JP2010138136A - 新規ホスフィンボラン化合物及びその製造方法並びに水素−ホスフィンボラン化合物の製造方法 - Google Patents
新規ホスフィンボラン化合物及びその製造方法並びに水素−ホスフィンボラン化合物の製造方法 Download PDFInfo
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- JP2010138136A JP2010138136A JP2008317786A JP2008317786A JP2010138136A JP 2010138136 A JP2010138136 A JP 2010138136A JP 2008317786 A JP2008317786 A JP 2008317786A JP 2008317786 A JP2008317786 A JP 2008317786A JP 2010138136 A JP2010138136 A JP 2010138136A
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- Prior art keywords
- group
- phosphine
- borane compound
- general formula
- formula
- 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.)
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- -1 phosphine-borane compound Chemical class 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 48
- 229910000085 borane Inorganic materials 0.000 claims description 44
- 125000004437 phosphorous atom Chemical group 0.000 claims description 18
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
- 239000003446 ligand Substances 0.000 abstract description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000011914 asymmetric synthesis Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- SLRCCWJSBJZJBV-AJNGGQMLSA-N sparteine Chemical compound C1N2CCCC[C@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-AJNGGQMLSA-N 0.000 description 4
- 229960001945 sparteine Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 0 *NC(P(*)(*)*)=O Chemical compound *NC(P(*)(*)*)=O 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 3
- LJPFWCBUSPMLGW-UHFFFAOYSA-N B.CPC(C)(C)C Chemical compound B.CPC(C)(C)C LJPFWCBUSPMLGW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PKPBCVSCCPTDIU-UHFFFAOYSA-N B.P Chemical class B.P PKPBCVSCCPTDIU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([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
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 230000006340 racemization Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- DRZBLHZZDMCPGX-VXKWHMMOSA-N (r)-tert-butyl-[3-[tert-butyl(methyl)phosphanyl]quinoxalin-2-yl]-methylphosphane Chemical compound C1=CC=C2N=C([P@](C)C(C)(C)C)C([P@](C)C(C)(C)C)=NC2=C1 DRZBLHZZDMCPGX-VXKWHMMOSA-N 0.000 description 1
- DRZBLHZZDMCPGX-FGZHOGPDSA-N (s)-tert-butyl-[3-[tert-butyl(methyl)phosphanyl]quinoxalin-2-yl]-methylphosphane Chemical compound C1=CC=C2N=C([P@@](C)C(C)(C)C)C([P@@](C)C(C)(C)C)=NC2=C1 DRZBLHZZDMCPGX-FGZHOGPDSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SPSSDDOTEZKOOV-UHFFFAOYSA-N 2,3-dichloroquinoxaline Chemical compound C1=CC=C2N=C(Cl)C(Cl)=NC2=C1 SPSSDDOTEZKOOV-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003890 2-phenylbutyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BNVPSHQBVAGUBZ-FJXQXJEOSA-N B.C1(=CC=CC=C1)[C@H](C)NC(=O)P Chemical compound B.C1(=CC=CC=C1)[C@H](C)NC(=O)P BNVPSHQBVAGUBZ-FJXQXJEOSA-N 0.000 description 1
- WNEJLZDEDLSCQY-UHFFFAOYSA-N B.CPC Chemical compound B.CPC WNEJLZDEDLSCQY-UHFFFAOYSA-N 0.000 description 1
- 229930008564 C01BA04 - Sparteine Natural products 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- JJSCUXAFAJEQGB-QMMMGPOBSA-N [(1s)-1-isocyanatoethyl]benzene Chemical compound O=C=N[C@@H](C)C1=CC=CC=C1 JJSCUXAFAJEQGB-QMMMGPOBSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- SLRCCWJSBJZJBV-UHFFFAOYSA-N alpha-isosparteine Natural products C1N2CCCCC2C2CN3CCCCC3C1C2 SLRCCWJSBJZJBV-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical group 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
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- CFFBBJBFIIKTCH-UHFFFAOYSA-N borane methylphosphane Chemical compound B.CP CFFBBJBFIIKTCH-UHFFFAOYSA-N 0.000 description 1
- BWJRMVLPCQPWGR-UHFFFAOYSA-N boron;phosphane Chemical compound [B].P BWJRMVLPCQPWGR-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UQWQCMSYGMAGKF-UHFFFAOYSA-N hexane;lithium Chemical compound [Li].CCCCCC UQWQCMSYGMAGKF-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 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
- C07F9/5036—Phosphines containing the structure -C(=X)-P or NC-P
-
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C07F9/54—Quaternary phosphonium compounds
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- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
- C07F9/5414—Acyclic saturated phosphonium compounds substituted by B, Si, P or a metal
-
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- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5428—Acyclic unsaturated phosphonium compounds
-
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- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650905—Six-membered rings having the nitrogen atoms in the positions 1 and 2
- C07F9/650947—Six-membered rings having the nitrogen atoms in the positions 1 and 2 condensed with carbocyclic rings or carbocyclic ring systems
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65688—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphonium compound
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Abstract
【解決手段】下記一般式(P−1)で表されるホスフィンボラン化合物。下記一般式(P−2)で表される水素−ホスフィンボラン化合物と下記一般式(3)で表される光学活性イソシアネート化合物とをカップリング反応に付す上記ホスフィンボラン化合物の製造方法。下記式中、R1及びR2は、それぞれ水素原子、炭化水素又は置換炭化水素基を示し、それらが存在することによりリン原子に不斉が生じるように選択してもよく又は不斉が生じないように選択してもよく、R3は不斉炭化水素基又は不斉炭化水素基を示す。
【選択図】なし
Description
で表されることを特徴とするホスフィンボラン化合物。
で表されることを特徴とする上記ホスフィンボラン化合物。
で表される水素−ホスフィンボラン化合物と、一般式(3)
で表される光学活性イソシアネート化合物とをカップリング反応に付すことを特徴とするホスフィンボラン化合物の製造方法。
で表される水素−ホスフィンボラン化合物と、一般式(3)
で表される光学活性イソシアネート化合物とをカップリング反応に付した後、光学分割により精製することを特徴とするホスフィンボラン化合物の製造方法。
で表される。
で表される。
で表される。下記一般式(2)で表される水素−ホスフィンボラン化合物としては、例えばラセミを用いることができる。
(b)(SP)−アダマンチル(メチル)[N−((S)−1−フェニルエチル)カルバモイル]ホスフィンボラン、又は(RP)−アダマンチル(メチル)[N−((S)−1−フェニルエチル)カルバモイル]ホスフィンボラン
3L四つ口フラスコに、機械撹拌シール、温度計、等圧滴下ろうと及び排気部を備えた。そこへ、ラセミ−tert−ブチルメチルホスフィンボラン141.8g(1202mmol)及びTHF600ccを入れ、ラセミ−tert−ブチルメチルホスフィンボランを溶解させ、10℃以下に保持しながら1.59mol/Lのn−ブチルリチウム−ヘキサン溶液75cc(119mmol)を滴下した。続いて、同温度にて(S)−(−)−α−メチルベンジルイソシアネート176.8g(1201mmol)を滴下した。その後室温に戻し、一晩撹拌熟成した。5重量%塩酸90g加えて反応を停止した後、ヘキサン240cc及び水240ccを加えて2層に分画した。水層を除去し、有機層を2.5重量%重曹水240g、続いて水240ccで洗い、濃縮して粗生物を白色フレーク状固体として得た(348.3g)。粗生物を酢酸エチル240cc+ヘキサン1800ccで晶析し、ろ過、乾燥して無色粉末を得た。NMR分析により、得られた無色粉末は表題化合物と同定された。NMR分析結果を以下に示す。また、得られた無色粉末は、収量118.6g(447mmol)、収率37%(イソシアネートから)、ジアステレオマー過剰率>97%deであった。尚、ジアステレオマー過剰率は、1H−NMRのSPおよびRPの特定部プロトンの面積比から決定した。
1H−NMR(CDCl3);
(SP)−体(目的物);−0.5−1(3H,m),1.14(9H,d,14.7Hz),1.45(3H,d,10.5Hz),1.53(3H,d,6.9Hz),5.15(1H,pent,6.9Hz),7.2−7.4(6H,m).
(RP)−体;−0.5−1(3H,m),1.25(9H,d,14.7Hz),1.42(3H,d,10.5Hz),1.53(3H,d,6.9Hz),5.15(1H,pent,6.9Hz),7.2−7.4(6H,m).
200cc四つ口フラスコに、機械撹拌シール、温度計及び排気部を備え、そこへ、実施例1で得られた(SP)−tert−ブチル(メチル)[N−((S)−1−フェニルエチル)カルバモイル]ホスフィン−ボラン10.03g(37.8mmol)及びDMF100ccを入れ、ホスフィン−ボランを溶解させた後、氷水浴にて10℃以下とした。ここに50重量%水酸化カリウム水溶液21.26g(189mmol)とメタノール25ccを添加した。次に、氷水浴をはずして18時間撹拌熟成した。次いで、500cc三角フラスコに冷水100ccと石油エーテル100ccを入れ、ここに反応液を分散させることで反応を停止した。水層と有機層とを分離し、水層を石油エーテル100ccで再抽出し、先に分離した有機層と合わせた後、水50ccで2回洗い、無水硫酸ナトリウムにて乾燥した。シリカゲルカラムクロマトグラフィー(ワコーゲルC200)にて精製し、無色粉末を得た。NMR分析により、得られた無色粉末は表題化合物と同定された。NMR分析結果を以下に示す。また、得られた無色粉末は、収量3.01g(25.5mmol)、収率67%であった。
1H−NMR(CDCl3);
−0.5−1(3H,m),1.22(9H,d,14.7Hz),1.32(3H,dd,10.5Hz,6.0Hz),4.4(1H,dm,355Hz).
300cc四つ口フラスコに、機械撹拌シール、温度計及び排気部を備え、そこへ、実施例1で得られた(SP)−tert−ブチル(メチル)[N−((S)−1−フェニルエチル)カルバモイル]ホスフィン−ボラン7.97g(30.1mmol)及びDMF30ccを入れ、ホスフィン−ボランを溶解させた後、氷水浴にて10℃以下とした。ここに10重量%水酸化カリウム−メタノール溶液3.37g(6.0mmol、20mol%)を添加した。次に、氷水浴をはずして室温にて18時間撹拌熟成した。次いで、5%塩酸3.07g(4.2mmol)を入れて反応停止し、ヘキサン30ccと水60ccを入れて反応液を2層に分画した。水層と有機層とを分離し、水層をヘキサン10ccで3回再抽出し、先に分離した有機層と合わせた後、有機層を水30cc、ついで20%食塩水30gで洗い、無水硫酸ナトリウムにて乾燥した。シリカゲルカラムクロマトグラフィー(ワコーゲルC200)にて精製し、無色粉末として得た。収量は2.57g(21.8mmol)であり、収率は72.5%であった。得られた無色粉末は、NMR分析が実施例2で得られた化合物と同等のチャート形状を示したことから、表題化合物と同定された。
実施例2で得られた(R)−tert−ブチルメチルホスフィン−ボランを使用して、不斉ホスフィン配位子として知られる(S,S)−2,3−ビス(tert−ブチルメチルホスフィノ)キノキサリン〔略称:(S,S)−QuinoxP*〕を合成する使用例を次に示す。
1H−NMR(CDCl3);上記文献に記載のものと同等。
比旋光度;+53.5°([α]D 22(c=1,CHCl3)、文献値(R,R)−QuinoxPとして、−54.3°)
実施例2で得られた(R)−tert−ブチルメチルホスフィン−ボランを使用して、不斉ホスフィン配位子の前駆体として知られる(R,R)−1,2−ビス(tert−ブチルメチルホスフィノ)エタン−ジボラン〔略称(R,R)−BisP*−diborane〕を合成する使用例を次に示す。
1H−NMR(CDCl3);J. A. C. S., 120 (1998), 1635-1636記載のものと同等。
比旋光度;+9°([α]D 27(c=1,CHCl3)、文献値(S,S)−BisP*−diboraneとして、−9.1°)
Claims (7)
- 上記R3が(S)−1−フェニルエチル基又は(R)−1−フェニルエチル基であることを特徴とする請求項1又は2記載のホスフィンボラン化合物。
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GB0921703A GB2466365A (en) | 2008-12-15 | 2009-12-11 | Phosphine-borane compounds |
CN200910254275.7A CN101747377B (zh) | 2008-12-15 | 2009-12-14 | 膦硼烷化合物及其制造方法以及氢-膦硼烷化合物的制造方法 |
US12/637,999 US8338391B2 (en) | 2008-12-15 | 2009-12-15 | Phosphine-borane compound and method for producing the same, and method for producing hydrogen-phosphine-borane compound |
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WO2011126045A1 (ja) * | 2010-04-09 | 2011-10-13 | 日本化学工業株式会社 | ピラジン誘導体の製造方法 |
WO2011129365A1 (ja) * | 2010-04-14 | 2011-10-20 | 日本化学工業株式会社 | 抗がん剤 |
KR101785950B1 (ko) | 2013-11-26 | 2017-11-15 | 완후아 케미컬(닝보) 코퍼레이션 리미티드 | 우레트디온기를 함유하는 이소시아네이트 단독중합체의 제조방법 |
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JP2972887B1 (ja) * | 1998-10-29 | 1999-11-08 | 千葉大学長 | 光学活性ビスホスフィノメタン並びにそれらのロジウム又は銅錯体を用いる不斉合成 |
JP2007056007A (ja) * | 2005-07-25 | 2007-03-08 | Chiba Univ | 2,3−ビス(ジアルキルホスフィノ)ピラジン誘導体及びその製造方法、並びに該誘導体を配位子とする金属錯体 |
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US7608709B2 (en) * | 2005-07-25 | 2009-10-27 | National University Corporation Chiba University | 2, 3-bis(dialkylphosphino)pyrazine derivative, process of producing the same, and metal complex having the same as ligand |
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JP2972887B1 (ja) * | 1998-10-29 | 1999-11-08 | 千葉大学長 | 光学活性ビスホスフィノメタン並びにそれらのロジウム又は銅錯体を用いる不斉合成 |
JP2007056007A (ja) * | 2005-07-25 | 2007-03-08 | Chiba Univ | 2,3−ビス(ジアルキルホスフィノ)ピラジン誘導体及びその製造方法、並びに該誘導体を配位子とする金属錯体 |
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Cited By (5)
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WO2011126045A1 (ja) * | 2010-04-09 | 2011-10-13 | 日本化学工業株式会社 | ピラジン誘導体の製造方法 |
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WO2011129365A1 (ja) * | 2010-04-14 | 2011-10-20 | 日本化学工業株式会社 | 抗がん剤 |
JP5646606B2 (ja) * | 2010-04-14 | 2014-12-24 | 日本化学工業株式会社 | 抗がん剤の製造方法 |
KR101785950B1 (ko) | 2013-11-26 | 2017-11-15 | 완후아 케미컬(닝보) 코퍼레이션 리미티드 | 우레트디온기를 함유하는 이소시아네이트 단독중합체의 제조방법 |
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