JP2004026655A - Method for manufacturing alkenylphosphorus compound - Google Patents
Method for manufacturing alkenylphosphorus compound Download PDFInfo
- Publication number
- JP2004026655A JP2004026655A JP2002142955A JP2002142955A JP2004026655A JP 2004026655 A JP2004026655 A JP 2004026655A JP 2002142955 A JP2002142955 A JP 2002142955A JP 2002142955 A JP2002142955 A JP 2002142955A JP 2004026655 A JP2004026655 A JP 2004026655A
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- JP
- Japan
- Prior art keywords
- group
- general formula
- same
- represented
- phosphorus compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- -1 acetylene compound Chemical class 0.000 claims abstract description 84
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 125000001424 substituent group Chemical group 0.000 claims description 36
- 229910052698 phosphorus Inorganic materials 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 31
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 25
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 239000003446 ligand Substances 0.000 claims description 15
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000004450 alkenylene group Chemical group 0.000 claims description 5
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000005530 alkylenedioxy group Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 4
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical class P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 7
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 14
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- QCYXGORGJYUYMT-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QCYXGORGJYUYMT-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- IQUAECJNIZFLIC-UHFFFAOYSA-N benzhydrylphosphane nickel Chemical compound [Ni].PC(C1=CC=CC=C1)C1=CC=CC=C1.PC(C1=CC=CC=C1)C1=CC=CC=C1.PC(C1=CC=CC=C1)C1=CC=CC=C1.PC(C1=CC=CC=C1)C1=CC=CC=C1 IQUAECJNIZFLIC-UHFFFAOYSA-N 0.000 description 2
- WBMDPNTUYFBKNY-UHFFFAOYSA-N benzhydrylphosphane nickel Chemical compound [Ni].C1(=CC=CC=C1)C(C1=CC=CC=C1)P WBMDPNTUYFBKNY-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- OTJZCIYGRUNXTP-UHFFFAOYSA-N but-3-yn-1-ol Chemical compound OCCC#C OTJZCIYGRUNXTP-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GOQJMMHTSOQIEI-UHFFFAOYSA-N hex-5-yn-1-ol Chemical compound OCCCCC#C GOQJMMHTSOQIEI-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- WEGVIDVCQHPAKB-UHFFFAOYSA-N nickel;triethylphosphane Chemical compound [Ni].CCP(CC)CC.CCP(CC)CC.CCP(CC)CC.CCP(CC)CC WEGVIDVCQHPAKB-UHFFFAOYSA-N 0.000 description 2
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- DMOVPHYFYSASTC-UHFFFAOYSA-N nona-1,8-diyne Chemical compound C#CCCCCCC#C DMOVPHYFYSASTC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- NFRYVRNCDXULEX-UHFFFAOYSA-N (2-diphenylphosphanylphenyl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C(=CC=CC=1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 NFRYVRNCDXULEX-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- CBYDUPRWILCUIC-UHFFFAOYSA-N 1,2-diethynylbenzene Chemical compound C#CC1=CC=CC=C1C#C CBYDUPRWILCUIC-UHFFFAOYSA-N 0.000 description 1
- 125000004815 1,2-dimethylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([*:2])C([H])([H])[H] 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- DKFHWNGVMWFBJE-UHFFFAOYSA-N 1-ethynylcyclohexene Chemical group C#CC1=CCCCC1 DKFHWNGVMWFBJE-UHFFFAOYSA-N 0.000 description 1
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
- LWISLHRIEATKTM-UHFFFAOYSA-N 2-Ethynylthiophene Chemical compound C#CC1=CC=CS1 LWISLHRIEATKTM-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- UXFIKVWAAMKFQE-UHFFFAOYSA-N 5-chloropent-1-yne Chemical compound ClCCCC#C UXFIKVWAAMKFQE-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BTBORDOYETVCHQ-UHFFFAOYSA-N C(=O)=C1C(C(C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1)=C=O)=C=O.[Ni] Chemical compound C(=O)=C1C(C(C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1)=C=O)=C=O.[Ni] BTBORDOYETVCHQ-UHFFFAOYSA-N 0.000 description 1
- YZHYPNYQVYAQDT-UHFFFAOYSA-N CCCCCCC(=C)P1(=O)OC(C)(C)C(C)(C)O1 Chemical compound CCCCCCC(=C)P1(=O)OC(C)(C)C(C)(C)O1 YZHYPNYQVYAQDT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CXEWXNACPFOORN-FQLXRVMXSA-N [(1r,2r)-2-diphenylphosphanylcyclopentyl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P([C@H]1[C@@H](CCC1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 CXEWXNACPFOORN-FQLXRVMXSA-N 0.000 description 1
- SNIYGPDAYLBEMK-UHFFFAOYSA-M [I-].[Mg+]C1=CC=CC=C1 Chemical compound [I-].[Mg+]C1=CC=CC=C1 SNIYGPDAYLBEMK-UHFFFAOYSA-M 0.000 description 1
- LAQYTBYMZXHCLC-UHFFFAOYSA-N [cyclohexyloxy(oxido)phosphaniumyl]benzene Chemical compound C=1C=CC=CC=1P(=O)OC1CCCCC1 LAQYTBYMZXHCLC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 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
- NEEDEQSZOUAJMU-UHFFFAOYSA-N but-2-yn-1-ol Chemical compound CC#CCO NEEDEQSZOUAJMU-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000005724 cycloalkenylene group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000004410 cyclooctyloxy group Chemical group C1(CCCCCCC1)O* 0.000 description 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000131 cyclopropyloxy group Chemical group C1(CC1)O* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- JZUYMDPYNGVRSD-UHFFFAOYSA-N dimethyl(phenyl)phosphane nickel Chemical compound [Ni].CP(C1=CC=CC=C1)C JZUYMDPYNGVRSD-UHFFFAOYSA-N 0.000 description 1
- UJNLHRZSJZQQOB-UHFFFAOYSA-N dimethyl(phenyl)phosphane;nickel Chemical compound [Ni].CP(C)C1=CC=CC=C1.CP(C)C1=CC=CC=C1.CP(C)C1=CC=CC=C1.CP(C)C1=CC=CC=C1 UJNLHRZSJZQQOB-UHFFFAOYSA-N 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- FTNAYPLICVXRBN-UHFFFAOYSA-N ethene;nickel;triphenylphosphane Chemical compound [Ni].C=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FTNAYPLICVXRBN-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- YJSXLGKPMXKZJR-UHFFFAOYSA-N ethoxy-oxo-phenylphosphanium Chemical compound CCO[P+](=O)C1=CC=CC=C1 YJSXLGKPMXKZJR-UHFFFAOYSA-N 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000001634 furandiyl group Chemical group O1C(=C(C=C1)*)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- MELUCTCJOARQQG-UHFFFAOYSA-N hex-2-yne Chemical compound CCCC#CC MELUCTCJOARQQG-UHFFFAOYSA-N 0.000 description 1
- INVGOSUVGOZKSG-UHFFFAOYSA-N hex-2-ynenitrile Chemical compound CCCC#CC#N INVGOSUVGOZKSG-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- ZPFZQRQDUOHLJK-UHFFFAOYSA-N nickel;prop-2-enenitrile Chemical compound [Ni].C=CC#N.C=CC#N ZPFZQRQDUOHLJK-UHFFFAOYSA-N 0.000 description 1
- JWUCQXRCGHGEBZ-UHFFFAOYSA-N nickel;tricyclohexylphosphane Chemical compound [Ni].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JWUCQXRCGHGEBZ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- MDROPVLMRLHTDK-UHFFFAOYSA-N penta-1,4-diyne Chemical compound C#CCC#C MDROPVLMRLHTDK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5316—Unsaturated acyclic phosphine oxides or thioxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4015—Esters of acyclic unsaturated acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、アルケニルホスホン酸エステル、アルケニルホスフィン酸エステル及びアルケニルホスフィンオキシド化合物等のアルケニルリン化合物の製造方法に関するものである。アルケニルリン化合物は、その基本骨格が天然に見出され、酵素などと作用することにより、それ自身が生理活性を示すことが知られている。同化合物は、各種触媒反応の補助配位子等として広く用いられる第３級ホスフィン等に容易に変換される極めて有用な化合物でもある。更に、同化合物は、求核剤やラジカル種と容易に反応し、Ｈｏｒｎｅｒ−Ｗｉｔｔｉｇ反応に用いることもできるなど、精密化学品の合成の面でも有用性が高い一群の化合物である。
【０００２】
【従来の技術】
このようなアルケニルリン化合物を炭素−リン結合の生成を伴って合成する方法としては、一般的には、対応するアルケニルハライド化合物を水素化ホスホン酸エステル、水素化ホスフィン酸エステル及び二置換ホスフィンオキシド（以下、これらのリン化合物を総称してＰ−Ｈ化合物と呼ぶ。）で置換する方法が考えられる。しかし、この方法では、反応に伴って同時に生成するハロゲン化水素を捕捉するための塩基の添加が必要であり、これによって、大量のハロゲン化水素塩を併産する。また、その出発原料であるアルケニルハライド化合物は、工業的には必ずしも入手が容易でなく、また一般に毒性を有する。このため、この方法は、工業的に有利な方法とは考えられない。一方、触媒を用いて、Ｐ−Ｈ化合物のアセチレンへの付加によるアルケニルリン化合物の製造法も最近報告されているが（日本国特許第２７７５４２６号、第２７７７９８５号、第２８４９７１２号、第３００７９８４号、第３０４１３９６号等）、何れも高価なパラジウム又はロジウム触媒を使用する方法であり、且つこれらの方法は何れも生成物の選択性があまり高くない。
【０００３】
【発明が解決しようとする課題】
本発明は、Ｐ−Ｈ化合物を出発原料とし、安価な触媒を用いて、アルケニルリン化合物を製造する方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明者らは、容易に入手可能なＰ−Ｈ化合物とアセチレン化合物の反応について鋭意研究を重ねた結果、安価なニッケル触媒存在下でこの付加反応が進行し、容易に対応するアルケニルリン化合物を与えることを見出し、本発明を完成するに至った。
【０００５】
即ち、本発明は、ニッケルを含んでなる触媒の存在下に、一般式［１］
Ｒ１（Ｃ≡ＣＲ２）ｎ ［１］
（式中、ｎは１又は２であり、ｎが１の場合のＲ１及びＲ２、並びにｎが２の場合のＲ２は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、同シクロアルキル基、同アルケニル基、同シクロアルケニル基、同アリール基、同アラルキル基、同ヘテロアリール基、同アルコキシ基、同シクロアルコキシ基、同アラルキロキシ基、同アリールオキシ基、同シリル基、又はフェロセニル基を示す。また、ｎが２の場合のＲ１は、置換基を有していてもよいアルキレン基、同シクロアルキレン基、同アルケニレン基、同シクロアルケニレン基、同アリーレン基、同アラルキレン基、同ヘテロアリーレン基、同アルキレンジオキシ基、同シクロアルキレンジオキシ基、同アラルキレンジオキシ基、同アリーレンジオキシ基、同シリレン基、又はフェロセニレン基を示す。）で表されるアセチレン化合物を、一般式［２］
ＨＰ（Ｏ）Ｘ１Ｘ２ ［２］
［式中、Ｘ１はＯＲ３又はＲ３を示し、Ｘ２はＯＲ４又はＲ４を示す（但し、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）。］で表されるリン化合物と反応させることを特徴とする、一般式［３］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）Ｘ１Ｘ２］｝ｎ ［３］
又は／及び一般式［４］
Ｒ１｛Ｃ［Ｐ（Ｏ）Ｘ１Ｘ２］＝ＣＨＲ２｝ｎ ［４］
（式中、ｎ、Ｒ１、Ｒ２、Ｘ１及びＸ２は前記と同じ。）で表されるアルケニルリン化合物の製造方法に関する。
【０００６】
【発明の実施の形態】
上記一般式［１］、［３］及び［４］において、ｎが１の場合のＲ１及びＲ２、並びにｎが２の場合のＲ２で示される、置換基を有していても良いアルキル基のアルキル基としては、例えば、炭素数が１〜２０、好ましくは１〜１０、より好ましくは１〜６の直鎖状又は分枝状のアルキル基が挙げられ、より具体的には、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第二級ブチル基、第三級ブチル基、ペンチル基、ヘキシル基などが挙げられる。
また、置換基を有していてもよいシクロアルキル基のシクロアルキル基としては、例えば、炭素数３〜３０、好ましくは３〜２０、より好ましくは３〜１２の単環、多環又は縮合環式のシクロアルキル基が挙げられ、より具体的には、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基、シクロドデシル基等が挙げられる。
置換基を有していてもよいアルケニル基のアルケニル基としては、例えば、前記した炭素数２以上のアルキル基に１個以上の二重結合を有するものが挙げられ、より具体的には、アリル基、１−プロペニル基、イソプロペニル基、２−ブテニル基、１，３−ブタジエニル基、２−ペンテニル基、２−ヘキセニル基等が挙げられる。
置換基を有していてもよいシクロアルケニル基のシクロアルケニル基としては、前記したシクロアルキル基に１個以上の二重結合を有するものが挙げられ、より具体的には、シクロプロペニル基、シクロペンテニル基、シクロヘキセニル基、シクロオクテニル基等が挙げられる。
【０００７】
置換基を有していてもよいアリール基のアリール基としては、例えば、炭素数６〜３０、好ましくは６〜２０、より好ましくは６〜１４の単環、多環又は縮合環式の芳香族炭化水素基が挙げられ、より具体的には、例えば、フェニル基、トリル基、キシリル基、ナフチル基、メチルナフチル基、アントリル基、フェナントリル基、ビフェニル基等が挙げられる。
置換基を有していてもよいアラルキル基のアラルキル基としては、例えば、炭素数７〜３０、好ましくは７〜２０、より好ましくは７〜１５の単環、多環又は縮合環式のアラルキル基が挙げられ、より具体的には、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ナフチルエチル基等が挙げられる。
置換基を有していてもよいヘテロアリール基のヘテロアリール基としては、酸素、窒素、イオウなどのヘテロ原子を含む各種の複素芳香環基が挙げられ、それに含まれる炭素数は通常４〜１２、好ましくは４〜８である。その具体例としては、チエニル基、フリル基、ピリジル基、ピロリル基などが挙げられる。
置換基を有していてもよいアルコキシ基のアルコキシ基としては、例えば炭素数１〜８、好ましくは１〜４のアルコキシ基が挙げられ、その具体例としては、メトキシ基、エトキシ基、ブトキシ基などが挙げられる。
置換基を有していてもよいシクロアルコキシ基のシクロアルコキシ基としては、例えば、炭素数３〜３０、好ましくは３〜２０、より好ましくは３〜１２の単環、多環又は縮合環式のシクロアルコキシ基が挙げられ、より具体的には、シクロプロピルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロオクチルオキシ基、シクロドデシルオキシ基等が挙げられる。
置換基を有していてもよいアラルキロキシ基としては、例えば、炭素数７〜３０、好ましくは７〜２０、より好ましくは７〜１５の単環、多環又は縮合環式のアラルキロキシ基が挙げられ、より具体的には、例えば、ベンジルオキシ基、フェネチルオキシ基、ナフチルメチルオキシ基、ナフチルエチルオキシ基等が挙げられる。
置換基を有していてもよいアリールオキシ基のアリールオキシ基としては、例えば、炭素数６〜３０、好ましくは６〜２０、より好ましくは６〜１４の単環、多環又は縮合環式の芳香族炭化水素基を有するアリールオキシ基が挙げられ、より具体的には、例えば、フェノキシ基、トリルオキシ基、キシリルオキシ基、ナフトキシ基、メチルナフチルオキシ基、アントリルオキシ基、フェナントリルオキシ基、ビフェニルオキシ基等が挙げられる。
【０００８】
これらアルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、アラルキル基、ヘテロアリール基、アルコキシ基、シクロアルコキシ基、アラルキロキシ基及びアリールオキシ基の置換基としては、例えばメチル基、エチル基、プロピル基等のアルキル基、水酸基、例えばメトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシ基、例えば塩素、臭素、フッ素等のハロゲン原子、シアノ基、例えばジメチルアミノ基、ジエチルアミノ基等のジアルキルアミノ基、例えばメトキシカルボニル基、エトキシカルボニル基等のアルコキシカルボニル基、シリル基、例えばトリメチルシリル基、トリエチルシリル基、ｔ−ブチルジメチルシリル基、トリフェニルシリル基等の置換シリル基、例えばｔ−ブチルジメチルシロキシ基等のシロキシ基等が挙げられる。
【０００９】
また、置換基を有していてもよいシリル基としては、例えばアルキル基、アリール基、アラルキル基、アルコキシ基等で置換されたものが含まれる。その具体例としては、トリメチルシリル基、トリエチルシリル基、トリフェニルシリル基、フェニルジメチルシリル基、トリメトキシシリル基、ｔ−ブチルジメチルシリル基等が挙げられる。
【００１０】
ｎが２の場合のＲ１で示される置換基を有していてもよいアルキレン基、置換基を有していてもよいシクロアルキレン基、置換基を有していてもよいアルケニレン基、置換基を有していてもよいシクロアルケニレン基、置換基を有していてもよいアリーレン基、置換基を有していてもよいアラルキレン基、置換基を有していてもよいヘテロアリーレン基、置換基を有していてもよいアルキレンジオキシ基、置換基を有していてもよいシクロアルキレンジオキシ基、置換基を有していてもよいアリーレンジオキシ基、置換基を有していてもよいシリレン基、又はフェロセニレン基は前記したｎが１の場合のＲ１から水素１原子を取り除いた二価の残基、或いは水素１原子を酸素１原子に置き換えた二価の残基の中から選ばれ、その具体例としては、メチレン基、エチレン基、トリメチレン基、メチルエチレン基、テトラメチレン基、１，２−ジメチルエチレン基、ペンタメチレン基、ヘキサメチレン基、シクロヘキシレン基、フェニレン基、ナフチレン基、フェニルメチレン基、フランジイル基、２−ブテンジイル基、テトラメチレンジオキシ基、テトラリンジイルオキシ基、フェニレンジオキシ基、ジメチルシリレン基、フェロセニレン基等が挙げられる。
【００１１】
本発明の製造方法において好ましく用いられる、上記一般式［１］で示されるアセチレン化合物を例示すると、無置換アセチレン、メチルアセチレン、ブチン、１−ヘキシン、２−ヘキシン、１−オクチン、４−オクチン、１−ブチン−４−オール、２−ブチン−１−オール、３−ブチン−１−オール、５−ヘキシン−１−オール、１−オクチン−３−オール、５−クロロ−１−ペンチン、フェニルアセチレン、トリメチルシリルアセチレン、エチニルチオフェン、ヘキシノニトリル、シクロヘキセニルアセチレン、エチニルフェロセン、１，４−ペンタジイン、１，８−ノナジイン、ジエチニルベンゼンなどが挙げられるが、これらに限定されるものではない。
【００１２】
上記一般式［２］において、Ｘ１がＯＲ３でＸ２がＯＲ４である場合には、一般式［２］で表されるリン化合物（Ｐ−Ｈ化合物）は、下記一般式［２ａ］
ＨＰ（Ｏ）（ＯＲ３）（ＯＲ４） ［２ａ］
（式中、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）で表される水素化ホスホン酸エステルとなり、反応により生成する一般式［３］又は／及び一般式［４］で表されるアルケニルリン化合物は、下記一般式［３ａ］又は／及び一般式［４ａ］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）（ＯＲ３）（ＯＲ４）］｝ｎ ［３ａ］
Ｒ１｛Ｃ［Ｐ（Ｏ）（ＯＲ３）（ＯＲ４）］＝ＣＨＲ２｝ｎ ［４ａ］
（式中、ｎ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記と同じ。）で表されるアルケニルリン化合物となる。
【００１３】
上記一般式［２］において、Ｘ１がＯＲ３でＸ２がＲ４である場合には、一般式［２］で表されるリン化合物（Ｐ−Ｈ化合物）は、下記一般式［２ｂ］
ＨＰ（Ｏ）（ＯＲ３）Ｒ４ ［２ｂ］
（式中、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）で表される水素化ホスフィン酸エステルとなり、反応により生成する一般式［３］又は／及び一般式［４］で表されるアルケニルリン化合物は、下記一般式［３ｂ］又は／及び一般式［４ｂ］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）（ＯＲ３）Ｒ４］｝ｎ ［３ｂ］
Ｒ１｛Ｃ［Ｐ（Ｏ）（ＯＲ３）Ｒ４］＝ＣＨＲ２｝ｎ ［４ｂ］
（式中、ｎ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記と同じ。）で表されるアルケニルリン化合物となる。
【００１４】
上記一般式［２］において、Ｘ１がＲ３でＸ２がＲ４である場合には、一般式［２］で表されるリン化合物（Ｐ−Ｈ化合物）は、下記一般式［２ｃ］
ＨＰ（Ｏ）Ｒ３Ｒ４ ［２ｃ］
（式中、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）で表される二置換ホスフィンオキシドとなり、反応により生成する一般式［３］又は／及び一般式［４］で表されるアルケニルリン化合物は、下記一般式［３ｃ］又は／及び一般式［４ｃ］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）Ｒ３Ｒ４］｝ｎ ［３ｃ］
Ｒ１｛Ｃ［Ｐ（Ｏ）Ｒ３Ｒ４］＝ＣＨＲ２｝ｎ ［４ｃ］
（式中、ｎ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記と同じ。）で表されるアルケニルリン化合物となる。
【００１５】
一般式［２ａ］、［３ａ］、［４ａ］、［２ｂ］、［３ｂ］、［４ｂ］、［２ｃ］、［３ｃ］及び［４ｃ］において、Ｒ３及びＲ４で示される、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基、同アリール基における、アルキル基、シクロアルキル基、アラルキル基及びアリール基の定義並びに具体例としては、上記Ｒ１及びＲ２のところで挙げたものと同じものが挙げられる。また、これらの置換基も、上記Ｒ１及びＲ２のところで挙げたものと同じものが挙げられる。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成している場合の具体例としては、例えば、エチレン基、テトラメチルエチレン基、トリメチレン基、テトラメチレン基、オルトフェニレン基、オルトキシリレン基などが挙げられるが、これらに限定されるものではない。
【００１６】
本発明の製造方法において用いられる好適なＰ−Ｈ化合物を具体的に例示すると、ホスホン酸ジメチル、ホスホン酸ジエチル、ホスホン酸ジブチル、ホスホン酸ジフェニル、４，４，５，５−テトラメチル−１，３，２−ジオキサホスホラン−２−オキシド、フェニルホスフィン酸エチル、フェニルホスフィン酸シクロヘキシル、ジフェニルホスフィンオキシドなどが挙げられるが、これらに限定されるものではない
【００１７】
アセチレン化合物とＰ−Ｈ化合物化合物の使用比率は、一般的にモル比で１：１が好ましいが、これより大きくても小さくても、反応の生起を阻害するものではない。
【００１８】
本発明に係る反応は、ニッケルを含んでなる触媒、就中、ニッケル錯体触媒の存在下において好ましい速度で進行する。
ニッケル錯体触媒としては、種々の構造のものを用いることが出来るが、好適なものは、いわゆる低原子価のニッケル錯体触媒である。
また、３級ホスフィンや３級ホスファイト等の３価のリン化合物を配位子とする低原子価のニッケル錯体も好ましく用いることが出来る。
更に、反応系中で容易に低原子価錯体に変換し得る前駆体錯体を用い、反応系中で低原子価ニッケル錯体を形成させて反応させることも好ましい態様である。更にまた、３級ホスフィンや３級ホスファイト等の３価のリン化合物を配位子として含まない同金属錯体と、３級ホスフィンや３級ホスファイト等の３価のリン化合物とを併用し、反応系中で３級ホスフィンや３級ホスファイト等の３価のリン化合物を配位子とする低原子価錯体を形成させて使用する方法や、３級ホスフィンや３級ホスファイト等の３価のリン化合物を配位子とする低原子価錯体に同種又は異種の３級ホスフィン、３級ホスファイト等の３価のリン化合物を更に添加して使用する方法等も好ましい態様である。
これらのいずれかの方法で有利な性能を発揮する配位子としては、種々の３級ホスフィンや３級ホスファイト等の３価のリン化合物を挙げることが出来る。
【００１９】
好適に用いることが出来る配位子を例示すると、例えば、トリフェニルホスフィン、ジフェニルメチルホスフィン、フェニルジメチルホスフィン、トリエチルホスフィン、トリシクロヘキシルホスフィン、１，４−ビス（ジフェニルホスフィノ）ブタン、１，３−ビス（ジフェニルホスフィノ）プロパン、１，２−ビス（ジフェニルホスフィノ）エタン、１，１’−ビス（ジフェニルホスフィノ）フェロセン、１，２−ビス（ジフェニルホスフィノ）ベンゼン、トランス−１，２−ビス（ジフェニルホスフィノ）シクロペンタン、トリエチルホスフィン、トリメチルホスフィン、トリメチルホスファイト、トリフェニルホスファイト等が挙げられる。
【００２０】
これらの配位子と組み合わせて又は単独で用いられる、３級ホスフィンや３級ホスファイトを配位子として含まない錯体としては、例えば、ビス（アクリロニトリル）ニッケル、ビス（１，５−シクロオクタジエン）ニッケル［Ｎｉ（ｃｏｄ）２ ］、ビス（π−アリル）ニッケル、ニッケロセン、ニッケルカルボニル、（π−シクロペンタジエニル）（π−アリル） ニッケル、酢酸ニッケル、臭化ニッケル等が挙げられる。
【００２１】
また、３級ホスフィンやホスファイトを配位子として含んでなる錯体としては、
例えば、ビス（トリシクロヘキシルホスフィン）ニッケル、ジクロロビス（トリフェニルホスフィン）ニッケル、ジメチルビス（ジフェニルメチルホスフィン）ニッケル、（エチレン）ビス（トリフェニルホスフィン）ニッケル、テトラキス（トリフェニルホスフィン）ニッケル［Ｎｉ（ＰＰｈ３）４］、テトラキス（ジフェニルメチルホスフィン）ニッケル、テトラキス（ジメチルフェニルホスフィン）ニッケル、テトラキス（トリエチルホスフィン）ニッケル、ジカルボニルビストリフェニルホスフィンニッケル、（トリカルボニル）（トリフェニルホスフィン）ニッケル［Ｎｉ（ＣＯ）３（ＰＰｈ３）］、テトラキス（トリフェニルホスファイト）ニッケル等が挙げられ、特に好適に用いられるホスフィン又はホスファイト錯体としては、テトラキス（トリフェニルホスフィン）ニッケル、テトラキス（ジフェニルメチルホスフィン）ニッケル、テトラキス（ジメチルフェニルホスフィン）ニッケル、テトラキス（トリエチルホスフィン）ニッケル、テトラキス（トリフェニルホスファイト）ニッケルなどが挙げられる。
【００２２】
前駆体錯体を用い反応系中で低原子価ニッケル錯体を発生させる方法においては、前駆ニッケル錯体の構造によっては低原子価にするための処理剤を併用することが好ましい。その際に用いられる処理剤としては、還元剤やグリニャール試薬等が挙げられ、より具体的には、例えば、水素化ホウ素ナトリウム、水素化アルミニウムリチウム、水素化ナトリウム等の水素化物、トリエチルアルミニウム、フェニルリチウム、ブチルリチウム、金属リチウム、金属ナトリウム、ナトリウムアマルガム、金属亜鉛、臭化メチルマグネシウム、沃化フェニルマグネシウム、臭化イソプロピルマグネシウム等が挙げられる。
前駆ニッケル錯体の具体例としては、例えば、ジクロロビス（トリフェニルホスフィン）ニッケル、ジクロロビス（ジフェニルメチルホスフィン）ニッケル、ジクロロビス（ジメチルフェニルホスフィン）ニッケル、クロロフェニルビス（トリフェニルホスフィン）ニッケルなどが挙げられるが、これらに限定されるものではない。
【００２３】
本発明の反応において用いられる上記の触媒は反応に応じて好適なものを１種又は２種以上適宜選択して用いられる。
本発明の反応に用いられるニッケル触媒の使用量はいわゆる触媒量で良く、アセチレン化合物に対して２０モル％以下で足りるが、通常は１０モル％以下で十分である。
なお、３価のリン化合物を配位子として用いる場合のこれらの使用量は、特に厳密な制限ではないが、リンのニッケルに対する原子比があまりに過剰であると触媒活性を低下させる傾向にあるので、一般的にはその原子比で５０以下、好ましくは１０以下に設定するのが好ましい。
【００２４】
ニッケルを含んでなる触媒は、単独でも活性を示すが、ホスフィン酸添加剤と共に用いることも出来る。特に位置異性体が生じる反応においては、ホスフィン酸添加物を併用することにより位置選択性が高まるので、そのような場合には併用するのが望ましい。
これらのホスフィン酸は、例えば一般式［５］
ＨＯ−Ｐ（Ｏ）（Ｒ５）２ ［５］
（式中、Ｒ５はアルキル基、シクロアルキル基、アリール基、又はアラルキル基を示す。）で表される。
【００２５】
一般式［５］において、Ｒ５がアルキル基の場合のアルキル基としては、例えば炭素数１〜６、好ましくは１〜４のアルキル基が挙げられ、その具体例としては、例えば、メチル基、エチル基、ｎ−又はｉｓｏ−プロピル基、ｎ−、ｉｓｏ−、ｓｅｃ−又はｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基などが挙げられる。
Ｒ５がシクロアルキル基の場合のシクロアルキル基としては、例えば炭素数３〜１２、好ましくは５〜１２のシクロアルキル基が挙げられ、その具体例としては、例えば、シクロペンチル基、シクロヘキシル基、シクロオクチル基、シクロドデシル基などが挙げられる。
Ｒ５がアリール基の場合のアリール基としては、例えば炭素数６〜１４、好ましくは６〜１０のアリール基が挙げられ、その具体例としては、例えば、フェニル基、ナフチル基などが挙げられ、さらにそれらの置換体（トリル基、キシリル基、ベンジルフェニル基など）も包含される。
Ｒ５がアラルキル基の場合のアラルキル基としては、例えば炭素数７〜１５、好ましくは７〜１１のアラルキル基が挙げられ、その具体例としては、例えばベンジル基、フェネチル基、ナフチルメチル基などが挙げられる。
Ｒ５で示されるアルキル基、シクロアルキル基、アリール基又はアラルキル基は，反応に不活性な置換基、例えば、メトキシ基、メトキシカルボニル基、シアノ基、ジメチルアミノ基、フルオロ基、クロロ基、ヒドロキシ基などで置換されていてもよい。
【００２６】
本発明で用いられるホスフィン酸の具体例としては、例えばジフェニルホスフィン酸やジメチルホスフィン酸などが挙げられる。その使用量は、用いるＰ−Ｈ化合物に対して等モル以下、好ましくは、０．１〜１０モル％である。
【００２７】
反応は特に溶媒を用いなくてもよいが、必要に応じて溶媒中で実施することもできる。溶媒としては、トルエン、キシレン等の炭化水素系溶媒、ジオキサン、テトラヒドロフラン（ＴＨＦ）、ジイソプロピルエーテル、ジメトキシエタン等のエーテル系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトン、メチルエチルケトン等のケトン類、アセトニトリル、プロピオノニトリル等のニトリル系溶媒、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）等のアミド系溶媒等、種々のものが使用できる。また、これらは単独若しくは２種以上の混合物として使用することも出来る。
【００２８】
反応温度は、あまりに低温では反応が有利な速度で進行せず、あまりに高温では触媒が分解するので、一般的には、−２０℃から３００℃の範囲から選ばれ、好ましくは０℃から１５０℃の範囲で実施される。反応時間は、用いるアセチレン化合物及びＰ−Ｈ化合物の種類や反応温度その他の反応条件等により自ずから異なるが、通常数時間〜数十時間程度である。
【００２９】
本反応は空気中等の酸素の存在下でも進行するが、本反応系中で作用する触媒活性種は酸素に敏感なので、反応の実施は窒素、アルゴン、メタン等の不活性ガス雰囲気で行うのが好ましい。反応混合物からの生成物の分離は、クロマトグラフィー、蒸留、再結晶等によって容易に達成される。
【００３０】
【実施例】
本発明を以下の実施例によって更に具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではない。
【００３１】
実施例１
１，４−ジオキサン １ミリリットルに、ＨＰ（Ｏ）（ＯＣＭｅ２−Ｍｅ２ＣＯ）１ミリモル、１−オクチン １ミリモル、触媒として Ｎｉ（ｃｏｄ）２ （１０モル％）を用い、窒素雰囲気下、室温で５時間反応させたところ、２−（１−オクテン−２−イル）−４，４，５，５−テトラメチル−１，３，２−ジオキサホスホラン２−オキシドが３６％の収率で得られた。
【００３２】
実施例２
実施例１と同様の反応条件下、触媒として Ｎｉ（ｃｏｄ）２ （１０モル％）とＰｈ２Ｐ（ＣＨ２）３ＰＰｈ２（１０モル％）を用い、反応を行ったところ、２−（１−オクテン−２−イル）−４，４，５，５−テトラメチル−１，３，２−ジオキサホスホラン２−オキシドが７２％の収率で得られた。
【００３３】
実施例３〜１８
実施例２と同様の反応条件下、種々のニッケル触媒を用いてＨＰ（Ｏ）（ＯＣＭｅ２−Ｍｅ２ＣＯ）とアセチレン類の反応を行った。結果を表１にまとめて示す。
【００３４】
【表１】
実施例１９
１−オクチンの代わりに、フェニルアセチレンを用いて実施例１６と同様の反応条件下で反応を行ったところ、ＣＨ２＝Ｃ（Ｐｈ）［Ｐ（Ｏ）（ＯＣＭｅ２−Ｍｅ２ＣＯ）］が９９％の収率で得られた。
【００３６】
実施例２０
アセチレンガス（１気圧）を用い、実施例１９と同様の反応条件下で反応を行ったところ、ＣＨ２＝ＣＨ［Ｐ（Ｏ）（ＯＣＭｅ２−Ｍｅ２ＣＯ）］が９５％の収率で得られた。
【００３７】
実施例２１
ＨＰ（Ｏ）（ＯＣＭｅ２−Ｍｅ２ＣＯ）の代わりに、（ＭｅＯ）２Ｐ（Ｏ）Ｈを用い、実施例１６と同様の反応条件下で、１−オクチンとの反応を行ったところ、ＣＨ２＝Ｃ（ｎ−Ｃ６Ｈ１３）［Ｐ（Ｏ）（ＯＭｅ）２］と（Ｅ）−ＣＨ（ｎ−Ｃ６Ｈ１３）＝ＣＨ［Ｐ（Ｏ）（ＯＭｅ）２］の混合物（比率＝１００：４６）が９７％の収率で得られた。
【００３８】
実施例２２
実施例２１の反応をジフェニルホスフィン酸（１０モル％）共存下で行ったところ、ＣＨ２＝Ｃ（ｎ−Ｃ６Ｈ１３）［Ｐ（Ｏ）（ＯＭｅ）２］が９６％の収率で選択的に生成した。
【００３９】
実施例２３
実施例２２と同様の反応条件下で、アセチレン化合物として１，８−ノナジインを用いて（ＭｅＯ）２Ｐ（Ｏ）Ｈとの反応を行ったところ、ＣＨ２＝Ｃ［Ｐ（Ｏ）（ＯＭｅ）２］−（ＣＨ２）５−［Ｐ（Ｏ）（ＯＭｅ）２］Ｃ＝ＣＨ２が９１％の収率で生成した。
【００４０】
実施例２４
１−オクチンの代わりにアセチレンガス（１気圧）を用い、実施例２１と同じ反応条件下で反応を行ったところ、ＣＨ２＝ＣＨ［Ｐ（Ｏ）（ＯＭｅ）２］が９２％の収率で得られた。
【００４１】
実施例２５
実施例１９と同じ反応条件下で、ＨＰ（Ｏ）（ＯＥｔ）Ｐｈを用い、フェニルアセチレンとの反応を行ったところ、［（Ｅ）−２−フェニルエテニル］フェニルホスフィン酸エチルと（１−フェニルエテニル）フェニルホスフィン酸エチルの混合物（比率＝２９：７１）が５６％の収率で得られた。
【００４２】
実施例２６
実施例２５の反応をジフェニルホスフィン酸（１０モル％）共存下で行ったところ、（１−フェニルエテニル）フェニルホスフィン酸エチルが９８％の収率で選択的に生成した。
【００４３】
実施例２７
実施例２６と同じ反応条件下で、フェニルアセチレンの代わりに１−オクチンを用いて、反応を行ったところ、ＣＨ２＝Ｃ（ｎ−Ｃ６Ｈ１３）［Ｐ（Ｏ）Ｐｈ（ＯＥｔ）］が８８％の収率で選択的に生成した。
【００４４】
実施例２８
実施例２６と同じ反応条件下で、フェニルアセチレンの代わりにトリメチルシリルアセチレンを用いて、反応を行ったところ、（Ｅ）−ＣＨ（ＳｉＭｅ３）＝ＣＨ［Ｐ（Ｏ）Ｐｈ（ＯＥｔ）］が９２％の収率で選択的に生成した。
【００４５】
実施例２９
実施例２６と同じ反応条件下で、フェニルアセチレンの代わりに２−エチニルチオフェンを用いて、反応を行ったところ、［１−（２−チエニル）エテニル］フェニルホスフィン酸エチルが６３％の収率で選択的に生成した。
【００４６】
実施例３０
実施例２４と同じ反応条件下で、（ＭｅＯ）２Ｐ（Ｏ）Ｈの代わりにＨＰ（Ｏ）Ｐｈ２を用い、フェニルアセチレンとの反応を行ったところ、ＣＨ２＝Ｃ（Ｐｈ）［Ｐ（Ｏ）Ｐｈ２］と（Ｅ）−ＣＨ（Ｐｈ）＝ＣＨ［Ｐ（Ｏ）Ｐｈ２］の混合物（比率＝５６：４４）が９３％の収率で得られた。
【００４７】
実施例３１
実施例３０の反応をジフェニルホスフィン酸（１０モル％）共存下で行ったところ、ＣＨ２＝Ｃ（Ｐｈ）［Ｐ（Ｏ）Ｐｈ２］が９８％の収率で選択的に生成した。
【００４８】
【発明の効果】
本発明は、医薬・農薬などの生理活性物質や触媒調製用配位子等の合成中間体として有用なアルケニルリン化合物（アルケニルホスホン酸エステル、アルケニルホスフィン酸エステル及びアルケニルホスフィンオキシド化合物）の高収率で且つ実用性の高い製造方法を提供するものである。本発明のアルケニルリン化合物の合成方法は、触媒として比較的安価なニッケル錯体触媒を使用し、アセチレン類にＰ−Ｈ化合物（水素化ホスホン酸エステル、水素化ホスフィン酸エステル及び二置換ホスフィンオキシド）を反応させるだけで、簡便、安全、且つ効率的に合成することができ、生成物の分離精製も容易である。従って、本発明は工業的に多大の効果をもたらす。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an alkenyl phosphorus compound such as an alkenyl phosphonic acid ester, an alkenyl phosphinic acid ester, and an alkenyl phosphine oxide compound. It is known that alkenyl phosphorus compounds themselves show physiological activity when their basic skeleton is found in nature and act with enzymes and the like. The compound is also a very useful compound that can be easily converted to tertiary phosphine or the like widely used as an auxiliary ligand or the like in various catalytic reactions. Further, the compound is a group of compounds having high utility also in synthesizing fine chemicals, for example, it easily reacts with a nucleophile or a radical species and can be used for Horner-Wittig reaction.
[0002]
[Prior art]
As a method of synthesizing such an alkenyl phosphorus compound with generation of a carbon-phosphorus bond, generally, a corresponding alkenyl halide compound is converted to a hydrogenated phosphonic acid ester, a hydrogenated phosphinic acid ester and a disubstituted phosphine oxide ( Hereinafter, these phosphorus compounds are collectively referred to as a PH compound.). However, in this method, it is necessary to add a base for capturing the hydrogen halide produced simultaneously with the reaction, thereby producing a large amount of a hydrogen halide salt. Further, the alkenyl halide compound as the starting material is not always easily available industrially and generally has toxicity. Therefore, this method is not considered to be an industrially advantageous method. On the other hand, a method for producing an alkenyl phosphorus compound by addition of a P-H compound to acetylene using a catalyst has also been recently reported (Japanese Patent Nos. 2,775,426, 2,779,985, 2,498,712, and 3007984; No. 3041396), all of these methods use an expensive palladium or rhodium catalyst, and none of these methods has a very high product selectivity.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing an alkenyl phosphorus compound using a PH compound as a starting material and using an inexpensive catalyst.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on the reaction between an easily available PH compound and an acetylene compound. As a result, this addition reaction proceeds in the presence of an inexpensive nickel catalyst, and the corresponding alkenyl phosphorus compound is easily converted. It was found that the present invention was given, and the present invention was completed.
[0005]
That is, the present invention provides a method for producing a catalyst of the general formula [1] in the presence of a catalyst containing nickel.
R 1 (C @ CR 2 ) n [1]
(Wherein, n is 1 or 2, and when n is 1, R 1 And R 2 , And R when n is 2 2 Are each independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, a heteroaryl group, It represents an alkoxy group, a cycloalkoxy group, an aralkyloxy group, an aryloxy group, a silyl group, or a ferrocenyl group. Further, when n is 2, R 1 Is an optionally substituted alkylene group, the same cycloalkylene group, the same alkenylene group, the same cycloalkenylene group, the same arylene group, the same aralkylene group, the same heteroarylene group, the same alkylenedioxy group, the same cycloalkyl group. A dioxy group, an aralkylenedioxy group, an arylenedioxy group, a silylene group, or a ferrosenylene group. The acetylene compound represented by the general formula [2]
HP (O) X 1 X 2 [2]
Where X 1 Is OR 3 Or R 3 And X 2 Is OR 4 Or R 4 (Where R 3 And R 4 Each independently represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. Also, R 3 And R 4 Each group may be bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself from each group to form a cyclic structure. ). [3] characterized by reacting with a phosphorus compound represented by the general formula [3]:
R 1 ｛CH = CR 2 [P (O) X 1 X 2 ]｝ n [3]
Or / and general formula [4]
R 1 ｛C [P (O) X 1 X 2 ] = CHR 2 ｝ n [4]
(Where n, R 1 , R 2 , X 1 And X 2 Is the same as above. )).
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
In the above general formulas [1], [3] and [4], R when n is 1 1 And R 2 , And R when n is 2 2 As the alkyl group of the alkyl group optionally having substituent (s), for example, a linear or branched alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms And more specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, hexyl group And the like.
The cycloalkyl group of the cycloalkyl group which may have a substituent includes, for example, a monocyclic, polycyclic or condensed ring having 3 to 30, preferably 3 to 20, and more preferably 3 to 12 carbon atoms. Examples include the cycloalkyl group of the formula, more specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and the like.
Examples of the alkenyl group of the alkenyl group which may have a substituent include, for example, those having one or more double bonds in the alkyl group having 2 or more carbon atoms, and more specifically, allyl. Groups, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group and the like.
Examples of the cycloalkenyl group of the cycloalkenyl group which may have a substituent include those having one or more double bonds in the above-described cycloalkyl group, and more specifically, a cyclopropenyl group and a cycloalkyl group Examples include a pentenyl group, a cyclohexenyl group, and a cyclooctenyl group.
[0007]
Examples of the aryl group of the aryl group which may have a substituent include, for example, a monocyclic, polycyclic or condensed ring aromatic having 6 to 30, preferably 6 to 20, and more preferably 6 to 14 carbon atoms. Examples include a hydrocarbon group, and more specifically, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and the like.
Examples of the aralkyl group of the aralkyl group which may have a substituent include, for example, a monocyclic, polycyclic or condensed aralkyl group having 7 to 30, preferably 7 to 20, and more preferably 7 to 15 carbon atoms. And more specifically, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and the like.
Examples of the heteroaryl group of the heteroaryl group which may have a substituent include various heteroaromatic ring groups containing a hetero atom such as oxygen, nitrogen, and sulfur, and the number of carbon atoms contained therein is usually 4 to 12 , Preferably 4 to 8. Specific examples thereof include a thienyl group, a furyl group, a pyridyl group, and a pyrrolyl group.
Examples of the alkoxy group of the optionally substituted alkoxy group include an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, and a butoxy group. And the like.
Examples of the cycloalkoxy group of the cycloalkoxy group which may have a substituent include, for example, a monocyclic, polycyclic or condensed cyclic compound having 3 to 30, preferably 3 to 20, and more preferably 3 to 12 carbon atoms. A cycloalkoxy group is mentioned, and more specifically, a cyclopropyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cyclooctyloxy group, a cyclododecyloxy group and the like are mentioned.
Examples of the aralkyloxy group which may have a substituent include a monocyclic, polycyclic or fused cyclic aralkyloxy group having 7 to 30, preferably 7 to 20, and more preferably 7 to 15 carbon atoms. More specifically, examples include a benzyloxy group, a phenethyloxy group, a naphthylmethyloxy group, a naphthylethyloxy group, and the like.
Examples of the aryloxy group of the aryloxy group which may have a substituent include, for example, a monocyclic, polycyclic or condensed cyclic one having 6 to 30, preferably 6 to 20, and more preferably 6 to 14 carbon atoms. Examples include an aryloxy group having an aromatic hydrocarbon group, and more specifically, for example, a phenoxy group, a tolyloxy group, a xylyloxy group, a naphthoxy group, a methylnaphthyloxy group, an anthryloxy group, a phenanthryloxy group, And a biphenyloxy group.
[0008]
Examples of the substituents of these alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, aralkyl group, heteroaryl group, alkoxy group, cycloalkoxy group, aralkyloxy group and aryloxy group include, for example, methyl group, ethyl group , An alkyl group such as a propyl group, a hydroxyl group such as a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, such as a halogen atom such as chlorine, bromine and fluorine, a cyano group such as a dimethylamino group and a diethylamino group. A dialkylamino group, for example, an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; a silyl group, for example, a substituted silyl group such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triphenylsilyl group; Such siloxy group such Chirushirokishi group.
[0009]
The silyl group which may have a substituent includes, for example, those substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group and the like. Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, a trimethoxysilyl group, a t-butyldimethylsilyl group, and the like.
[0010]
R when n is 2 1 An alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, an alkenylene group which may have a substituent, a cyclo which may have a substituent Alkenylene group, arylene group which may have a substituent, aralkylene group which may have a substituent, heteroarylene group which may have a substituent, alkyl which may have a substituent A dioxy group, a cycloalkylenedioxy group which may have a substituent, an arylenedioxy group which may have a substituent, a silylene group which may have a substituent, or a ferrosenylene group is the aforementioned R when n is 1 1 Selected from divalent residues obtained by removing one hydrogen atom from, or divalent residues obtained by replacing one hydrogen atom with one oxygen atom. Specific examples thereof include a methylene group, an ethylene group, a trimethylene group, Methylethylene group, tetramethylene group, 1,2-dimethylethylene group, pentamethylene group, hexamethylene group, cyclohexylene group, phenylene group, naphthylene group, phenylmethylene group, furandiyl group, 2-butenediyl group, tetramethylenedi Examples thereof include an oxy group, a tetralindiyloxy group, a phenylenedioxy group, a dimethylsilylene group, and a ferrocenylene group.
[0011]
Examples of the acetylene compound represented by the general formula [1] preferably used in the production method of the present invention include unsubstituted acetylene, methylacetylene, butyne, 1-hexyne, 2-hexyne, 1-octyne, 4-octyne, 1-butyn-4-ol, 2-butyn-1-ol, 3-butyn-1-ol, 5-hexyn-1-ol, 1-octin-3-ol, 5-chloro-1-pentyne, phenylacetylene , Trimethylsilylacetylene, ethynylthiophene, hexynonitrile, cyclohexenylacetylene, ethynylferrocene, 1,4-pentadiyne, 1,8-nonadiyne, diethynylbenzene, and the like, but are not limited thereto.
[0012]
In the above general formula [2], X 1 Is OR 3 And X 2 Is OR 4 In the case of the phosphorus compound (P—H compound) represented by the general formula [2], the following general formula [2a]
HP (O) (OR 3 ) (OR 4 ) [2a]
(Where R 3 And R 4 Each independently represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. Also, R 3 And R 4 Each group may be bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself from each group to form a cyclic structure. ), And the alkenyl phosphorus compound represented by the general formula [3] or / and the general formula [4] produced by the reaction is represented by the following general formula [3a] or / and the general formula [3] 4a]
R 1 ｛CH = CR 2 [P (O) (OR 3 ) (OR 4 )]｝ n [3a]
R 1 ｛C [P (O) (OR 3 ) (OR 4 )] = CHR 2 ｝ n [4a]
(Where n, R 1 , R 2 , R 3 And R 4 Is the same as above. )).
[0013]
In the above general formula [2], X 1 Is OR 3 And X 2 Is R 4 In the case of the phosphorus compound (P—H compound) represented by the general formula [2], the following general formula [2b]
HP (O) (OR 3 ) R 4 [2b]
(Where R 3 And R 4 Each independently represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. Also, R 3 And R 4 Each group may be bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself from each group to form a cyclic structure. The alkenyl phosphorus compound represented by the general formula [3] or / and the general formula [4] which is converted into a hydrogenated phosphinic ester represented by the following general formula [3b] or / and the general formula [3] 4b]
R 1 ｛CH = CR 2 [P (O) (OR 3 ) R 4 ]｝ n [3b]
R 1 ｛C [P (O) (OR 3 ) R 4 ] = CHR 2 ｝ n [4b]
(Where n, R 1 , R 2 , R 3 And R 4 Is the same as above. )).
[0014]
In the above general formula [2], X 1 Is R 3 And X 2 Is R 4 In the case of the phosphorus compound (P—H compound) represented by the general formula [2], the following general formula [2c]
HP (O) R 3 R 4 [2c]
(Where R 3 And R 4 Each independently represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. Also, R 3 And R 4 Each group may be bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself from each group to form a cyclic structure. The alkenyl phosphorus compound represented by the general formula [3] or / and the general formula [4], which is a disubstituted phosphine oxide represented by the following general formula [3c] or / and the general formula [4c] ]
R 1 ｛CH = CR 2 [P (O) R 3 R 4 ]｝ n [3c]
R 1 ｛C [P (O) R 3 R 4 ] = CHR 2 ｝ n [4c]
(Where n, R 1 , R 2 , R 3 And R 4 Is the same as above. )).
[0015]
In the general formulas [2a], [3a], [4a], [2b], [3b], [4b], [2c], [3c] and [4c], R 3 And R 4 In the alkyl group optionally having a substituent, the same cycloalkyl group, the same aralkyl group, the same aryl group, in the definition of alkyl group, cycloalkyl group, aralkyl group and aryl group and specific examples, R above 1 And R 2 And the same ones listed above. In addition, these substituents also correspond to the above R 1 And R 2 And the same ones listed above. Also, R 3 And R 4 Specific examples of the case where a ring structure is formed by bonding to each other with a residue or a bond that excludes one hydrogen atom or the group itself from each group to form a cyclic structure include, for example, ethylene group, tetramethylethylene group, trimethylene Group, tetramethylene group, orthophenylene group, orthoxylylene group and the like, but are not limited thereto.
[0016]
Specific examples of suitable PH compounds used in the production method of the present invention include dimethyl phosphonate, diethyl phosphonate, dibutyl phosphonate, diphenyl phosphonate, 4,4,5,5-tetramethyl-1, Examples include, but are not limited to, 3,2-dioxaphosphorane-2-oxide, ethyl phenylphosphinate, cyclohexyl phenylphosphinate, diphenylphosphine oxide, and the like.
[0017]
In general, the molar ratio of the acetylene compound and the PH compound is preferably 1: 1. However, if the molar ratio is larger or smaller than this, it does not inhibit the occurrence of the reaction.
[0018]
The reaction according to the invention proceeds at a favorable rate in the presence of a catalyst comprising nickel, in particular a nickel complex catalyst.
Although various structures can be used as the nickel complex catalyst, a preferable one is a so-called low-valent nickel complex catalyst.
Further, a low-valent nickel complex having a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand can also be preferably used.
Further, it is also a preferable embodiment to use a precursor complex which can be easily converted to a low-valent complex in the reaction system and form a low-valent nickel complex in the reaction system to cause a reaction. Furthermore, the same metal complex containing no trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand and a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite are used in combination, A method in which a low-valent complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand is formed in a reaction system and used, or a trivalent phosphine or a tertiary phosphite or the like is used. A preferred embodiment is a method in which a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite of the same or different kind is further added to a low-valent complex having a phosphorus compound as a ligand.
Examples of the ligand exhibiting advantageous performance by any of these methods include various tertiary phosphorus compounds such as tertiary phosphine and tertiary phosphite.
[0019]
Illustrative ligands that can be suitably used include, for example, triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, triethylphosphine, tricyclohexylphosphine, 1,4-bis (diphenylphosphino) butane, 1,3- Bis (diphenylphosphino) propane, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino) ferrocene, 1,2-bis (diphenylphosphino) benzene, trans-1,2 -Bis (diphenylphosphino) cyclopentane, triethylphosphine, trimethylphosphine, trimethylphosphite, triphenylphosphite and the like.
[0020]
Examples of a complex that does not contain tertiary phosphine or tertiary phosphite as a ligand used in combination with these ligands or alone include bis (acrylonitrile) nickel and bis (1,5-cyclooctadiene). ) Nickel [Ni (cod) 2 ], Bis (π-allyl) nickel, nickelocene, nickel carbonyl, (π-cyclopentadienyl) (π-allyl) nickel, nickel acetate, nickel bromide and the like.
[0021]
Further, as a complex containing tertiary phosphine or phosphite as a ligand,
For example, bis (tricyclohexylphosphine) nickel, dichlorobis (triphenylphosphine) nickel, dimethylbis (diphenylmethylphosphine) nickel, (ethylene) bis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel [Ni (PPh 3 ) 4 ], Tetrakis (diphenylmethylphosphine) nickel, tetrakis (dimethylphenylphosphine) nickel, tetrakis (triethylphosphine) nickel, dicarbonylbistriphenylphosphinenickel, (tricarbonyl) (triphenylphosphine) nickel [Ni (CO) 3 (PPh 3 )], Tetrakis (triphenylphosphite) nickel and the like. Particularly preferred phosphines or phosphite complexes are tetrakis (triphenylphosphine) nickel, tetrakis (diphenylmethylphosphine) nickel, and tetrakis (dimethylphenylphosphine). ) Nickel, tetrakis (triethylphosphine) nickel, tetrakis (triphenylphosphite) nickel and the like.
[0022]
In the method of generating a low-valent nickel complex in a reaction system using a precursor complex, it is preferable to use a treating agent for lowering the valence depending on the structure of the precursor nickel complex. Examples of the treating agent used at that time include a reducing agent and a Grignard reagent, and more specifically, for example, sodium borohydride, lithium aluminum hydride, hydrides such as sodium hydride, triethylaluminum, phenyl Examples include lithium, butyl lithium, metallic lithium, metallic sodium, sodium amalgam, metallic zinc, methylmagnesium bromide, phenylmagnesium iodide, and isopropylmagnesium bromide.
Specific examples of the precursor nickel complex include, for example, dichlorobis (triphenylphosphine) nickel, dichlorobis (diphenylmethylphosphine) nickel, dichlorobis (dimethylphenylphosphine) nickel, and chlorophenylbis (triphenylphosphine) nickel. However, the present invention is not limited to this.
[0023]
One or more of the above-mentioned catalysts used in the reaction of the present invention are suitably selected according to the reaction and used.
The amount of the nickel catalyst used in the reaction of the present invention may be a so-called catalytic amount, which is sufficient to be 20 mol% or less based on the acetylene compound, but usually 10 mol% or less is sufficient.
The use amount of these trivalent phosphorus compounds when they are used as the ligand is not particularly strictly limited. However, if the atomic ratio of phosphorus to nickel is too large, the catalytic activity tends to decrease. Generally, it is preferable to set the atomic ratio to 50 or less, preferably 10 or less.
[0024]
Catalysts comprising nickel exhibit activity alone, but can also be used with phosphinic acid additives. Particularly, in a reaction in which a regioisomer is generated, regioselectivity is enhanced by the combined use of a phosphinic acid additive.
These phosphinic acids have, for example, the general formula [5]
HO-P (O) (R 5 ) 2 [5]
(Where R 5 Represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. ).
[0025]
In the general formula [5], R 5 When is an alkyl group, examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples thereof include, for example, a methyl group, an ethyl group, n- or iso-propyl. Groups, n-, iso-, sec- or tert-butyl group, n-pentyl group, n-hexyl group and the like.
R 5 When is a cycloalkyl group, examples of the cycloalkyl group include a cycloalkyl group having 3 to 12 carbon atoms, preferably 5 to 12 carbon atoms, and specific examples thereof include, for example, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. , Cyclododecyl group and the like.
R 5 When is an aryl group, the aryl group includes, for example, an aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, and specific examples thereof include, for example, a phenyl group and a naphthyl group. (Tolyl group, xylyl group, benzylphenyl group, etc.).
R 5 When is an aralkyl group, the aralkyl group includes, for example, an aralkyl group having 7 to 15 carbon atoms, preferably 7 to 11 carbon atoms, and specific examples thereof include, for example, a benzyl group, a phenethyl group, and a naphthylmethyl group. .
R 5 The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by is a substituent inert to the reaction, for example, methoxy group, methoxycarbonyl group, cyano group, dimethylamino group, fluoro group, chloro group, hydroxy group, etc. May be substituted.
[0026]
Specific examples of the phosphinic acid used in the present invention include, for example, diphenylphosphinic acid and dimethylphosphinic acid. The amount of use is not more than equimolar to the P-H compound used, preferably 0.1 to 10 mol%.
[0027]
The reaction does not particularly require the use of a solvent, but can be carried out in a solvent if necessary. Examples of the solvent include hydrocarbon solvents such as toluene and xylene, ether solvents such as dioxane, tetrahydrofuran (THF), diisopropyl ether and dimethoxyethane, ester solvents such as ethyl acetate and butyl acetate, and ketones such as acetone and methyl ethyl ketone. Various solvents such as nitrile solvents such as acetonitrile and propiononitrile, and amide solvents such as N, N-dimethylformamide (DMF) can be used. These can be used alone or as a mixture of two or more.
[0028]
The reaction temperature is generally selected from the range of −20 ° C. to 300 ° C., preferably 0 ° C. to 150 ° C., since the reaction does not proceed at an advantageous rate at a too low temperature and the catalyst decomposes at a too high temperature. It is carried out within the range. The reaction time varies depending on the kind of the acetylene compound and the PH compound used, the reaction temperature and other reaction conditions, but is usually about several hours to several tens of hours.
[0029]
This reaction proceeds even in the presence of oxygen such as in air, but since the catalytically active species acting in this reaction system is sensitive to oxygen, the reaction should be performed in an inert gas atmosphere such as nitrogen, argon, or methane. preferable. Separation of the product from the reaction mixture is easily achieved by chromatography, distillation, recrystallization, and the like.
[0030]
【Example】
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
[0031]
Example 1
To 1 ml of 1,4-dioxane, add HP (O) (OCMe 2 -Me 2 CO) 1 mmol, 1-octyne 1 mmol, Ni (cod) as catalyst 2 (10 mol%) and reacted for 5 hours at room temperature under a nitrogen atmosphere. 2- (1-octen-2-yl) -4,4,5,5-tetramethyl-1,3,2- Dioxaphosphorane 2-oxide was obtained in a yield of 36%.
[0032]
Example 2
Under the same reaction conditions as in Example 1, Ni (cod) was used as the catalyst. 2 (10 mol%) and Ph 2 P (CH 2 ) 3 PPh 2 (10 mol%), the reaction was carried out to give 2- (1-octen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide Was obtained with a yield of 72%.
[0033]
Examples 3 to 18
Under the same reaction conditions as in Example 2, HP (O) (OCMe) 2 -Me 2 CO) and acetylenes. The results are summarized in Table 1.
[0034]
[Table 1]
Example 19
The reaction was carried out under the same reaction conditions as in Example 16 using phenylacetylene instead of 1-octyne. 2 = C (Ph) [P (O) (OCMe 2 -Me 2 CO)] in a yield of 99%.
[0036]
Example 20
The reaction was carried out under the same reaction conditions as in Example 19 using acetylene gas (1 atm). 2 = CH [P (O) (OCMe 2 -Me 2 CO)] in a yield of 95%.
[0037]
Example 21
HP (O) (OCMe 2 -Me 2 (MeO) instead of (CO) 2 When P (O) H was used to react with 1-octyne under the same reaction conditions as in Example 16, CH 2 = C (n-C 6 H 13 ) [P (O) (OMe) 2 ] And (E) -CH (n-C 6 H 13 ) = CH [P (O) (OMe) 2 (Ratio = 100: 46) in a yield of 97%.
[0038]
Example 22
When the reaction of Example 21 was carried out in the presence of diphenylphosphinic acid (10 mol%), CH 2 = C (n-C 6 H 13 ) [P (O) (OMe) 2 Was selectively produced in a 96% yield.
[0039]
Example 23
Under the same reaction conditions as in Example 22, using 1,8-nonadiyne as an acetylene compound (MeO) 2 Reaction with P (O) H resulted in CH 2 = C [P (O) (OMe) 2 ]-(CH 2 ) 5 -[P (O) (OMe) 2 ] C = CH 2 Was produced in a 91% yield.
[0040]
Example 24
When acetylene gas (1 atm) was used instead of 1-octyne and the reaction was carried out under the same reaction conditions as in Example 21, CH 2 = CH [P (O) (OMe) 2 Was obtained in a 92% yield.
[0041]
Example 25
The reaction with phenylacetylene was performed using HP (O) (OEt) Ph under the same reaction conditions as in Example 19, and ethyl [(E) -2-phenylethenyl] phenylphosphinate and (1- A mixture of ethyl (phenylethenyl) phenylphosphinates (ratio = 29: 71) was obtained in a yield of 56%.
[0042]
Example 26
When the reaction of Example 25 was carried out in the presence of diphenylphosphinic acid (10 mol%), ethyl (1-phenylethenyl) phenylphosphinate was selectively produced at a yield of 98%.
[0043]
Example 27
The reaction was carried out under the same reaction conditions as in Example 26 except that 1-octyne was used instead of phenylacetylene. 2 = C (n-C 6 H 13 ) [P (O) Ph (OEt)] was selectively produced in 88% yield.
[0044]
Example 28
The reaction was conducted under the same reaction conditions as in Example 26 except that trimethylsilylacetylene was used instead of phenylacetylene. 3 ) = CH [P (O) Ph (OEt)] was selectively produced in 92% yield.
[0045]
Example 29
The reaction was carried out under the same reaction conditions as in Example 26 using 2-ethynylthiophene instead of phenylacetylene, and ethyl [1- (2-thienyl) ethenyl] phenylphosphinate was obtained at a yield of 63%. Selectively generated.
[0046]
Example 30
Under the same reaction conditions as in Example 24, (MeO) 2 HP (O) Ph instead of P (O) H 2 Was reacted with phenylacetylene to obtain CH 2 = C (Ph) [P (O) Ph 2 ] And (E) -CH (Ph) = CH [P (O) Ph 2 (Ratio = 56:44) in a yield of 93%.
[0047]
Example 31
When the reaction of Example 30 was carried out in the presence of diphenylphosphinic acid (10 mol%), CH 2 = C (Ph) [P (O) Ph 2 Was selectively produced in a yield of 98%.
[0048]
【The invention's effect】
The present invention provides a high yield of alkenyl phosphorus compounds (alkenyl phosphonates, alkenyl phosphinates and alkenyl phosphine oxide compounds) useful as synthetic intermediates for physiologically active substances such as pharmaceuticals and agricultural chemicals and ligands for preparing catalysts. And a highly practical manufacturing method. In the method for synthesizing the alkenyl phosphorus compound of the present invention, a relatively inexpensive nickel complex catalyst is used as a catalyst, and a PH compound (hydrogenated phosphonate, hydrogenated phosphinate and disubstituted phosphine oxide) is added to acetylenes. The simple, safe and efficient synthesis can be achieved simply by reacting, and the product can be easily separated and purified. Therefore, the present invention has a great effect industrially.
Claims (10)
Ｒ１（Ｃ≡ＣＲ２）ｎ ［１］
（式中、ｎは１又は２であり、ｎが１の場合のＲ１及びＲ２、並びにｎが２の場合のＲ２は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、同シクロアルキル基、同アルケニル基、同シクロアルケニル基、同アリール基、同アラルキル基、同ヘテロアリール基、同アルコキシ基、同シクロアルコキシ基、同アラルキロキシ基、同アリールオキシ基、同シリル基、又はフェロセニル基を示す。また、ｎが２の場合のＲ１は、置換基を有していてもよいアルキレン基、同シクロアルキレン基、同アルケニレン基、同シクロアルケニレン基、同アリーレン基、同アラルキレン基、同ヘテロアリーレン基、同アルキレンジオキシ基、同シクロアルキレンジオキシ基、同アラルキレンジオキシ基、同アリーレンジオキシ基、同シリレン基、又はフェロセニレン基を示す。）で表されるアセチレン化合物を、一般式［２］
ＨＰ（Ｏ）Ｘ１Ｘ２ ［２］
［式中、Ｘ１はＯＲ３又はＲ３を示し、Ｘ２はＯＲ４又はＲ４を示す（但し、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）。］で表されるリン化合物と反応させることを特徴とする、一般式［３］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）Ｘ１Ｘ２］｝ｎ ［３］
又は／及び一般式［４］
Ｒ１｛Ｃ［Ｐ（Ｏ）Ｘ１Ｘ２］＝ＣＨＲ２｝ｎ ［４］
（式中、ｎ、Ｒ１、Ｒ２、Ｘ１及びＸ２は前記と同じ。）で表されるアルケニルリン化合物の製造方法。In the presence of a catalyst comprising nickel, the compound of the general formula [1]
R 1 (C≡CR 2 ) n [1]
(Wherein, n is 1 or 2, R 2 in the case of R 1 and R 2 when n is 1, and n is 2 are each independently a hydrogen atom, substituted Good alkyl group, the same cycloalkyl group, the same alkenyl group, the same cycloalkenyl group, the same aryl group, the same aralkyl group, the same heteroaryl group, the same alkoxy group, the same cycloalkoxy group, the same aralkyloxy group, the same aryloxy group, R 1 when n is 2 is an alkylene group, a cycloalkylene group, an alkenylene group, an alkenylene group, an arylene group, or an arylene group, which may have a substituent; Group, the same aralkylene group, the same heteroarylene group, the same alkylenedioxy group, the same cycloalkylenedioxy group, the same aralkylenedioxy group, the same arylenedioxy group, The silylene group, or ferrocenylene a group.) Acetylene compound represented by the general formula [2]
HP (O) X 1 X 2 [2]
[In the formula, X 1 represents OR 3 or R 3 , and X 2 represents OR 4 or R 4 (provided that R 3 and R 4 are each independently an alkyl which may have a substituent. A cycloalkyl group, an aralkyl group, or an aryl group, and a bond formed by removing a single hydrogen atom or the group itself from each of R 3 and R 4 , Structure may be formed). [3] characterized by reacting with a phosphorus compound represented by the general formula [3]:
R 1 {CH = CR 2 [P (O) X 1 X 2 ]} n [3]
Or / and general formula [4]
R 1 {C [P (O ) X 1 X 2] = CHR 2} n [4]
(Where n, R 1 , R 2 , X 1 and X 2 are the same as described above).
（式中、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）で表される水素化ホスホン酸エステルであり、一般式［３］又は／及び一般式［４］で表されるアルケニルリン化合物が、下記一般式［３ａ］又は／及び一般式［４ａ］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）（ＯＲ３）（ＯＲ４）］｝ｎ ［３ａ］
Ｒ１｛Ｃ［Ｐ（Ｏ）（ＯＲ３）（ＯＲ４）］＝ＣＨＲ２｝ｎ ［４ａ］
（式中、ｎ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記と同じ。）で表されるアルケニルリン化合物である請求項１に記載の製造方法。The phosphorus compound represented by the general formula [2] is represented by the following general formula [2a] HP (O) (OR 3 ) (OR 4 ) [2a]
(Wherein, R 3 and R 4 each independently represent an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. In addition, R 3 and R 4 Which may be bonded to each other by a residue or a bond formed by removing one hydrogen atom or the group itself from each group to form a cyclic structure), and represented by the general formula The alkenyl phosphorus compound represented by [3] or / and the general formula [4] is represented by the following general formula [3a] or / and the general formula [4a]
R 1 {CH = CR 2 [P (O) (OR 3 ) (OR 4 )]} n [3a]
R 1 ｛C [P (O) (OR 3 ) (OR 4 )] = CHR 2 ｝ n [4a]
(Where n, R 1 , R 2 , R 3, and R 4 are the same as described above).
ＨＰ（Ｏ）（ＯＲ３）Ｒ４ ［２ｂ］
（式中、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）で表される水素化ホスフィン酸エステルであり、一般式［３］又は／及び一般式［４］で表されるアルケニルリン化合物が、下記一般式［３ｂ］又は／及び一般式［４ｂ］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）（ＯＲ３）Ｒ４］｝ｎ ［３ｂ］
Ｒ１｛Ｃ［Ｐ（Ｏ）（ＯＲ３）Ｒ４］＝ＣＨＲ２｝ｎ ［４ｂ］
（式中、ｎ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記と同じ。）で表されるアルケニルリン化合物である請求項１に記載の製造方法。The phosphorus compound represented by the general formula [2] is represented by the following general formula [2b]
HP (O) (OR 3 ) R 4 [2b]
(Wherein, R 3 and R 4 each independently represent an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. In addition, R 3 and R 4 A hydrogen atom or a phosphinic acid ester represented by the general formula: The alkenyl phosphorus compound represented by the general formula [3] or / and the general formula [4] is represented by the following general formula [3b] or / and the general formula [4b]
R 1 {CH = CR 2 [P (O) (OR 3 ) R 4 ]} n [3b]
R 1 {C [P (O) (OR 3 ) R 4 ] = CHR 2 } n [4b]
(Where n, R 1 , R 2 , R 3, and R 4 are the same as described above).
ＨＰ（Ｏ）Ｒ３Ｒ４ ［２ｃ］
（式中、Ｒ３及びＲ４は、それぞれ独立して、置換基を有していても良いアルキル基、同シクロアルキル基、同アラルキル基又は同アリール基を示す。また、Ｒ３及びＲ４それぞれの基から一個の水素原子又は基そのものを除いてなる残基又は結合手で互いに結合し、環状構造を形成していてもよい。）で表される二置換ホスフィンオキシドであり、一般式［３］又は／及び一般式［４］で表されるアルケニルリン化合物が、下記一般式［３ｃ］又は／及び一般式［４ｃ］
Ｒ１｛ＣＨ＝ＣＲ２［Ｐ（Ｏ）Ｒ３Ｒ４］｝ｎ ［３ｃ］
Ｒ１｛Ｃ［Ｐ（Ｏ）Ｒ３Ｒ４］＝ＣＨＲ２｝ｎ ［４ｃ］
（式中、ｎ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記と同じ。）で表されるアルケニルリン化合物である請求項１に記載の製造方法。The phosphorus compound represented by the general formula [2] is represented by the following general formula [2c]
HP (O) R 3 R 4 [2c]
(Wherein, R 3 and R 4 each independently represent an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. In addition, R 3 and R 4 A divalent substituted phosphine oxide represented by the general formula [ 3] or / and the alkenyl phosphorus compound represented by the general formula [4] is represented by the following general formula [3c] or / and the general formula [4c]
R 1 {CH = CR 2 [P (O) R 3 R 4 ]} n [3c]
R 1 {C [P (O ) R 3 R 4] = CHR 2} n [4c]
(Where n, R 1 , R 2 , R 3, and R 4 are the same as described above).
ＨＯ−Ｐ（Ｏ）（Ｒ５）２ ［５］
（式中、Ｒ５はアルキル基、シクロアルキル基、アリール基、又はアラルキル基を示す。）で表されるホスフィン酸の存在下に行う、請求項１〜９の何れかに記載の製造方法。The reaction is performed according to the general formula [5]
HO-P (O) (R 5) 2 [5]
(Wherein, R 5 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.) The method according to any one of claims 1 to 9, which is performed in the presence of a phosphinic acid represented by
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002142955A JP3836395B2 (en) | 2002-05-17 | 2002-05-17 | Process for producing alkenyl phosphorus compound |
| PCT/JP2003/005807 WO2003097654A1 (en) | 2002-05-17 | 2003-05-09 | Method for producing an alkenyl phosphorus compound |
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| JP2002142955A JP3836395B2 (en) | 2002-05-17 | 2002-05-17 | Process for producing alkenyl phosphorus compound |
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| JP2003311170A Division JP3836460B2 (en) | 2003-09-03 | 2003-09-03 | Method for producing alkenyl phosphorus compound |
| JP2003311169A Division JP3836459B2 (en) | 2003-09-03 | 2003-09-03 | Process for producing alkenylphosphonic acid ester |
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| JP3836395B2 JP3836395B2 (en) | 2006-10-25 |
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| WO (1) | WO2003097654A1 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004043492A (en) * | 2003-09-03 | 2004-02-12 | Japan Science & Technology Corp | Method for producing alkenyl phosphorus compound |
| JP2005232060A (en) * | 2004-02-18 | 2005-09-02 | National Institute Of Advanced Industrial & Technology | Method for producing organophosphorus compound |
| JP2005232065A (en) * | 2004-02-18 | 2005-09-02 | National Institute Of Advanced Industrial & Technology | Method for producing phosphorus-containing butadiene compound |
| JP2005255807A (en) * | 2004-03-10 | 2005-09-22 | National Institute Of Advanced Industrial & Technology | Phosphorus-containing organic polymer and its preparation method |
| JP5388856B2 (en) * | 2007-10-18 | 2014-01-15 | 片山化学工業株式会社 | Catalysts for phosphorus-containing compounds and sulfur-containing compounds |
| JP2014087752A (en) * | 2012-10-30 | 2014-05-15 | Toray Eng Co Ltd | Microreactor system, method of producing compound using the same, and method of producing alkenyl phosphorus compound |
| JP2014132089A (en) * | 2014-03-07 | 2014-07-17 | National Institute Of Advanced Industrial & Technology | Method for producing alkenylphosphorus compound, method for producing alkenylphosphorus compound polymer and method for producing alkenylphosphorus compound copolymer |
| JP2014525459A (en) * | 2011-08-31 | 2014-09-29 | マリンクロッド エルエルシー | Remote assembly of targeted nanoparticles using H-phosphonate-ene / H-phosphonate-inhydrophosphonylation reaction |
| JP2015110617A (en) * | 2015-01-20 | 2015-06-18 | 国立研究開発法人産業技術総合研究所 | Alkenyl phosphorus compound, alkenyl phosphorus compound polymer and alkenyl phosphorus compound copolymer |
| WO2017043552A1 (en) * | 2015-09-11 | 2017-03-16 | 丸善石油化学株式会社 | Method for producing alkenyl phosphorus compound |
| WO2021106982A1 (en) * | 2019-11-27 | 2021-06-03 | 丸善石油化学株式会社 | Method for producing alkenyl phosphorus compound |
| JP2021084875A (en) * | 2019-11-27 | 2021-06-03 | 丸善石油化学株式会社 | Method for producing alkenylphosphorus compound |
| WO2021106981A1 (en) * | 2019-11-27 | 2021-06-03 | 丸善石油化学株式会社 | Complex compound and production method therefor |
| CN114031638A (en) * | 2021-12-09 | 2022-02-11 | 浙江万盛股份有限公司 | Preparation method of diaryl alkylphosphonate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10350676A1 (en) * | 2003-10-30 | 2005-06-02 | Basf Ag | Process for the preparation of an alkenylphosphonic acid derivative |
| DE10350674A1 (en) | 2003-10-30 | 2005-06-02 | Basf Ag | Process for the preparation of an alkenylphosphonic acid derivative |
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| US3673285A (en) * | 1969-11-12 | 1972-06-27 | Hooker Chemical Corp | Preparation of vinyl organo-phosphorous compounds |
| JPH09241276A (en) * | 1996-03-07 | 1997-09-16 | Agency Of Ind Science & Technol | Production of alkenylphosphine oxide compound |
| JP2002179691A (en) * | 2000-11-02 | 2002-06-26 | Basf Ag | Method for producing alkenylphosphonic acid derivative |
| JP2004043492A (en) * | 2003-09-03 | 2004-02-12 | Japan Science & Technology Corp | Method for producing alkenyl phosphorus compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0794190B1 (en) * | 1996-03-07 | 2002-04-24 | National Institute of Advanced Industrial Science and Technology | Method of producing alkenylphosphine oxide or bis (alkenylphosphine oxide) |
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- 2002-05-17 JP JP2002142955A patent/JP3836395B2/en not_active Expired - Lifetime
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- 2003-05-09 WO PCT/JP2003/005807 patent/WO2003097654A1/en active Application Filing
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| US3673285A (en) * | 1969-11-12 | 1972-06-27 | Hooker Chemical Corp | Preparation of vinyl organo-phosphorous compounds |
| JPH09241276A (en) * | 1996-03-07 | 1997-09-16 | Agency Of Ind Science & Technol | Production of alkenylphosphine oxide compound |
| JP2002179691A (en) * | 2000-11-02 | 2002-06-26 | Basf Ag | Method for producing alkenylphosphonic acid derivative |
| JP2004043492A (en) * | 2003-09-03 | 2004-02-12 | Japan Science & Technology Corp | Method for producing alkenyl phosphorus compound |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004043492A (en) * | 2003-09-03 | 2004-02-12 | Japan Science & Technology Corp | Method for producing alkenyl phosphorus compound |
| JP2005232060A (en) * | 2004-02-18 | 2005-09-02 | National Institute Of Advanced Industrial & Technology | Method for producing organophosphorus compound |
| JP2005232065A (en) * | 2004-02-18 | 2005-09-02 | National Institute Of Advanced Industrial & Technology | Method for producing phosphorus-containing butadiene compound |
| JP2005255807A (en) * | 2004-03-10 | 2005-09-22 | National Institute Of Advanced Industrial & Technology | Phosphorus-containing organic polymer and its preparation method |
| JP5388856B2 (en) * | 2007-10-18 | 2014-01-15 | 片山化学工業株式会社 | Catalysts for phosphorus-containing compounds and sulfur-containing compounds |
| JP2014525459A (en) * | 2011-08-31 | 2014-09-29 | マリンクロッド エルエルシー | Remote assembly of targeted nanoparticles using H-phosphonate-ene / H-phosphonate-inhydrophosphonylation reaction |
| JP2014087752A (en) * | 2012-10-30 | 2014-05-15 | Toray Eng Co Ltd | Microreactor system, method of producing compound using the same, and method of producing alkenyl phosphorus compound |
| JP2014132089A (en) * | 2014-03-07 | 2014-07-17 | National Institute Of Advanced Industrial & Technology | Method for producing alkenylphosphorus compound, method for producing alkenylphosphorus compound polymer and method for producing alkenylphosphorus compound copolymer |
| JP2015110617A (en) * | 2015-01-20 | 2015-06-18 | 国立研究開発法人産業技術総合研究所 | Alkenyl phosphorus compound, alkenyl phosphorus compound polymer and alkenyl phosphorus compound copolymer |
| WO2017043552A1 (en) * | 2015-09-11 | 2017-03-16 | 丸善石油化学株式会社 | Method for producing alkenyl phosphorus compound |
| JPWO2017043552A1 (en) * | 2015-09-11 | 2018-06-28 | 丸善石油化学株式会社 | Process for producing alkenyl phosphorus compound |
| US10479809B2 (en) | 2015-09-11 | 2019-11-19 | Maruzen Petrochemical Co., Ltd. | Method for producing alkenyl phosphorus compound |
| WO2021106982A1 (en) * | 2019-11-27 | 2021-06-03 | 丸善石油化学株式会社 | Method for producing alkenyl phosphorus compound |
| JP2021084875A (en) * | 2019-11-27 | 2021-06-03 | 丸善石油化学株式会社 | Method for producing alkenylphosphorus compound |
| WO2021106981A1 (en) * | 2019-11-27 | 2021-06-03 | 丸善石油化学株式会社 | Complex compound and production method therefor |
| JP7282017B2 (en) | 2019-11-27 | 2023-05-26 | 丸善石油化学株式会社 | Method for producing alkenyl phosphorus compound |
| EP3971222A4 (en) * | 2019-11-27 | 2024-02-21 | Maruzen Petrochemical Co., Ltd. | Complex compound and production method therefor |
| CN114031638A (en) * | 2021-12-09 | 2022-02-11 | 浙江万盛股份有限公司 | Preparation method of diaryl alkylphosphonate |
| CN114031638B (en) * | 2021-12-09 | 2024-02-20 | 浙江万盛股份有限公司 | Preparation method of diaryl alkylphosphonate |
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| WO2003097654A1 (en) | 2003-11-27 |
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