取り込
まれた量から計算した収率９９％）得た。Example 1 Production of Ru-I-[(S) -Tol-BINAP]: Ru 2 C was placed in a reaction vessel of 300 ml capacity which had been previously purged with nitrogen.
l 4 [(S) -Tol-BINAP] 2 NEt 3 0.57
g (0.632 mmol), NaI 0.95 g (6.34)
mmol), (C 4 H 9 ) 4 NBr 2.0 mg (0.006)
3 mmol), methylene chloride 50 ml and distilled water 2
0 ml was added and the mixture was stirred at room temperature for 44 hours. After the reaction, the methylene chloride layer was collected with a syringe, the methylene chloride was distilled off under reduced pressure, and the resulting complex was dried under reduced pressure at 50 ° C. for 4 hours to give 0.65 g of the title black-purple complex (incorporating iodine). Yield 99%) was calculated.
【００６０】得られたＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ−Ｂ
ＩＮＡＰ］の物性値は次の通りであった。 分 解 温 度： ３５３℃ 元素分析値 ： Ｃ ５７.９７％, Ｈ ４.６９％31 Ｐ−ＮＭＲスペクトル： 図 １The obtained Ru-I-[(S) -Tol-B
The physical properties of [INAP] were as follows. Decomposition temperature: 353 ° C. Elemental analysis value: C 57.97%, H 4.69% 31 P-NMR spectrum: FIG.
【００６１】実 施 例 ２ Ｒｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］の製造：予
め窒素置換した３００ｍｌ容量の反応容器に、Ｒｕ2Ｃ
ｌ4［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］2ＮＥｔ3 １.４３
ｇ（１.５９ｍｍｏｌ）、ＫＩ ２.５８ｇ（１５.５４ｍ
ｍｏｌ）、（Ｃ4Ｈ9）4ＮＢｒ ５.１ｍｇ（０.０１６ｍ
ｍｏｌ）、塩化メチレン ４０ｍｌおよび蒸留水 ２０ｍ
ｌを入れ、室温で１６時間攪拌した。実施例１と同様に
処理して、標題の黒紫色の錯体を１.４９ｇ（ヨウ素が
取り込まれた量から計算した収率９１％）得た。Example 2 Production of Ru-I-[(S) -Tol-BINAP]: Ru 2 C was placed in a reaction vessel of 300 ml capacity which had been previously purged with nitrogen.
l 4 [(S) -Tol-BINAP] 2 NEt 3 1.43
g (1.59 mmol), KI 2.58 g (15.54 m)
mol), (C 4 H 9 ) 4 NBr 5.1 mg (0.016 m)
mol), methylene chloride 40 ml and distilled water 20 m
1 was added, and the mixture was stirred at room temperature for 16 hours. This was treated in the same manner as in Example 1 to obtain 1.49 g of the title black-purple complex (yield 91% calculated from the amount of iodine incorporated).
【００６２】実 施 例 ３ Ｒｕ−Ｉ−［（Ｓ）−ＢＩＮＡＰ］の製造：予め窒素置
換した３００ｍｌ容量の反応容器に、Ｒｕ2Ｃｌ
4［（Ｓ）−ＢＩＮＡＰ］2ＮＥｔ3 ０.８８ｇ（１.０４
ｍｍｏｌ）、ＮａＩ １.５６ｇ（１０.４０ｍｍｏ
ｌ）、（Ｃ4Ｈ9）4ＮＢｒ ３.３ｍｇ（０.０１０３ｍｍ
ｏｌ）、塩化メチレン ５０ｍｌおよび蒸留水 ２０ｍｌ
を入れ、室温で１６時間攪拌した。 実施例１と同様に
処理して、標題の黒紫色の錯体を１.００ｇ（ヨウ素が
取り込まれた量から計算した収率９８％）得た。Example 3 Production of Ru-I-[(S) -BINAP]: Ru 2 Cl was placed in a 300 ml reaction vessel previously purged with nitrogen.
4 [(S) -BINAP] 2 NEt 3 0.88 g (1.04)
mmol), 1.56 g of NaI (10.40 mmo)
l), (C 4 H 9 ) 4 NBr 3.3 mg (0.0103 mm)
ol), methylene chloride 50 ml and distilled water 20 ml
And stirred at room temperature for 16 hours. This was treated in the same manner as in Example 1 to obtain 1.00 g of the title black-purple complex (yield 98% calculated from the amount of iodine incorporated).
【００６３】得られたＲｕ−Ｉ−［（Ｓ）−ＢＩＮＡ
Ｐ］の物性値は以下の通りであった。 分 解 温 度： ３３３℃ 元素分析値 ： Ｃ ５５.９１％, Ｈ ３.９８％31 Ｐ−ＮＭＲスペクトル： 図 ２The obtained Ru-I-[(S) -BINA
The physical properties of [P] were as follows. Decomposition temperature: 333 ° C. Elemental analysis value: C 55.91%, H 3.98% 31 P-NMR spectrum: FIG.
【００６４】実 施 例 ４ Ｒｕ−Ｉ−［（Ｒ）−ｐ−Ｃｌ−ＢＩＮＡＰ］の製造：
予め窒素置換した３００ｍｌ容量の反応容器に、Ｒｕ2
Ｃｌ4［（Ｒ）−ｐ−Ｃｌ−ＢＩＮＡＰ］2ＮＥｔ3 ０.
５２ｇ（０.２６ｍｍｏｌ）、ＮａＩ ０.７９ｇ（５.２
６ｍｍｏｌ）、（Ｃ4Ｈ9）4ＮＢｒ １.０ｍｇ（０.００
３ｍｍｏｌ）、塩化メチレン ２０ｍｌおよび蒸留水 ８
ｍｌを入れ、室温で１６時間攪拌した。実施例１と同様
に処理して、標題の黒紫色の錯体を０.５１ｇ（ヨウ素
が取り込まれた量から計算した収率８８％）得た。Example 4 Preparation of Ru-I-[(R) -p-Cl-BINAP]:
Ru 2 was added to a 300 ml reaction vessel that had been previously purged with nitrogen.
Cl 4 [(R) -p-Cl-BINAP] 2 NEt 3 0.
52 g (0.26 mmol), NaI 0.79 g (5.2
6 mmol), (C 4 H 9 ) 4 NBr 1.0 mg (0.00
3 mmol), methylene chloride 20 ml and distilled water 8
ml was added, and the mixture was stirred at room temperature for 16 hours. This was treated in the same manner as in Example 1 to obtain 0.51 g of the title black-purple complex (yield 88% calculated from the amount of iodine incorporated).
【００６５】得られたＲｕ−Ｉ−［（Ｒ）−ｐ−Ｃｌ−
ＢＩＮＡＰ］の物性値は以下の通りであった。 分 解 温 度： ３４３℃ 元素分析値 ： Ｃ ５０.３４％, Ｈ ２.９１％31 Ｐ−ＮＭＲスペクトル： 図 ３The obtained Ru-I-[(R) -p-Cl-
BINAP] had the following physical properties. Decomposition temperature: 343 ° C. Elemental analysis value: C 50.34%, H 2.91% 31 P-NMR spectrum: FIG.
【００６６】実 施 例 ５ Ｒｕ−Ｉ−［（Ｓ）−ＯｃＨＢＩＮＡＰ］の製造：予め
窒素置換した３００ｍｌ容量の反応容器に、Ｒｕ2Ｃｌ4
［（Ｓ）−ＯｃＨＢＩＮＡＰ］2ＮＥｔ3 １.３６ｇ
（０.７９５ｍｍｏｌ）、ＮａＩ ２.３８ｇ（１５.９ｍ
ｍｏｌ）、（Ｃ4Ｈ9）4ＮＢｒ ３.２ｍｇ（０.０１ｍｍ
ｏｌ）、塩化メチレン ５０ｍｌおよび蒸留水 ２０ｍｌ
を入れ、室温で１６時間攪拌した。実施例１と同様に処
理して、標題の黒紫色の錯体を１.５６ｇ（ヨウ素が取
り込まれた量から計算した収率９９％）得た。Example 5 Production of Ru-I-[(S) -OcHBINAP]: Ru 2 Cl 4 was added to a reaction vessel of 300 ml capacity which had been previously purged with nitrogen.
[(S) -OcHBINAP] 2 NEt 3 1.36 g
(0.795 mmol), NaI 2.38 g (15.9 m)
mol), (C 4 H 9 ) 4 NBr 3.2 mg (0.01 mm
ol), methylene chloride 50 ml and distilled water 20 ml
And stirred at room temperature for 16 hours. This was treated in the same manner as in Example 1 to obtain 1.56 g of the title black-purple complex (yield 99% calculated from the amount of iodine incorporated).
【００６７】得られたＲｕ−Ｉ−［（Ｓ）−ＯｃＨＢＩ
ＮＡＰ］の物性値は以下の通りであった。 分 解 温 度： ３３３℃ 元素分析値 ： Ｃ ５８.０３％, Ｈ ５.２８％31 Ｐ−ＮＭＲスペクトル： 図 ４The obtained Ru-I-[(S) -OcHBI
The physical properties of [NAP] were as follows. Decomposition temperature: 333 ° C. Elemental analysis value: C 58.03%, H 5.28% 31 P-NMR spectrum: FIG.
【００６８】実 施 例 ６ Ｒｕ−Ｉ−［（Ｒ）−ｔ−Ｂｕ−ＢＩＮＡＰ］の製造：
予め窒素置換した３００ｍｌ容量の反応容器に、Ｒｕ2
Ｃｌ4［（Ｒ）−ｔ−Ｂｕ−ＢＩＮＡＰ］2ＮＥｔ3 ０.
１４２ｇ（０.０６７ｍｍｏｌ）、ＮａＩ ０.２ｇ（１.
３ｍｍｏｌ）、（Ｃ4Ｈ9）4ＮＢｒ ０.２ｍｇ（０.００
０７ｍｍｏｌ）、塩化メチレン ６ｍｌおよび蒸留水 ２
ｍｌを入れ、室温で１６時間攪拌した。実施例１と同様
に処理して、標題の黒紫色の錯体を０.１４３ｇ（ヨウ
素が取り込まれた量から計算した収率９０％）得た。Example 6 Preparation of Ru-I-[(R) -t-Bu-BINAP]:
Ru 2 was added to a 300 ml reaction vessel that had been previously purged with nitrogen.
Cl 4 [(R) -t-Bu-BINAP] 2 NEt 3 0.
142 g (0.067 mmol), NaI 0.2 g (1.
3 mmol), (C 4 H 9 ) 4 NBr 0.2 mg (0.00
07 mmol), 6 ml of methylene chloride and distilled water 2
ml was added, and the mixture was stirred at room temperature for 16 hours. This was treated in the same manner as in Example 1 to obtain 0.143 g of the title black-purple complex (yield 90% calculated from the amount of iodine incorporated).
【００６９】実 施 例 ７ （Ｒ）−４−メチル−２−オキセタノンの製造：１００
ｍｌ容量のステンレス製オートクレーブに、窒素雰囲気
下、実施例１で得たＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩ
ＮＡＰ］ ２０.３ｍｇ（０.０２ｍｍｏｌ）を秤り取
り、テトラヒドロフラン ３５ｍｌを加えて溶解した。
これに４−メチレン−２−オキセタノン５.０ｇ（５９.
５ｍｍｏｌ）を入れ、水素圧９０ｋｇ／ｃｍ2、反応温
度５０℃で３時間撹拌した。 得られた反応液をクライ
ゼンフラスコを用いて蒸留し、沸点７１℃〜７３℃／２
９ｍｍＨｇの留分４.７１ｇ（収率：９０％）を得た。Example 7 Preparation of (R) -4-methyl-2-oxetanone: 100
Ru-I-[(S) -Tol-BI obtained in Example 1 was placed in a stainless steel autoclave having a capacity of ml under a nitrogen atmosphere.
NAP] 20.3 mg (0.02 mmol) was weighed out and dissolved in 35 ml of tetrahydrofuran.
To this, 5.0 g of 4-methylene-2-oxetanone (59.
(5 mmol) was added, and the mixture was stirred at a hydrogen pressure of 90 kg / cm 2 and a reaction temperature of 50 ° C. for 3 hours. The obtained reaction liquid was distilled using a Claisen flask, and the boiling point was 71 ° C to 73 ° C / 2.
A fraction of 9 mmHg (4.71 g, yield: 90%) was obtained.
【００７０】生成物は、ガスクロマトグラフィーによる
標品との比較分析の結果、４−メチル−２−オキセタノ
ンであることが確認され、また、ダイセル化学工業株式
会社製光学活性カラム（ＣＨＩＲＡＬＣＥＬ ＯＡ）を
用いた高速液体クロマトグラフィーによる分析の結果、
このものは（Ｒ）体で光学純度は９３.９％ｅ.ｅ.であ
ることが確認された。The product was confirmed to be 4-methyl-2-oxetanone as a result of a comparative analysis by gas chromatography with a standard product. Further, an optically active column (CHIRALCEL OA) manufactured by Daicel Chemical Industries, Ltd. was used. As a result of analysis by high performance liquid chromatography used,
It was confirmed that this product was the (R) form with an optical purity of 93.9% ee.
【００７１】実 施 例 ８ （Ｒ）−４−メチル−２−オキセタノンの製造：１００
ｍｌ容量のステンレス製オートクレーブに、窒素雰囲気
下、実施例２で得たＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩ
ＮＡＰ］ ３０.７ｍｇ（０.０３ｍｍｏｌ）を秤り取
り、テトラヒドロフラン３５ｍｌを加えて溶解した。
これに４−メチレン−２−オキセタノン ５.０ｇ（５
９.５ｍｍｏｌ）を入れ、水素圧９０ｋｇ／ｃｍ2、反応
温度５０℃で７時間撹拌し、実施例７と同様に蒸留して
留分４.６０ｇ（収率：８８％）を得た。Example 8 Preparation of (R) -4-methyl-2-oxetanone: 100
Ru-I-[(S) -Tol-BI obtained in Example 2 was placed in a stainless steel autoclave having a volume of ml under a nitrogen atmosphere.
NAP] 30.7 mg (0.03 mmol) was weighed and dissolved in 35 ml of tetrahydrofuran.
4-methylene-2-oxetanone 5.0 g (5
(9.5 mmol) was added, and the mixture was stirred at a hydrogen pressure of 90 kg / cm 2 and a reaction temperature of 50 ° C. for 7 hours, and distilled in the same manner as in Example 7 to obtain 4.60 g of a fraction (yield: 88%).
【００７２】実施例７と同様に分析した結果、このもの
は（Ｒ）−４−メチル−２−オキセタノンで光学純度は
９３.１％ｅ.ｅ.であることが確認された。As a result of analysis in the same manner as in Example 7, it was confirmed that this was (R) -4-methyl-2-oxetanone and the optical purity was 93.1% ee.
【００７３】実 施 例 ９ （Ｒ）−４−メチル−２−オキセタノンの製造：１００
ｍｌ容量のステンレス製オートクレーブに、窒素雰囲気
下、実施例３で得たＲｕ−Ｉ−［（Ｓ）−ＢＩＮＡＰ］
５８.１ｍｇ（０.０６ｍｍｏｌ）を秤り取り、テトラ
ヒドロフラン３５ｍｌを加えて溶解した。 これに４−
メチレン−２−オキセタノン ５.０ｇ（５９.４ｍｍｏ
ｌ）を入れ、水素圧９０ｋｇ／ｃｍ2、反応温度５０℃
で１８.５時間撹拌し、実施例７と同様に蒸留して留分
４.５０ｇ（収率：８８％）を得た。Example 9 Preparation of (R) -4-methyl-2-oxetanone: 100
Ru-I-[(S) -BINAP] obtained in Example 3 was placed in a stainless steel autoclave with a volume of ml under a nitrogen atmosphere.
58.1 mg (0.06 mmol) was weighed out and dissolved in 35 ml of tetrahydrofuran. 4-
Methylene-2-oxetanone 5.0 g (59.4 mmo
l), hydrogen pressure 90 kg / cm 2 , reaction temperature 50 ° C.
The mixture was stirred for 18.5 hours and distilled in the same manner as in Example 7 to obtain a fraction of 4.50 g (yield: 88%).
【００７４】実施例７と同様に分析した結果、このもの
は（Ｒ）−４−メチル−２−オキセタノンで光学純度は
９４.１％ｅ.ｅ.であることが確認された。As a result of analysis in the same manner as in Example 7, it was confirmed that this was (R) -4-methyl-2-oxetanone and the optical purity was 94.1% ee.
【００７５】実 施 例 １０ （Ｒ）−４−メチル−２−オキセタノンの製造：１００
ｍｌ容量のステンレス製オートクレーブに、窒素雰囲気
下、実施例１で得たＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩ
ＮＡＰ］ ３０.８ｍｇ（０.０３ｍｍｏｌ）を秤り取
り、トルエン３５ｍｌを加えて溶解した。 これに４−
メチレン−２−オキセタノン ５.１ｇ（６０.２ｍｍｏ
ｌ）を入れ、水素圧９０ｋｇ／ｃｍ2 、反応温度５０℃
で２０時間撹拌し、実施例７と同様に蒸留して留分３.
８４ｇ（収率：７６％）を得た。Example 10 Preparation of (R) -4-methyl-2-oxetanone: 100
Nitrogen atmosphere in a stainless steel autoclave of ml capacity
Below, Ru-I-[(S) -Tol-BI obtained in Example 1
NAP] Weigh out 30.8 mg (0.03 mmol)
Then, 35 ml of toluene was added and dissolved. 4-
Methylene-2-oxetanone 5.1 g (60.2 mmo
l), hydrogen pressure 90kg / cm2 , Reaction temperature 50 ℃
Stir for 20 hours and distill as in Example 7 to obtain a fraction 3.
84 g (yield: 76%) was obtained.
【００７６】実施例７と同様に分析した結果、このもの
は（Ｒ）−４−メチル−２−オキセタノンで光学純度は
９１.５％ｅ.ｅ.であることが確認された。As a result of analysis in the same manner as in Example 7, it was confirmed that this was (R) -4-methyl-2-oxetanone and the optical purity was 91.5% ee.
【００７７】実 施 例 １１ （Ｒ）−４−メチル−２−オキセタノンの製造：１００
ｍｌ容量のステンレス製オートクレーブに、窒素雰囲気
下、実施例１で得たＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩ
ＮＡＰ］ ６１.５ｍｇ（０.０６ｍｍｏｌ）を秤り取
り、酢酸エチル ３５ｍｌを加えて溶解した。 これに４
−メチレン−２−オキセタノン ５.２ｇ（６１.７ｍｍ
ｏｌ）を入れ、水素圧９０ｋｇ／ｃｍ2、反応温度５０
℃で３時間撹拌し、実施例７と同様に蒸留して留分４.
９８ｇ（収率：９４％）を得た。Example 11 Preparation of (R) -4-methyl-2-oxetanone: 100
Ru-I-[(S) -Tol-BI obtained in Example 1 was placed in a stainless steel autoclave having a capacity of ml under a nitrogen atmosphere.
NAP] 61.5 mg (0.06 mmol) was weighed out, and 35 ml of ethyl acetate was added and dissolved. To this 4
-Methylene-2-oxetanone 5.2 g (61.7 mm)
ol), hydrogen pressure 90 kg / cm 2 , reaction temperature 50
Stir for 3 hours at 0 ° C. and distill as in Example 7 to obtain fraction 4.
98 g (yield: 94%) was obtained.
【００７８】実施例７と同様に分析した結果、このもの
は（Ｒ）−４−メチル−２−オキセタノンで光学純度は
９３.８％ｅ.ｅ.であることが確認された。As a result of analysis in the same manner as in Example 7, it was confirmed that this was (R) -4-methyl-2-oxetanone and the optical purity was 93.8% ee.
【００７９】実 施 例 １２ （Ｒ）−４−メチル−２−オキセタノンの製造：１００
ｍｌ容量のステンレス製オートクレーブに、窒素雰囲気
下、実施例１で得たＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩ
ＮＡＰ］ ６１.５ｍｇ（０.０６ｍｍｏｌ）を秤り取
り、テトラヒドロフラン３２ｍｌおよびメタノール３ｍ
ｌを加えて溶解した。 これに４−メチレン−２−オキ
セタノン５.２ｇ（６１.７ｍｍｏｌ）を入れ、水素圧９
０ｋｇ／ｃｍ2、反応温度５０℃で１８時間撹拌し、実
施例７と同様に蒸留し、留分４.４１ｇ（収率：８４.６
％）を得た。Example 12 Preparation of (R) -4-methyl-2-oxetanone: 100
Ru-I-[(S) -Tol-BI obtained in Example 1 was placed in a stainless steel autoclave having a capacity of ml under a nitrogen atmosphere.
NAP] 61.5 mg (0.06 mmol) was weighed, tetrahydrofuran 32 ml and methanol 3 m
1 was added and dissolved. 5.2 g (61.7 mmol) of 4-methylene-2-oxetanone was added to this, and the hydrogen pressure was adjusted to
The mixture was stirred at 0 kg / cm 2 and a reaction temperature of 50 ° C. for 18 hours and distilled in the same manner as in Example 7 to obtain a fraction of 4.41 g (yield: 84.6).
%) Was obtained.
【００８０】実施例７と同様に分析した結果、このもの
は（Ｒ）−４−メチル−２−オキセタノンで光学純度は
９２.６％ｅ.ｅ.であることが確認された。As a result of analysis in the same manner as in Example 7, it was confirmed that this was (R) -4-methyl-2-oxetanone and the optical purity was 92.6% ee.
【００８１】実 施 例 １３ （Ｒ）−４−メチル−２−オキセタノンの製造：１００
ｍｌ容量のステンレス製オートクレーブに、窒素雰囲気
下、実施例１で得たＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ−ＢＩ
ＮＡＰ］ ６１.５ｍｇ（０.０６ｍｍｏｌ）を秤り取
り、酢酸エチル ３５ｍｌを加えて溶解した。 これに４
−メチレン−２−オキセタノン ５.２ｇ（６１.７ｍｍ
ｏｌ）を入れ、水素圧９０ｋｇ／ｃｍ2、反応温度５０
℃で３時間撹拌し、実施例７と同様に蒸留して留分４.
９８ｇ（収率：９４％）を得た。Example 13 Preparation of (R) -4-methyl-2-oxetanone: 100
Ru-I-[(S) -Tol-BI obtained in Example 1 was placed in a stainless steel autoclave having a capacity of ml under a nitrogen atmosphere.
NAP] 61.5 mg (0.06 mmol) was weighed out, and 35 ml of ethyl acetate was added and dissolved. To this 4
-Methylene-2-oxetanone 5.2 g (61.7 mm)
ol), hydrogen pressure 90 kg / cm 2 , reaction temperature 50
Stir for 3 hours at 0 ° C. and distill as in Example 7 to obtain fraction 4.
98 g (yield: 94%) was obtained.
【００８２】実施例７と同様に分析した結果、このもの
は（Ｒ）−４−メチル−２−オキセタノンで光学純度は
９３.８％ｅ.ｅ.であることが確認された。As a result of analysis in the same manner as in Example 7, it was confirmed that this was (R) -4-methyl-2-oxetanone and the optical purity was 93.8% ee.
【００８３】実 施 例 １４ （Ｓ）−４−メチル−２−オキセタノンの製造：実施例
４で得たＲｕ−Ｉ−［（Ｒ）−ｐ−Ｃｌ−ＢＩＮＡＰ］
５５.８ｍｇ（０.０５ｍｍｏｌ）、４−メチレン−２
−オキセタノン ４.２ｇ（５０.０ｍｍｏｌ）およびテ
トラヒドロフラン ２８ｍｌを用い、その他の条件は実
施例７と同様にして（Ｓ）−４−メチル−２−オキセタ
ノン ３.４２ｇ（収率８０％）を得た。 このものの光
学純度は９３.８％ｅ.ｅ.であった。Example 14 Preparation of (S) -4-methyl-2-oxetanone: Ru-I-[(R) -p-Cl-BINAP] obtained in Example 4.
55.8 mg (0.05 mmol), 4-methylene-2
-Oxetanone 4.2 g (50.0 mmol) and tetrahydrofuran 28 ml were used, and other conditions were the same as in Example 7 to obtain (S) -4-methyl-2-oxetanone 3.42 g (yield 80%). . The optical purity of this product was 93.8% ee.
【００８４】実 施 例 １５ （Ｒ）−４−メチル−２−オキセタノンの製造：実施例
５で得たＲｕ−Ｉ−［（Ｓ）−ＯｃＨＢＩＮＡＰ］ ４
９.３ｍｇ（０.０５ｍｍｏｌ）、４−メチレン−２−オ
キセタノン ４.２ｇ（５０.０ｍｍｏｌ）およびテトラ
ヒドロフラン ２８ｍｌを用い、その他の条件は実施例
７と同様にして（Ｒ）−４−メチル−２−オキセタノン
１.８９ｇ（収率４４％）を得た。 このものの光学純
度は９３.２％ｅ.ｅ.であった。Example 15 Preparation of (R) -4-methyl-2-oxetanone: Ru-I-[(S) -OcHBINAP] 4 obtained in Example 5.
9.3 mg (0.05 mmol), 4-methylene-2-oxetanone 4.2 g (50.0 mmol) and tetrahydrofuran 28 ml were used, and other conditions were the same as in Example 7 (R) -4-methyl-2. -Oxetanone 1.89 g (44% yield) was obtained. The optical purity of this product was 93.2% ee.
【００８５】比 較 例 １ ヨウ素原子で置換するかわりに、臭素原子で置換したル
テニウム−ブロム−光学活性ホスフィン錯体を製造し、
これを触媒として用いて光学活性４−メチル−２−オキ
セタノンを製造した。すなわち、実施例１に準じて、予
め窒素置換した３００ｍｌ容量の反応容器に、Ｒｕ2Ｃ
ｌ4［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］2ＮＥｔ3 ３.２２
ｇ（３.５７ｍｍｏｌ）、ＮａＢｒ ３.７０ｇ（３５.９
６ｍｍｏｌ）、（Ｃ4Ｈ9）4ＮＢｒ １２.０ｍｇ（０.０
３ｍｍｏｌ）、塩化メチレン １００ｍｌおよび蒸留水
８０ｍｌを入れ、室温で１６時間攪拌し、ルテニウム−
ブロム−光学活性ホスフィン錯体（以下、「Ｒｕ−Ｂｒ
−［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］」と略記する）を
２.６４ｇ（臭素が取り込まれた量から計算した収率９
８％）得た。Comparative Example 1 A ruthenium-bromine-optically active phosphine complex substituted with a bromine atom instead of the iodine atom was prepared,
Using this as a catalyst, optically active 4-methyl-2-oxetanone was produced. That is, according to Example 1, Ru 2 C was placed in a 300 ml-capacity reaction vessel previously purged with nitrogen.
l 4 [(S) -Tol-BINAP] 2 NEt 3 3.22
g (3.57 mmol), NaBr 3.70 g (35.9)
6 mmol), (C 4 H 9 ) 4 NBr 12.0 mg (0.0
3 mmol), methylene chloride 100 ml and distilled water
Add 80 ml and stir at room temperature for 16 hours.
Brom-optically active phosphine complex (hereinafter referred to as "Ru-Br
-[(S) -Tol-BINAP] "is 2.64 g (yield calculated from the amount of bromine incorporated 9
8%) was obtained.
【００８６】この錯体Ｒｕ−Ｂｒ−［（Ｓ）−Ｔｏｌ−
ＢＩＮＡＰ］ ５５.９ｍｇ（０.０６ｍｍｏｌ）を秤り
取り、実施例７に準じて、これを窒素雰囲気下、１００
ｍｌ容量のステンレス製オートクレーブに入れ、テトラ
ヒドロフラン ３５ｍｌを加えて溶解し、４−メチレン
−２−オキセタノン ５.１ｇ（６０.０ｍｍｏｌ）を入
れ、水素圧９０ｋｇ／ｃｍ2、反応温度５０℃で１８時
間撹拌し、（Ｒ）−４−メチル−２−オキセタノン ４.
７０ｇ（収率９２％）を得た。 このものの光学純度は
９２.４％ｅ.ｅ.であった。This complex Ru-Br-[(S) -Tol-
BINAP] 55.9 mg (0.06 mmol) was weighed out, and according to Example 7, this was 100% under nitrogen atmosphere.
Put it in a stainless steel autoclave of ml capacity, add 35 ml of tetrahydrofuran to dissolve it, add 5.1 g (60.0 mmol) of 4-methylene-2-oxetanone, stir at a hydrogen pressure of 90 kg / cm 2 and a reaction temperature of 50 ° C. for 18 hours. And (R) -4-methyl-2-oxetanone 4.
70 g (yield 92%) was obtained. The optical purity of this product was 92.4% ee.
【００８７】以上の結果より、本発明の錯体Ｒｕ−Ｉ−
［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］を触媒として用いた実
施例７の方が、臭素原子を置換したＲｕ−Ｂｒ−
［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］を触媒として用いた比
較例１よりも、はるかに短い反応時間で反応を終了する
ことができ、また、光学純度の高い生成物を得ることが
できることが明らかである。From the above results, the complex of the present invention Ru-I-
Example 7 using [(S) -Tol-BINAP] as a catalyst is Ru-Br- substituted with a bromine atom.
It is clear that the reaction can be completed in a much shorter reaction time than in Comparative Example 1 using [(S) -Tol-BINAP] as a catalyst, and that a product with high optical purity can be obtained. is there.
【００８８】比 較 例 ２ 従来より知られているハロゲン原子を配位したルテニウ
ム−ホスフィン錯体の製法に準じて、ヨウ素を配位した
錯体ＲｕＩ2［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］を製造
し、これを触媒として用いて光学活性４−メチル−２−
オキセタノンを製造した。Comparative Example 2 An iodine-coordinating complex RuI 2 [(S) -Tol-BINAP] was produced according to a conventionally known method for producing a ruthenium-phosphine complex having a halogen atom. Using this as a catalyst, optically active 4-methyl-2-
Oxetanone was produced.
【００８９】すなわち、野依らの方法（R.Noyori et a
l., J. Am. Chem. Soc., Vol.109, No,19, pp.5856-585
8 (1987)）に準じて、予め窒素置換した３００ｍｌ容量
の反応容器に、［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］Ｒｕ
（ＯＣＯＣＨ3）2 ２.３６ｇ（２.６０ｍｍｏｌ）、ヨ
ウ化水素を５７重量％含有する水溶液 ５.８５ｇ（ヨウ
化水素換算量２６.０７ｍｍｏｌ）、塩化メチレン ５０
ｍｌおよびメタノール５０ｍｌを入れ、室温で１時間攪
拌した。 溶媒を減圧留去した後、得られた錯体をさら
に５０℃で４時間減圧乾燥してＲｕＩ2［（Ｓ）−Ｔｏ
ｌ−ＢＩＮＡＰ］ ２.６４ｇ（収率９８％）を得た。That is, the method of Noyori et al. (R. Noyori et a
l., J. Am. Chem. Soc., Vol.109, No, 19, pp.5856-585
8 (1987)), add [(S) -Tol-BINAP] Ru to a 300 ml reaction vessel previously purged with nitrogen.
(OCOCH 3 ) 2 2.36 g (2.60 mmol), aqueous solution containing hydrogen iodide 57% by weight 5.85 g (hydrogen iodide conversion amount 26.07 mmol), methylene chloride 50
ml and 50 ml of methanol were added, and the mixture was stirred at room temperature for 1 hour. After the solvent was distilled off under reduced pressure, the obtained complex was further dried under reduced pressure at 50 ° C. for 4 hours to obtain RuI 2 [(S) -To.
1-BINAP] (2.64 g, yield 98%) was obtained.
【００９０】この錯体３０.８ｍｇ（０.０３ｍｍｏｌ）
を秤量し、実施例７に準じて、これを窒素雰囲気下、１
００ｍｌ容量のステンレス製オートクレーブに入れ、テ
トラヒドロフラン ３５ｍｌを加えて溶解し、４−メチ
レン−２−オキセタノン ５.３ｇ（６２.６ｍｍｏｌ）
を入れ、水素圧９０ｋｇ／ｃｍ2、反応温度５０℃で２
０時間撹拌し、（Ｒ）−４−メチル−２−オキセタノン
４.３０ｇ（収率８０％）を得た。 このものの光学純
度は９２.０％ｅ.ｅ.であった。30.8 mg (0.03 mmol) of this complex
Was weighed, and according to Example 7, this was placed under a nitrogen atmosphere,
Put it in a stainless steel autoclave with a volume of 00 ml, add 35 ml of tetrahydrofuran and dissolve it, 5.3 g (62.6 mmol) of 4-methylene-2-oxetanone
2 at a hydrogen pressure of 90 kg / cm 2 and a reaction temperature of 50 ° C.
After stirring for 0 hour, 4.30 g (yield 80%) of (R) -4-methyl-2-oxetanone was obtained. The optical purity of this product was 92.0% ee.
【００９１】以上の結果より、本発明の錯体Ｒｕ−Ｉ−
［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］を触媒として用いた実
施例７の方が、従来より知られているハロゲン原子を配
位したルテニウム−ホスフィン錯体の製法に準じて得ら
れるＲｕＩ2［（Ｓ）−Ｔｏｌ−ＢＩＮＡＰ］を触媒と
して用いた比較例２よりも、はるかに短い反応時間で反
応を終了することができ、また、光学純度の高い生成物
を得ることができることが明らかである。From the above results, the complex of the present invention Ru-I-
Example 7 using [(S) -Tol-BINAP] as a catalyst is RuI 2 [(S) obtained according to a conventionally known method for producing a ruthenium-phosphine complex in which a halogen atom is coordinated. It is clear that the reaction can be completed in a much shorter reaction time than in Comparative Example 2 using -Tol-BINAP] as a catalyst, and a product with high optical purity can be obtained.
【００９２】[0092]
【発明の効果】本発明の製法によって得られるルテニウ
ム−ヨード−光学活性ホスフィン錯体は、極めて高い触
媒活性を有し、かつ、不斉反応における高い不斉収率、
すなわち、光学純度が高い生成物を得ることができるた
め、経済的に有利な不斉合成用触媒として広く用いるこ
とができるものである。特に、この錯体を触媒として用
いて、４−メチレン−２−オキセタノンを不斉水素化す
ることにより、ポリマー原料等として有用な光学活性４
−メチル−２−オキセタノンを、短時間で効率よく、し
かも高い光学純度のものとして得ることができる。INDUSTRIAL APPLICABILITY The ruthenium-iodo-optically active phosphine complex obtained by the production method of the present invention has an extremely high catalytic activity and a high asymmetric yield in an asymmetric reaction,
That is, since a product having a high optical purity can be obtained, it can be widely used as an economically advantageous catalyst for asymmetric synthesis. In particular, by using this complex as a catalyst to asymmetrically hydrogenate 4-methylene-2-oxetanone, an optically active compound 4 useful as a polymer raw material or the like can be obtained.
-Methyl-2-oxetanone can be obtained in a short time efficiently and with high optical purity.
【図１】 実施例１で得たＲｕ−Ｉ−［（Ｓ）−Ｔｏｌ
−ＢＩＮＡＰ］の31 Ｐ−ＮＭＲスペクトルを示す図面。FIG. 1 Ru-I-[(S) -Tol obtained in Example 1
-BINAP]31 The drawing which shows a P-NMR spectrum.
【図２】 実施例３で得たＲｕ−Ｉ−［（Ｓ）−ＢＩＮ
ＡＰ］の31Ｐ−ＮＭＲスペクトルを示す図面。FIG. 2 Ru-I-[(S) -BIN obtained in Example 3
The drawing which shows the < 31 > P-NMR spectrum of [AP].
【図３】 実施例４で得たＲｕ−Ｉ−［（Ｒ）−ｐ−Ｃ
ｌ−ＢＩＮＡＰ］の 31Ｐ−ＮＭＲスペクトルを示す図
面。FIG. 3 Ru-I-[(R) -p-C obtained in Example 4
l-BINAP] 31The figure which shows P-NMR spectrum
surface.
【図４】 実施例５で得たＲｕ−Ｉ−［（Ｓ）−ＯｃＨ
ＢＩＮＡＰ］の31Ｐ−ＮＭＲスペクトルを示す図面。 以 上FIG. 4 Ru-I-[(S) -OcH obtained in Example 5
BINAP] shows the 31 P-NMR spectrum. that's all
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山口 明夫 神奈川県平塚市西八幡１丁目４番11号 高 砂香料工業株式会社総合研究所内 (72)発明者 萩原 利光 神奈川県平塚市西八幡１丁目４番11号 高 砂香料工業株式会社総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akio Yamaguchi 1-4-11 Nishihachiman, Hiratsuka-shi, Kanagawa Takasago International Corp. Research Institute (72) Toshimitsu Hagihara 1-chome, Nishihachiman, Hiratsuka-shi, Kanagawa No.4-11 Takasago International Corporation Research Center
Claims (2)
アルキル基を示す）または式（３） 【化２】 （ここで、Ｒ2はアリール基または炭素数３〜８のシク
ロアルキル基を、Ｒ3はメチル基またはメトキシ基を示
し、Ｒ4は水素原子、メチル基またはメトキシ基を、Ｒ5
は水素原子、メチル基、メトキシ基またはジ低級アルキ
ル置換アミノ基を示すか、Ｒ3とＲ4が一緒になって隣接
するフェニル基とともにテトラヒドロナフチル基を形成
する）で示される光学活性な第三級ホスフィンを示す］
で表されるルテニウム−光学活性ホスフィン錯体を、無
機ヨウ化物と反応させることを特徴とする、新規なルテ
ニウム−ヨード−光学活性ホスフィン錯体の製法。1. Formula (1) Ru 2 Cl 4 (CBP) 2 NEt 3 (1) [In the formula, Et represents an ethyl group, and CBP is represented by the formula (2): (Wherein R 1 represents an aryl group or a cycloalkyl group having 3 to 8 carbon atoms) or a compound represented by the formula (3): (Here, R 2 represents an aryl group or a cycloalkyl group having 3 to 8 carbon atoms, R 3 represents a methyl group or a methoxy group, R 4 represents a hydrogen atom, a methyl group or a methoxy group, R 5
Is a hydrogen atom, a methyl group, a methoxy group or a di-lower alkyl-substituted amino group, or R 3 and R 4 together form a tetrahydronaphthyl group with the adjacent phenyl group). Grade phosphine]
A method for producing a novel ruthenium-iodo-optically active phosphine complex, which comprises reacting a ruthenium-optically active phosphine complex represented by: with an inorganic iodide.
水素化し光学活性４−メチル−２−オキセタノンを製造
する方法において、触媒として、式（１） Ｒｕ2Ｃｌ4（ＣＢＰ）2ＮＥｔ3 （１） ［式中、Ｅｔはエチル基を示し、ＣＢＰは式（２） 【化３】 （ここでＲ1はアリール基または炭素数３〜８のシクロ
アルキル基を示す）または式（３） 【化４】 （ここで、Ｒ2はアリール基または炭素数３〜８のシク
ロアルキル基を、Ｒ3はメチル基またはメトキシ基を示
し、Ｒ4は水素原子、メチル基またはメトキシ基を、Ｒ5
は水素原子、メチル基、メトキシ基またはジ低級アルキ
ル置換アミノ基を示すか、Ｒ3とＲ4が一緒になって隣接
するフェニル基とともにテトラヒドロナフチル基を形成
する）で示される光学活性な第三級ホスフィンを示す］
で表されるルテニウム−光学活性ホスフィン錯体を、無
機ヨウ化物と反応させることによって得られる、ルテニ
ウム−ヨード−光学活性ホスフィン錯体を用いることを
特徴とする光学活性４−メチル−２−オキセタノンの製
法。2. A method for producing optically active 4-methyl-2-oxetanone by asymmetrically hydrogenating 4-methylene-2-oxetanone, wherein the catalyst of formula (1) Ru 2 Cl 4 (CBP) 2 NEt 3 ( 1) [In the formula, Et represents an ethyl group, and CBP is represented by the formula (2): (Wherein R 1 represents an aryl group or a cycloalkyl group having 3 to 8 carbon atoms) or a compound represented by the formula (3): (Here, R 2 represents an aryl group or a cycloalkyl group having 3 to 8 carbon atoms, R 3 represents a methyl group or a methoxy group, R 4 represents a hydrogen atom, a methyl group or a methoxy group, R 5
Is a hydrogen atom, a methyl group, a methoxy group or a di-lower alkyl-substituted amino group, or R 3 and R 4 together form a tetrahydronaphthyl group with the adjacent phenyl group). Grade phosphine]
A method for producing an optically active 4-methyl-2-oxetanone, which comprises using a ruthenium-iodo-optically active phosphine complex obtained by reacting a ruthenium-optically active phosphine complex represented by the formula with an inorganic iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01311594A JP3437623B2 (en) | 1994-01-12 | 1994-01-12 | Method for producing ruthenium-iodo-optically active phosphine complex and method for producing optically active 4-methyl-2-oxetanone using this complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01311594A JP3437623B2 (en) | 1994-01-12 | 1994-01-12 | Method for producing ruthenium-iodo-optically active phosphine complex and method for producing optically active 4-methyl-2-oxetanone using this complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07206885A true JPH07206885A (en) | 1995-08-08 |
| JP3437623B2 JP3437623B2 (en) | 2003-08-18 |
Family
ID=11824161
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01311594A Expired - Fee Related JP3437623B2 (en) | 1994-01-12 | 1994-01-12 | Method for producing ruthenium-iodo-optically active phosphine complex and method for producing optically active 4-methyl-2-oxetanone using this complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3437623B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841343A3 (en) * | 1996-11-08 | 1998-11-25 | Takasago International Corporation | Ruthenium-optically active phosphine complex, process for the preparation thereof and process for the preparation of optically active 4-methyl-2-oxetanone using same |
| JP2009191063A (en) * | 2008-01-18 | 2009-08-27 | Erick M Carreira | Process for producing optically active substance of [4- (2-diphenylphosphanylnaphthalen-1-yl) phthalazin-1-yl]-(1-phenylethyl) amine |
| CN106478716A (en) * | 2016-09-18 | 2017-03-08 | 江苏欣诺科催化剂有限公司 | A kind of synthetic method of organic phosphorus compound |
-
1994
- 1994-01-12 JP JP01311594A patent/JP3437623B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841343A3 (en) * | 1996-11-08 | 1998-11-25 | Takasago International Corporation | Ruthenium-optically active phosphine complex, process for the preparation thereof and process for the preparation of optically active 4-methyl-2-oxetanone using same |
| JP2009191063A (en) * | 2008-01-18 | 2009-08-27 | Erick M Carreira | Process for producing optically active substance of [4- (2-diphenylphosphanylnaphthalen-1-yl) phthalazin-1-yl]-(1-phenylethyl) amine |
| CN106478716A (en) * | 2016-09-18 | 2017-03-08 | 江苏欣诺科催化剂有限公司 | A kind of synthetic method of organic phosphorus compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3437623B2 (en) | 2003-08-18 |
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