CN1788011A - 制备膦-硼烷络合物的方法 - Google Patents
制备膦-硼烷络合物的方法 Download PDFInfo
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- CN1788011A CN1788011A CNA2004800129125A CN200480012912A CN1788011A CN 1788011 A CN1788011 A CN 1788011A CN A2004800129125 A CNA2004800129125 A CN A2004800129125A CN 200480012912 A CN200480012912 A CN 200480012912A CN 1788011 A CN1788011 A CN 1788011A
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- CN
- China
- Prior art keywords
- optionally substituted
- borane
- group
- phosphine
- complex
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- PKPBCVSCCPTDIU-UHFFFAOYSA-N B.P Chemical class B.P PKPBCVSCCPTDIU-UHFFFAOYSA-N 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000005843 halogen group Chemical group 0.000 claims abstract description 16
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 15
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 12
- 229910000085 borane Inorganic materials 0.000 claims abstract description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 11
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 10
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- BWJRMVLPCQPWGR-UHFFFAOYSA-N boron;phosphane Chemical compound [B].P BWJRMVLPCQPWGR-UHFFFAOYSA-N 0.000 claims description 13
- 125000003282 alkyl amino group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical group [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- -1 aryl triflates Chemical class 0.000 description 54
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 125000001424 substituent group Chemical group 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000004679 31P NMR spectroscopy Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- QKZWXPLBVCKXNQ-UHFFFAOYSA-N (2-methoxyphenyl)-[2-[(2-methoxyphenyl)-phenylphosphanyl]ethyl]-phenylphosphane Chemical compound COC1=CC=CC=C1P(C=1C=CC=CC=1)CCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1 QKZWXPLBVCKXNQ-UHFFFAOYSA-N 0.000 description 2
- GKZIPAQOHJQRTP-UHFFFAOYSA-N (2-methoxyphenyl)methyl-[2-[(2-methoxyphenyl)methyl-phenylphosphanyl]ethyl]-phenylphosphane Chemical compound COC1=CC=CC=C1CP(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)CC1=CC=CC=C1OC GKZIPAQOHJQRTP-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZHIPXAFNKGZMSC-UHFFFAOYSA-N bis(4-methylphenyl)-oxophosphanium Chemical compound C1=CC(C)=CC=C1[P+](=O)C1=CC=C(C)C=C1 ZHIPXAFNKGZMSC-UHFFFAOYSA-N 0.000 description 2
- MCQRPQCQMGVWIQ-UHFFFAOYSA-N boron;methylsulfanylmethane Chemical compound [B].CSC MCQRPQCQMGVWIQ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HJPHBJYOODQSLK-UHFFFAOYSA-N dicyclohexyl(oxo)phosphanium Chemical compound C1CCCCC1[P+](=O)C1CCCCC1 HJPHBJYOODQSLK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 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 2
- 125000005935 hexyloxycarbonyl group Chemical group 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
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ADRUTLJVBQXMTI-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1.C1COCO1 ADRUTLJVBQXMTI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- WGOBPPNNYVSJTE-UHFFFAOYSA-N 1-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 WGOBPPNNYVSJTE-UHFFFAOYSA-N 0.000 description 1
- WILMTQKUPOOLFE-UHFFFAOYSA-N 1-methoxy-4-(4-methoxyphenyl)phosphonoylbenzene Chemical compound C1=CC(OC)=CC=C1P(=O)C1=CC=C(OC)C=C1 WILMTQKUPOOLFE-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004485 2-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- FWXAUDSWDBGCMN-UHFFFAOYSA-N 3-diphenylphosphanylbutan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-UHFFFAOYSA-N 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
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Classifications
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- 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
-
- 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
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种制备由通式(I)表示的膦-硼烷络合物或其盐的方法:[其中R1、R2和R3各自独立地是氢、卤素、任选取代的烷基、任选取代的环烷基、任选取代的芳基、或者任选取代的杂环基(条件在于,R1和R2与其相邻的磷原子可以一起形成4-至6-员环)],其特征在于将通式(II)表示的化合物在溶剂中、在硼烷试剂存在下进行转化:[其中各符号定义同上]。
Description
技术领域
本发明涉及一种制备膦-硼烷络合物的方法。
背景技术
膦-硼烷络合物这类化合物通常不会在空气或水中分解,但是容易与胺作用释出硼烷而转化为膦,因此它被用于合成很多与膦相当的有机磷化合物。例如,Heteroatom Chemistry,No.3,p.563-575,1992中描述了用作不对称还原反应的配体的1,2-双[(邻茴香基)苯基膦基]乙烷(DIPAMP)的下述合成方法的反应方案。
另外,Tetrahedron Letters,No.40.p.201-204,1999中报道了通过将芳基三氟甲磺酸酯(aryltriflate)在钯催化剂存在下进行反应合成得到三芳基膦。
[X=OTf,ONf]
已经先后报道过下述方法用于制备膦-硼烷络合物:
1)通过将氧化膦在氯化铈、硼氢化钠和氢化铝锂存在下反应得到膦-硼烷络合物的方法(Journal of the American Chemical Society,No.107,p.5301-5303,1985);
2)通过将氧化膦在三氟甲磺酸甲酯、氢化铝锂和硼烷-四氢呋喃络合物存在下反应得到膦-硼烷络合物的方法(Organic Letters,No.3,p.87-90,2001);
3)通过将膦作为起始原料与硼烷-四氢呋喃络合物反应得到膦-硼烷络合物的方法(Angewandte Chemie Internatioal Edition,No.18,p.781-782,1979);
4)通过将氯代膦作为起始原料与氢化铝锂和硼烷-四氢呋喃络合物反应得到膦-硼烷络合物的方法(Journal of the American Chemical Society,No.112,p.5244-5252,1990);
5)通过将氧化膦在二乙基硼烷存在下反应得到膦-硼烷络合物的方法(Chemische Berichte,No.120,p.1117-1123,1987);以及
6)通过将环状氧化膦在硼烷-二甲硫醚络合物存在下反应得到膦-硼烷络合物的方法(Journal of the Chemical Society,Perkin Transactions 1,p.4451-4455,2000)。
发明内容
由于三价有机磷化合物容易氧化,因而在上述方法3)和4)中用作反应试剂时不稳定,并且在上述方法1)、2)和4)中分别使用了氢化铝锂作为还原剂,因此其纯化变得相当复杂,同时在安全方面也存在问题。在合成方法5)中很难选择性地只得到膦-硼烷络合物,方法6)中仅仅报道了环状膦-硼烷络合物的合成实施例。
本发明人对制备用于有机磷化合物合成的膦-硼烷络合物的方法进行了深入研究,第一次发现当将由下式(II)表示的化合物或其盐:
其中R1、R2和R3相同或不同,且独立地表示氢原子、卤素原子、任选取代的烷基、任选取代的环烷基、任选取代的芳基、或任选取代的杂环基,条件在于R1和R2与其相邻的磷原子可以一起形成4-至6-员环(在后文某些情形中缩写为化合物(II)),在溶剂中、在硼烷试剂存在下反应,在温和条件下可以高收率地得到由下式(I)表示的膦-硼烷络合物或其盐:
其中各符号定义同上(在后文某些情形中缩写为化合物(I))。本发明基于上述发现而得以完成。
也就是说,本发明涉及:
(1)一种制备由下式表示的膦-硼烷络合物或其盐的方法:
其中R1、R2和R3相同或不同,且独立地表示氢原子、卤素原子、任选取代的烷基、任选取代的环烷基、任选取代的芳基、或任选取代的杂环基,条件在于R1和R2与其相邻的磷原子可以一起形成4-至6-员环,所述方法包括将由下式表示的化合物或其盐在溶剂中、在硼烷试剂存在下进行转化:
其中各符号定义同上;
(2)根据上述(1)的方法,其中R3是氢原子;
(3)根据上述(2)的方法,其中R1和R2与其相邻的磷原子一起形成5-员环;
(4)根据上述(1)的方法,其中R1和R2相同或不同,且独立地表示氢原子、卤素原子、任选取代的烷基、任选取代的环烷基、任选取代的芳基、或任选取代的杂环基,条件在于R1和R2与其相邻的磷原子可以一起形成4-至6-员环;R3表示卤素原子、任选取代的烷基、任选取代的环烷基、任选取代的芳基、或任选取代的杂环基;
(5)根据上述(4)的方法,其中R1和R2与其相邻的磷原子一起形成4-或6-员环;
(6)根据上述(2)或(4)的方法,其中R1和R2相同或不同,且独立地表示任选取代的芳基;
(7)根据上述(6)的方法,其中R1和R2相同或不同,且独立地表示任选被1-5个低级烷基、低级烷氧基、卤素原子、单-低级烷基氨基、或二-低级烷基氨基取代的苯基;
(8)根据上述(2)或(4)的方法,其中R1和R2相同或不同,且独立地表示低级烷基或低级环烷基;
(9)根据上述(1)的方法,其中所述硼烷试剂是硼烷-四氢呋喃络合物;等。
发明的最佳方案
在上述式中,R1、R2和R3相同或不同,且独立地表示氢原子、卤素原子、任选取代的烷基、任选取代的环烷基、或任选取代的芳基。
R1、R2和R3所表示的“卤素原子”包括氟、氯、溴和碘。
R1、R2和R3所表示的“任选取代的烷基”中的烷基包括低级烷基(例如C1-6烷基,如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、己基等)。
烷基上的取代基实例包括(1)硝基,(2)亚硝基,(3)氰基,(4)羟基,(5)低级烷氧基(例如C1-6烷氧基,如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、戊氧基、己氧基等),(6)甲酰基,(7)低级烷基羰基(例如C1-6烷基羰基,如乙酰基、丙酰基、丁酰基、异丁酰基、戊酰基、异戊酰基、新戊酰基等),(8)低级烷氧基羰基(例如C1-6烷氧基-羰基,如甲氧羰基、乙氧羰基、丙氧羰基、异丙氧羰基、丁氧羰基、异丁氧羰基、仲丁氧羰基、叔丁氧羰基、戊氧羰基、己氧羰基等),(9)羧基,(10)N-单-低级烷基氨甲酰基(例如N-单C1-6烷基氨甲酰基,如N-甲基氨甲酰基、N-乙基氨甲酰基、N-丙基氨甲酰基、N-异丙基氨甲酰基、N-丁基氨甲酰基、N-异丁基氨甲酰基、N-叔丁基氨甲酰基等),(11)N,N-二-低级烷基氨甲酰基(例如N,N-二-C1-6烷基氨甲酰基,如N,N-二甲基氨甲酰基、N,N-二乙基氨甲酰基、N,N-二丙基氨甲酰基、N,N-二异丙基氨甲酰基、N-乙基-N-甲基氨甲酰基等),(12)卤素原子(例如氟、氯、溴和碘),(13)单-低级烷基氨基(例如单-C1-6烷基氨基,如甲氨基、乙氨基、丙氨基、异丙氨基、丁氨基、异丁氨基、仲丁氨基、叔丁氨基、戊氨基、己氨基等),以及(14)二-低级烷基氨基(例如二-C1-6烷基氨基,如二甲基氨基、二乙基氨基、二丙基氨基、二异丙基氨基、二丁基氨基、N-乙基-N-甲基氨基等)。它们可以在任意可能的位置上具有1-3个选自上述基团中的取代基。
R1、R2和R3所表示的“任选取代的环烷基”中的环烷基包括低级环烷基(例如C3-6环烷基,如环丙基、环丁基、环己基等)。
“环烷基”上的取代基包括与在“任选取代的烷基”上的取代基中例举的具有相同数目的相同取代基。
R1、R2和R3所表示的“任选取代的芳基”中的芳基包括C6-10芳基例如苯基、1-萘基和2-萘基等,以及多环芳香烃例如联苯基、萘基-苯基等。
“芳基”上的取代基实例包括(1)硝基,(2)亚硝基,(3)氰基,(4)羟基,(5)低级烷基(例如C1-6烷基,如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、己基等),(6)低级烷氧基(例如C1-6烷氧基,如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、戊氧基、己氧基等),(7)甲酰基,(8)低级烷基羰基(例如C1-6烷基羰基,如乙酰基、丙酰基、丁酰基、异丁酰基、戊酰基、异戊酰基、新戊酰基等),(9)低级烷氧基羰基(例如C1-6烷氧基-羰基,如甲氧羰基、乙氧羰基、丙氧羰基、异丙氧羰基、丁氧羰基、异丁氧羰基、仲丁氧羰基、叔丁氧羰基、戊氧羰基、己氧羰基等),(10)羧基,(11)N-单-低级烷基氨甲酰基(例如N-单-C1-6烷基氨甲酰基,如N-甲基氨甲酰基、N-乙基氨甲酰基、N-丙基氨甲酰基、N-异丙基氨甲酰基、N-丁基氨甲酰基、N-异丁基氨甲酰基、N-叔丁基氨甲酰基等),(12)N,N-二-低级烷基氨甲酰基(例如N,N-二-C1-6烷基氨甲酰基,如N,N-二甲基氨甲酰基、N,N-二乙基氨甲酰基、N,N-二丙基氨甲酰基、N,N-二异丙基氨甲酰基、N-乙基-N-甲基氨甲酰基等),(13)卤素原子(例如氟、氯、溴和碘),(14)单-低级烷基氨基(例如单-C1-6烷基氨基,如甲氨基、乙氨基、丙氨基、异丙氨基、丁氨基、异丁氨基、仲丁氨基、叔丁氨基、戊氨基、己氨基等),(15)二-低级烷基氨基(例如二-C1-6烷基氨基,如二甲基氨基、二乙基氨基、二丙基氨基、二异丙基氨基、二丁基氨基、N-乙基-N-甲基氨基等),以及(16)卤代-低级烷基(例如卤代-C1-6烷基,如氟代甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、氯代甲基、二氯甲基、三氯甲基等)。它们可以在任意可能的位置上具有1-5个选自上述基团中的取代基。
R1、R2和R3所表示的“任选取代的杂环基”中的杂环基包括1-吡咯基、2-吡咯基、3-吡咯基、1-咪唑基、2-咪唑基、4-咪唑基、5-咪唑基、1-吡咯烷基、2-吡咯烷基、3-吡咯烷基、吡咯啉基、1-咪唑烷基、2-咪唑烷基、3-咪唑烷基、4-咪唑烷基、咪唑啉基、2-吡啶基、3-吡啶基、4-吡啶基、吡啶基(pyradinyl)、2-嘧啶基、4-嘧啶基、5-嘧啶基、1-哌啶基、2-哌啶基、3-哌啶基、4-哌啶基、2-噁唑基、4-噁唑基、5-噁唑基、2-呋喃基、3-呋喃基、2-吡喃基、3-吡喃基、4-吡喃基、5-吡喃基、6-吡喃基、1,3-二氧戊环(dioxolan)-2-基、1,3-二氧戊环-4-基、1,4-二氧戊环-2-基、1,4-二氧戊环-3-基等。
“杂环基”上的取代基包括与在“任选取代的芳基”上的取代基中例举的具有相同数目的相同取代基。
当R1和R2与其相邻的磷原子一起形成4-至6-员环时,化合物(II)包括例如具有由下式表示的结构的化合物:
其中环A、环B和环C可以具有取代基;R3定义同上。上述例举的环上的取代基包括与在“任选取代的芳基”上的取代基中例举的具有相同数目的相同取代基。
优选地,R1和R2相同或不同,且独立地表示任选取代的烷基、任选取代的环烷基、或任选取代的芳基。
其中,更加优选低级烷基、低级环烷基、或任选被取代的C6-10芳基。尤其优选任选被1-5个低级烷基、低级烷氧基、卤素原子、单-低级烷基氨基或二-低级烷基氨基取代的苯基。具体地说,更加优选任选被1-3个低级烷基、低级烷氧基、卤素原子、单-低级烷基氨基或二-低级烷基氨基取代的苯基。
R3优选为氢原子。
化合物(I)和化合物(II)的盐的实例包括与无机酸(例如盐酸、氢溴酸、硝酸、硫酸、磷酸等)形成的盐,和与有机酸(例如甲酸、乙酸、三氟乙酸、富马酸、草酸、酒石酸、马来酸、柠檬酸、琥珀酸、苹果酸、甲磺酸、苯磺酸、对甲苯磺酸等)形成的盐。如果化合物(I)和(II)具有酸性基团例如羧基等的话,可以使用其与无机碱(例如碱金属或碱土金属,如钠、钾、钙、镁等、以及氨)形成的盐或与有机碱(例如三甲胺、三乙胺、吡啶、甲基吡啶、乙醇胺、二乙醇胺、三乙醇胺、二环己胺、N,N’-二苄基乙二胺等)形成的盐。
可用于本发明中的“硼烷试剂”的实例包括硼烷-四氢呋喃络合物、硼烷-二甲硫醚络合物、硼烷-胺络合物(例如硼烷-氨络合物、硼烷-叔丁基胺络合物、硼烷-二甲胺络合物、硼烷-三乙胺络合物、硼烷-三甲胺络合物、硼烷-4-乙基吗啉络合物、硼烷-2,6-二甲基吡啶络合物、硼烷-吗啉络合物、硼烷-4-甲基吗啉络合物、硼烷-4-苯基吗啉络合物、硼烷-哌嗪络合物、硼烷-吡啶络合物、硼烷-N,N-二乙基苯胺络合物、硼烷-N,N-二异丙基苯胺络合物等)等。其中,优选硼烷-四氢呋喃络合物。
本发明方法就是将化合物(II)或其盐与硼烷试剂在溶剂中反应得到化合物(I)或其盐。
相对于1摩尔化合物(II)而言,所使用的硼烷试剂的用量为大约0.5-10摩尔,优选为大约3-5摩尔。
上述反应可以在惰性有机溶剂或惰性含水有机溶剂中进行。有机溶剂的实例包括烃类(例如己烷、戊烷、环己烷等)、芳香烃类(例如甲苯、苯、氯苯等)、醚类(例如二异丙醚、二乙醚、四氢呋喃、1,4-二噁烷、1,2-二甲氧基乙烷等)、卤代烃类(例如氯仿、二氯甲烷、1,2-二氯乙烷、四氯化碳等)、腈类(例如乙腈、丙腈等)等。这些溶剂可以单独使用,也可以以混合溶剂的形式使用。溶剂的优选实例包括芳香烃类、醚类和卤代烃类。进一步优选的实例包括芳香烃类(甲苯和苯)。
反应中的反应温度为大约0-40℃,优选为大约20-30℃。向反应中加入上述硼烷试剂的时间为0小时或者更长的时间,优选为大约0.5小时或者更长,进一步优选为大约2小时或者更长。通常,加料是在大约5小时内完成。反应的反应时间为大约0.5-24小时,优选为大约1-5小时。
制备的产物可以按照常规方法由反应混合物分离得到,然后方便地通过诸如重结晶法、蒸馏法、色谱法等分离手段进行纯化。
下面将参照实施例和参考实施例对本发明进行更加详细的说明。然而,本发明并不受这些实施例和参考实施例的限制。在实施例中,使用下面的装置测定相应的物理特性。1H核磁共振光谱仪(1H-NMR):DPX300(由Bruker制造):内标物:四甲基硅烷。13C-核磁共振光谱仪(13C-NMR):DPX300(由Bruker制造):内标物:CDCl3。31P-核磁共振光谱仪(31P-NMR):DPX300(由Bruker制造),内标物:85% H3PO4水溶液。
参考实施例1
二(对甲苯基)氧化膦(phosphine oxide)
在氮气流中,将镁(58.41g,3.48当量)、微量碘和1,2-二溴乙烷的四氢呋喃(400mL)溶液在室温下搅拌1小时。在22℃下加入对溴甲苯(411.11g,3.48当量)的四氢呋喃(2000mL)溶液后,混合物在40℃下搅拌1小时。然后在20℃下加入亚磷酸二乙酯(94.76g,0.69mol)的四氢呋喃(160mL)溶液,混合物在24℃下搅拌30分钟。在4℃下向其中加入6M-HCl(320mL),再加入水(320mL)和甲苯(1000mL),所得到的混合物在室温下搅拌30分钟。反应混合物分层后,有机层依次用水(320mL)、5% NaHO3水溶液(320mL)和5%NaCl水溶液(320mL)洗涤。有机层减压过滤,滤液减压浓缩。残余物由正己烷重结晶并干燥(在减压下于40℃)得到标题化合物(87.12g,白色粉末)。收率为54.8%。
1H-NMR(300MHz,CDCl3,TMS)δ:2.39(s,6H),7.27-7.30(m,4H),7.54(s,1H),7.57(s,1H),7.59(s,1H),7.61(s,1H),8.03(d,1H,JH-P=477.6Hz)。
13C-NMR(75MHz,CDCl3,CDCl3)δ:23.01,129.16,130.53,130.85,131.02,131.99,132.15,144.38,144.41。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:22.67(双五重峰(dquint),JH-P=477.6Hz,JHCC-P=13.3Hz)。
参考实施例2
二萘基氧化膦
在氩气氛下,将镁(2.94g,2.00当量)、微量碘和1,2-二氯甲烷的四氢呋喃(60mL)溶液在室温下搅拌1小时。在27℃下加入2-溴萘(25.00g,2.00当量)的四氢呋喃(20mL)溶液后,混合物在40℃下搅拌45分钟。然后在-9℃下加入亚磷酸二乙酯(9.77g,0.06mol)的四氢呋喃(10mL)溶液后,将混合物在2℃下搅拌3小时。再在-5℃下向其中加入水(20mL),接着加入甲苯(60mL)和6M-HCl(20mL)。所得到的混合物分层后,将获得的有机层依次用5%NaHCO3水溶液和5% NaCl水溶液洗涤。有机层用无水硫酸镁干燥并自然过滤,所得到的滤液减压浓缩。残余物由异丙醚/正己烷重结晶并干燥(在减压下于40℃)得到标题化合物(9.621g,白色粉末)。收率为53.0%。
1H-NMR(300MHz,CDCl3,TMS)δ:7.49-7.64(m,6.5H),7.86-7.95(m,6H),8.40(d,2H,J=15.7Hz),9.15(0.5H)。
13C-NMR(75MHz,CDCl3,CDCl3)δ:125.07,125.23,127.13,127.76,127.93,128.41,128.81,128.96,132.43,132.62,132.82,132.96,135.05。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:22.99(双五重峰,JH-P=481.0Hz,JHCC-P=13.4Hz)。
参考实施例3
二环己基氧化膦
在氩气氛于38-43℃,将溴代环己烷(50.00g,2.00当量)加入至镁(7.05g,1.93当量)和微量碘的四氢呋喃(70mL)中。混合物在5℃下搅拌1小时。然后在5℃下加入亚磷酸二乙酯(20.70g,0.15mol),混合物在5℃下搅拌2小时。在5℃下向其中加入水(50mL),再加入6M-HCl(50mL)和甲苯(70mL),所得到的混合物分层。将所得到的有机层依次用水、5% NaHCO3水溶液和5% NaCl水溶液洗涤,有机层用无水硫酸镁干燥并自然过滤。滤液减压浓缩。残余物由庚烷重结晶并干燥(在减压下于40℃)得到标题化合物(10.5g,白色粉末)。收率为37.6%。
1H-NMR(300MHz,CDCl3,TMS)δ:1.25-1.98(m,22H),6.28(d,1H,JH-P=433.6Hz)。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:50.07(d,JH-P=433.5Hz)。
参考实施例4
二-对甲氧基苯基氧化膦
在氮气流中,将镁(19.45g,4.00当量)、微量碘和1,2-二溴乙烷的四氢呋喃(140mL)溶液在室温下搅拌30分钟。在25-30℃下加入1-溴-4-甲氧基苯(151.47g,4.00当量)的四氢呋喃(650mL)溶液后,混合物在40℃下搅拌1小时。然后,在25-30℃下向其中加入亚磷酸二乙酯(27.71g,0.20mol)的四氢呋喃(60mL)溶液。再在0-5℃下向其中加入6M-HCl(110mL),接着再加入水(110mL)和甲苯(110mL)。反应混合物分层后,将所得到的有机层依次用水(110mL)、5% NaHCO3水溶液(110mL)和5% NaCl水溶液(110mL)洗涤。有机层用硫酸镁(25g)干燥并减压浓缩。残余物由正己烷重结晶并干燥(在减压下于40℃)得到标题化合物(15.71g,白色粉末)。收率为30.0%。
1H-NMR(300MHz,CDCl3,TMS)δ:3.85(s,6H),6.98(d,2H,J=2.1Hz),7.01(d,2H,J=2.1Hz),7.57(s,1H),7.60(s,1H),7.62(s,1H),7.65(s,1H),8.03(d,1H,JH-P=477Hz)。
13C-NMR(75MHz,CDCl3,CDCl3)δ:55.31,114.29,114.28,122.27,123.70,132.51,132.68,162.87。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:21.19(dq,JH-P=477Hz,JH-CCP=13Hz)。
实施例1
二苯基膦-硼烷络合物
在氩气氛于室温(25℃),将2mL甲苯和1mL四氢呋喃加入至二苯基氧化膦(0.4078g,2.0mmol)中,搅拌混合物得到悬浮液。然后向该悬浮液中加入1.02mol/L硼烷-四氢呋喃络合物(6mL,3.06当量)。反应溶液减压浓缩后,残余物溶解于甲苯中,通过硅胶柱色谱法(硅胶25g,甲苯)纯化,将所需的级分减压浓缩。残余物由正己烷重结晶并干燥(在减压下于40℃)得到标题化合物(0.2982g,透明油状物)。收率为70.3%。
1H-NMR(300MHz,CDCl3,TMS)δ:0.51-1.75(m,3H),6.31(dq,1H,JH-P=378.7Hz,J=7.0Hz),7.42-7.52(m,6H),7.64-7.71(m,4H)。
13C-NMR(75MHz,CDCl3,CDCl3)δ:125.50,126.26,128.66,128.80,131.28,131.31,132.54,132.67。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:0.69-1.69(m),3.83-4.83(m)。
实施例2
二(对甲苯基)膦-硼烷络合物
在氩气氛于室温(25℃),将32mL甲苯加入至参考实施例1中合成得到的双(对甲苯基)氧化膦(7.11g,30.9mmol)中,搅拌混合物得到悬浮液。然后向该悬浮液中加入1.02mol/L硼烷-四氢呋喃络合物(100mL,3.30当量)。反应混合物减压浓缩后,将残余物溶解于甲苯中,通过硅胶柱色谱法(硅胶25g,甲苯)纯化,将所需的级分减压浓缩。残余物由正己烷重结晶并干燥(在减压下于40℃)得到标题化合物(6.44g,白色粉末)。收率为91.4%。
1H-NMR(300MHz,CDCl3,TMS)δ:0.45-1.65(m,3H),2.37(s,6H),6.24(dq,1H,JH-P=377.5Hz,J=6.6Hz),7.22-7.25(m,4H),7.49-7.56(m,4H)。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:-1.43--0.18(m),1.81-3.00(m)。
实施例3
二萘基膦-硼烷络合物
在氩气氛于室温(25℃),将4mL甲苯加入至参考实施例2中合成得到的二萘基氧化膦(0.6061g,2.00mmol)中,搅拌混合物得到悬浮液。然后向该悬浮液中加入1.02mol/L硼烷-四氢呋喃络合物(5mL,2.55当量)。反应混合物通过硅胶柱色谱法纯化(硅胶15g,甲苯),将所需的级分减压浓缩。干燥残余物(在减压下于40℃)后,得到标题化合物(0.4577g,白色粉末)。收率为76.2%。
1H-NMR(300MHz,CDCl3,TMS)δ:0.60-1.85(m,3H),6.56(dq,1H,JH-P=378.7Hz,J=6.9Hz),7.52-8.31(m,14H)。
13C-NMR(75MHz,CDCl3,CDCl3)δ:124.40,125.16,128.53,129.22,129.31,129.61,129.96,130.30,130.43,134.20,134.36,135.91,135.94,135.99,136.14。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:1.10-2.21(m),3.92-4.95(m)。
实施例4
二环己基膦-硼烷络合物
在氩气氛于室温(25℃),将1mL甲苯加入至参考实施例3中合成得到的二环己基氧化膦(0.1106g,0.50mmol)中得到溶液。然后向该溶液中加入1.02mol/L硼烷-四氢呋喃络合物(1.5mL,3.06当量)。反应混合物减压浓缩。残余物溶解于甲苯中,然后用硅胶柱色谱法(硅胶10g,甲苯)纯化,将所需的级分减压浓缩。残余物由正己烷重结晶并干燥(在减压下于40℃)得到标题化合物(0.05g,白色粉末)。收率为4.3%。
1H-NMR(300MHz,CDCl3,TMS)δ:0.25-0.95(m,3H),1.27-1.90(m,22H),4.13(dq,1H,JH-P=351.1Hz,J=4.7Hz)。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:16.20-17.54(m),18.98-20.31(m)。
实施例5
二(对甲氧基苯基)膦-硼烷络合物
在氩气氛于室温(25℃),将80mL甲苯加入至参考实施例4中合成得到的二(对甲氧基苯基)氧化膦(13.11g,0.17mmol)中得到溶液。然后向该溶液中在2小时内加入1.02mol/L硼烷-四氢呋喃络合物(165mL,3.30当量)。加入硅胶(20g)后,将反应混合物过滤并减压浓缩。将所得到的残余物由正己烷重结晶并干燥(在减压下于40℃)得到标题化合物(11.1g,白色粉末)。收率为85%。
1H-NMR(300MHz,CDCl3,TMS)δ:0.26-1.65(m,3H),3.83(s,6H),6.26(dm,1H,JH-P=378Hz),6.94(s,1H),6.95(s,1H),6.96(s,1H),6.97(s,1H),7.55(s,1H),7.57(s,1H),7.58(s,1H),7.61(s,1H)。
13C-NMR(75MHz,CDCl3,CDCl3)δ:55.30,114.59,114.74,116.84,117.67,134.43,134.57,162.23。
31P-NMR(121MHz,CDCl3,85% H3PO4)δ:-4.5-(-3.2)(m),-1.6-0.4(m)。
工业应用
根据本发明的方法可以在温和条件下高收率制备得到可用作膦配体(例如1,2-双[(邻茴香基)苯基膦基]乙烷(DIPAMP);1,2-双(二苯基膦基)丙烷(PROPHOS);2,3-双(二苯基膦基)丁烷(CHIRAPHOS);2,4-双(二苯基膦基)戊烷(BDPP)等)的制备中间体的膦-硼烷络合物,上述膦配体可以与过渡金属(例如钌、铱、钯、镍、铑等)形成络合物用于不对称合成反应。
Claims (9)
2.根据权利要求1的方法,其中R3是氢原子。
3.根据权利要求2的方法,其中R1和R2与其相邻的磷原子一起形成5-员环。
4.根据权利要求1的方法,其中R1和R2相同或不同,且独立地表示氢原子、卤素原子、任选取代的烷基、任选取代的环烷基、任选取代的芳基、或任选取代的杂环基,条件在于R1和R2与其相邻的磷原子一起可以形成4-至6-员环;并且R3表示卤素原子、任选取代的烷基、任选取代的环烷基、任选取代的芳基、或任选取代的杂环基。
5.根据权利要求4的方法,其中R1和R2与其相邻的磷原子一起形成4-或6-员环。
6.根据权利要求2或4的方法,其中R1和R2相同或不同,且独立地表示任选取代的芳基。
7.根据权利要求6的方法,其中R1和R2相同或不同,且独立地表示任选被1-5个低级烷基、低级烷氧基、卤素原子、单-低级烷基氨基、或二-低级烷基氨基取代的苯基。
8.根据权利要求2或4的方法,其中R1和R2相同或不同,且独立地表示低级烷基或低级环烷基。
9.根据权利要求1的方法,其中所述硼烷试剂是硼烷-四氢呋喃络合物。
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