US20020058837A1 - 2,2 (Diarlyl) Vinylphosphine compound, palladium catalyst thereof, and process for producing arylamine, diaryl, or arylalkyne with the catalyst - Google Patents
2,2 (Diarlyl) Vinylphosphine compound, palladium catalyst thereof, and process for producing arylamine, diaryl, or arylalkyne with the catalyst Download PDFInfo
- Publication number
- US20020058837A1 US20020058837A1 US09/891,304 US89130401A US2002058837A1 US 20020058837 A1 US20020058837 A1 US 20020058837A1 US 89130401 A US89130401 A US 89130401A US 2002058837 A1 US2002058837 A1 US 2002058837A1
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- US
- United States
- Prior art keywords
- compound
- tbu
- group
- cyhx
- palladium
- Prior art date
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- -1 Vinylphosphine compound Chemical class 0.000 title claims abstract description 230
- 238000000034 method Methods 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 16
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 title claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052763 palladium Inorganic materials 0.000 title claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 59
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 39
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 30
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 28
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 110
- 238000006243 chemical reaction Methods 0.000 claims description 87
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 238000005576 amination reaction Methods 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 238000010485 C−C bond formation reaction Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000005948 methanesulfonyloxy group Chemical group 0.000 claims description 3
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 claims description 3
- OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 192
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 123
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 96
- 239000000243 solution Substances 0.000 description 79
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 78
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 63
- 239000011541 reaction mixture Substances 0.000 description 50
- 238000003786 synthesis reaction Methods 0.000 description 48
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 47
- 230000015572 biosynthetic process Effects 0.000 description 47
- 229920006395 saturated elastomer Polymers 0.000 description 44
- 239000002904 solvent Substances 0.000 description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 42
- 239000000203 mixture Substances 0.000 description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- 239000012299 nitrogen atmosphere Substances 0.000 description 38
- 238000005160 1H NMR spectroscopy Methods 0.000 description 36
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 35
- 150000001412 amines Chemical class 0.000 description 35
- 239000012141 concentrate Substances 0.000 description 34
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 34
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 34
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 31
- 239000013078 crystal Substances 0.000 description 28
- 238000002844 melting Methods 0.000 description 26
- 230000008018 melting Effects 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 125000001309 chloro group Chemical group Cl* 0.000 description 25
- 238000004817 gas chromatography Methods 0.000 description 25
- 150000004795 grignard reagents Chemical class 0.000 description 23
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 22
- QAOWDDALFFRROB-UHFFFAOYSA-N 4-tert-butyl-n,n-diphenylaniline Chemical compound C1=CC(C(C)(C)C)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 QAOWDDALFFRROB-UHFFFAOYSA-N 0.000 description 21
- 150000002148 esters Chemical class 0.000 description 21
- 239000011780 sodium chloride Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002585 base Substances 0.000 description 19
- 229920002554 vinyl polymer Polymers 0.000 description 18
- 239000011369 resultant mixture Substances 0.000 description 17
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000007818 Grignard reagent Substances 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 14
- 229910052794 bromium Inorganic materials 0.000 description 14
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 14
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 14
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 12
- 238000004679 31P NMR spectroscopy Methods 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- KIDXWDVZFZMXGM-UHFFFAOYSA-N n-(4-methoxyphenyl)-4-methylaniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(C)C=C1 KIDXWDVZFZMXGM-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 11
- 235000019270 ammonium chloride Nutrition 0.000 description 11
- 229910052740 iodine Inorganic materials 0.000 description 11
- 239000011630 iodine Substances 0.000 description 11
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- YMSBPYCREGBACF-UHFFFAOYSA-N dicyclohexyl(1,1-diphenylprop-1-en-2-yl)phosphane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=C(C)P(C1CCCCC1)C1CCCCC1 YMSBPYCREGBACF-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 7
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 6
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 239000004210 ether based solvent Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- JUEBDJZEVFVZKZ-UHFFFAOYSA-N (2-bromo-1-phenylprop-1-enyl)benzene Chemical compound C=1C=CC=CC=1C(=C(Br)C)C1=CC=CC=C1 JUEBDJZEVFVZKZ-UHFFFAOYSA-N 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- CYGZMOQFIMJEIT-UHFFFAOYSA-N ditert-butyl(1,1-diphenylprop-1-en-2-yl)phosphane Chemical compound C=1C=CC=CC=1C(=C(P(C(C)(C)C)C(C)(C)C)C)C1=CC=CC=C1 CYGZMOQFIMJEIT-UHFFFAOYSA-N 0.000 description 5
- AJVBXLXLODZUME-UHFFFAOYSA-N ethenyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=C)C1=CC=CC=C1 AJVBXLXLODZUME-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 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 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 4
- CRPLHUSISYCLKR-UHFFFAOYSA-N 4-[1-[4-(dimethylamino)phenyl]-2-diphenylphosphanylprop-1-enyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 CRPLHUSISYCLKR-UHFFFAOYSA-N 0.000 description 4
- GGJQKIZGLHFDTN-UHFFFAOYSA-N 4-[2-bromo-1-[4-(dimethylamino)phenyl]prop-1-enyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(=C(C)Br)C1=CC=C(N(C)C)C=C1 GGJQKIZGLHFDTN-UHFFFAOYSA-N 0.000 description 4
- 0 CC.CC.CC.CC.[1*]C(C)=C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound CC.CC.CC.CC.[1*]C(C)=C(C1=CC=CC=C1)C1=CC=CC=C1 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 239000004327 boric acid Substances 0.000 description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- AKJFBIZAEPTXIL-UHFFFAOYSA-N chloro(dicyclohexyl)phosphane Chemical compound C1CCCCC1P(Cl)C1CCCCC1 AKJFBIZAEPTXIL-UHFFFAOYSA-N 0.000 description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 4
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- 150000002366 halogen compounds Chemical class 0.000 description 2
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- 238000004949 mass spectrometry Methods 0.000 description 2
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- FRQONEWDWWHIPM-UHFFFAOYSA-N n,n-dicyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)C1CCCCC1 FRQONEWDWWHIPM-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- NCCHARWOCKOHIH-UHFFFAOYSA-N n-methylbenzamide Chemical compound CNC(=O)C1=CC=CC=C1 NCCHARWOCKOHIH-UHFFFAOYSA-N 0.000 description 1
- IAMYQZXSUPCVDX-UHFFFAOYSA-N naphthalen-1-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC2=CC=CC=C12 IAMYQZXSUPCVDX-UHFFFAOYSA-N 0.000 description 1
- XDMSBAHISPQMNW-UHFFFAOYSA-N naphthalen-1-yl methanesulfonate Chemical compound C1=CC=C2C(OS(=O)(=O)C)=CC=CC2=C1 XDMSBAHISPQMNW-UHFFFAOYSA-N 0.000 description 1
- WQWUQDVFRYMMCY-UHFFFAOYSA-N naphthalen-1-yl trifluoromethanesulfonate Chemical compound C1=CC=C2C(OS(=O)(=O)C(F)(F)F)=CC=CC2=C1 WQWUQDVFRYMMCY-UHFFFAOYSA-N 0.000 description 1
- LZTBZQSQFMLGQH-UHFFFAOYSA-N naphthalen-1-yloxyboronic acid Chemical compound C1=CC=C2C(OB(O)O)=CC=CC2=C1 LZTBZQSQFMLGQH-UHFFFAOYSA-N 0.000 description 1
- CWCMQKWNHUXBFQ-UHFFFAOYSA-N naphthalen-2-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=C(C=CC=C2)C2=C1 CWCMQKWNHUXBFQ-UHFFFAOYSA-N 0.000 description 1
- MTJASVATBFDNLJ-UHFFFAOYSA-N naphthalen-2-yl methanesulfonate Chemical compound C1=CC=CC2=CC(OS(=O)(=O)C)=CC=C21 MTJASVATBFDNLJ-UHFFFAOYSA-N 0.000 description 1
- MDWRQYBWVTXIIJ-UHFFFAOYSA-N naphthalen-2-yl trifluoromethanesulfonate Chemical compound C1=CC=CC2=CC(OS(=O)(=O)C(F)(F)F)=CC=C21 MDWRQYBWVTXIIJ-UHFFFAOYSA-N 0.000 description 1
- DCMWJXWYTURQIM-UHFFFAOYSA-N naphthalen-2-yloxyboronic acid Chemical compound C1=CC=CC2=CC(OB(O)O)=CC=C21 DCMWJXWYTURQIM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- NJIBRCDYKWNVBJ-UHFFFAOYSA-N phenanthren-9-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC2=CC=CC=C2C2=CC=CC=C12 NJIBRCDYKWNVBJ-UHFFFAOYSA-N 0.000 description 1
- XTTWKFFJJPFKDT-UHFFFAOYSA-N phenanthren-9-yl methanesulfonate Chemical compound C1=CC=C2C(OS(=O)(=O)C)=CC3=CC=CC=C3C2=C1 XTTWKFFJJPFKDT-UHFFFAOYSA-N 0.000 description 1
- XKWZLWKDYGSKCD-UHFFFAOYSA-N phenanthren-9-yl trifluoromethanesulfonate Chemical compound C1=CC=C2C(OS(=O)(=O)C(F)(F)F)=CC3=CC=CC=C3C2=C1 XKWZLWKDYGSKCD-UHFFFAOYSA-N 0.000 description 1
- WXVUCMFEGJUVTN-UHFFFAOYSA-N phenyl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=C1 WXVUCMFEGJUVTN-UHFFFAOYSA-N 0.000 description 1
- DTVYDCGCCHOJMQ-UHFFFAOYSA-N phenyl phenylmethanesulfonate Chemical compound C=1C=CC=CC=1OS(=O)(=O)CC1=CC=CC=C1 DTVYDCGCCHOJMQ-UHFFFAOYSA-N 0.000 description 1
- GRJHONXDTNBDTC-UHFFFAOYSA-N phenyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=C1 GRJHONXDTNBDTC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- YXCSPMRGMHOTBN-UHFFFAOYSA-N pyridin-2-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC=N1 YXCSPMRGMHOTBN-UHFFFAOYSA-N 0.000 description 1
- CTQCXFVXBNJCTE-UHFFFAOYSA-N pyridin-2-yl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=N1 CTQCXFVXBNJCTE-UHFFFAOYSA-N 0.000 description 1
- COLRMVLTWJTLFJ-UHFFFAOYSA-N pyridin-2-yl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=N1 COLRMVLTWJTLFJ-UHFFFAOYSA-N 0.000 description 1
- UWCKDPIKJXCITH-UHFFFAOYSA-N pyridin-3-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CN=C1 UWCKDPIKJXCITH-UHFFFAOYSA-N 0.000 description 1
- ORTHFUMGNOQMKO-UHFFFAOYSA-N pyridin-3-yl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CN=C1 ORTHFUMGNOQMKO-UHFFFAOYSA-N 0.000 description 1
- ZRNDSLLIAOLRJS-UHFFFAOYSA-N pyridin-3-yl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CN=C1 ZRNDSLLIAOLRJS-UHFFFAOYSA-N 0.000 description 1
- YNCBHZIEUPGMJD-UHFFFAOYSA-N pyridin-4-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=NC=C1 YNCBHZIEUPGMJD-UHFFFAOYSA-N 0.000 description 1
- XDBMXJRKMPIPMQ-UHFFFAOYSA-N pyridin-4-yl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=NC=C1 XDBMXJRKMPIPMQ-UHFFFAOYSA-N 0.000 description 1
- CTEFYDWUNZVMNS-UHFFFAOYSA-N pyridin-4-yl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=NC=C1 CTEFYDWUNZVMNS-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- QRNSKTJWPUQIJI-UHFFFAOYSA-N thiophen-2-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CS1 QRNSKTJWPUQIJI-UHFFFAOYSA-N 0.000 description 1
- XTXBSSJREWSPDF-UHFFFAOYSA-N thiophen-2-yl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CS1 XTXBSSJREWSPDF-UHFFFAOYSA-N 0.000 description 1
- NZCUVLVBMDNUBH-UHFFFAOYSA-N thiophen-2-yl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CS1 NZCUVLVBMDNUBH-UHFFFAOYSA-N 0.000 description 1
- OHOVBSAWJQSRDD-UHFFFAOYSA-N thiophen-2-yloxyboronic acid Chemical compound OB(O)OC1=CC=CS1 OHOVBSAWJQSRDD-UHFFFAOYSA-N 0.000 description 1
- NVFKOAXVSTVVHJ-UHFFFAOYSA-N thiophen-3-yl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CSC=C1 NVFKOAXVSTVVHJ-UHFFFAOYSA-N 0.000 description 1
- KKQIJBQRIKEEPV-UHFFFAOYSA-N thiophen-3-yl methanesulfonate Chemical compound CS(=O)(=O)OC=1C=CSC=1 KKQIJBQRIKEEPV-UHFFFAOYSA-N 0.000 description 1
- AWOPORQKKLNNEA-UHFFFAOYSA-N thiophen-3-yl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC=1C=CSC=1 AWOPORQKKLNNEA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- C07F9/5013—Acyclic unsaturated phosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Definitions
- the present invention relates to a novel 2,2-(diaryl)vinylphosphine compound and a palladium-phosphine catalyst obtained by causing a palladium compound to act on the 2,2-(diaryl)vinylphosphine compound.
- the invention further relates to a process for obtaining an arylamine, a diaryl and an arylalkyne in the presence of the palladium-phosphine catalyst.
- Phosphine compounds play an extremely important role as ligands required of these catalysts.
- phosphine compounds including triphenylphosphine function to stabilize the catalyst and accelerate the reaction (see Jiro Tsuji, Palladium Reagents and Catalysts , JOHN WILEY & SONS, 1995, pp. 125-188, pp. 290-340).
- Also disclosed is a method for synthesizing a diaryl compound by the carbon-carbon bond formation reaction of an aryl compound having a leaving group with an arylboric acid compound or an arylborate ester compound see A. F. Littke et al., J. Am. Chem. Soc., 2000, 122, pp. 4020-4028, D. Z. Adriano et al., Tetrahedron Letters, 2000, 41, pp. 8199-8202, and N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, pp. 2457-2483).
- An object of the invention is to provide a novel ligand useful in various catalytic reactions. Another object of the invention is to provide a process for producing an arylamine, a diaryl and an arylalkyne important as an intermediate for medicines and agricultural chemicals and as an organic electronic material using a catalyst containing the ligand.
- the invention includes the following.
- R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents
- R 2 and R 3 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents
- R 4 , R 5 , R 6 , and R 7 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, a phenyl group which may have one or more substituents, an alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom, a benzyl group, a naphthyl group, or a hal
- a palladium-phosphine catalyst obtained by causing a palladium compound to act on the 2,2-(diaryl)vinylphosphine compound described in 1 above.
- Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents; and X 1 is a halogen atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, or a toluenesulfonyloxy group
- X 1 is a halogen atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, or a toluenesulfonyloxy group
- a process for producing a diaryl which comprises using the palladium-phosphine catalyst described in 2 or 3 above in the carbon-carbon bond formation reaction of an aryl compound represented by the following general formula (2)
- R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents.
- R 1 is preferably a hydrogen atom, a lower alkyl group having 1 to 3 carbon atoms, an alicyclic group having 6 carbon atoms, or a phenyl group.
- R 1 include a hydrogen atom; an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, pentyl, or hexyl; an alicyclic group having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may have one or more substitutents, for example, a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a lower alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a di(lower al)
- R 2 and R 3 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents.
- R 2 and R 3 may be the same and different and each is a lower alkyl group having 1 to 4 carbon atoms, an alicyclic group having 6 carbon atoms, or a phenyl group.
- R 2 and R 3 include an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, pentyl or hexyl; an alicyclic group having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may have one or more substitutents, for example, a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a lower alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a di(lower alkyl)a
- R 4 , R 5 , R 6 , and R 7 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, a phenyl group which may have one or more substituents, an alkoxy group having 1 to 6 carbon atoms, a dialkylamino group in which each alkyl has 1 to 3 carbon atoms, a halogen atom, a benzyl group, a naphthyl group, or a halogen-substituted lower alkyl group having 1 or 2 carbon atoms, provided that R 4 and R 5 taken together and/or R 6 and R 7 taken together represent a fused benzene ring, a substituted fused benzene ring, a trimethylene group, a tetramethylene group, or a methylenedioxy group; and p, q, r, and s each is 0 to 5, provided that p
- R 4 , R 5 , R 6 , and R 7 may be the same or different and each is a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a di(lower alkyl)amino group in which each alkyl has 1 or 2 carbon atoms, or a halogen atom, provided that R 4 and R 5 may and R 6 and R 7 may together represent a fused benzene ring or a methylenedioxy group.
- p, q, r, and s each preferably is 0 to 2.
- R 4 , R 5 , R 6 , and R 7 include a hydrogen atom; a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl; an alicyclic group having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may have one or more substitutents, for example, a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a lower alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a di(
- R 4 and R 5 taken together and/or R 6 and R 7 taken together represent a fused benzene ring, a substituted fused benzene ring, a trimethylene group, a tetramethylene group, or a methylenedioxy group.
- Preferred examples of the 2,2-(diaryl)vinylphosphine compound of the invention include the compounds shown in Tables 1 to 17 given below. However, the compound of the invention should not be construed as being limited to these examples.
- 2,3-benzene means that the substituents fuse with the benzene ring to form an ⁇ -naphthyl group.
- the compound (1) of the invention is produced, for example, by the process shown by the following reaction formula.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , p, q, r, and s have the same meanings as defined above;
- X is a halogen atom; and
- R is a lower alkyl group having 1 to 4 carbon atoms.
- the process comprises the following five steps as shown above.
- First Step A step in which an alcohol compound (8) is obtained by a) a method comprising the reaction of a diaryl ketone (3) with a Grignard reagent (5), or by b) a method comprising the reaction of an ester (4) with a Grignard reagent (6) and/or another Grignard reagent.
- Second Step A step in which the alcohol compound (8) is dehydrated with an acid catalyst (e.g., p-toluenesulfonic acid) to obtain a vinyl compound (9).
- an acid catalyst e.g., p-toluenesulfonic acid
- Fourth Step A step in which the dihalide compound (10) is subjected to dehydrohalogenation optionally in the presence of a base (e.g., pyridine) to obtain a vinyl halide compound (11).
- a base e.g., pyridine
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , p, q, r, and s have the same meanings as defined above;
- X is a halogen atom; and
- R in the compound (4) is a lower alkyl group having 1 to 4 carbon atoms.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 include the same groups and atoms as enumerated above.
- Examples of X include a halogen atom such as fluorine, chlorine, bromine or iodine.
- R examples include a lower alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl.
- diaryl ketone (3) and the ester (4) may be used a commercial diaryl ketone compound and a commercial ester compound (e.g., ones manufactured by Tokyo Kasei Kogyo Co., Ltd. and Nacalai Tesque, Inc.) without any treatment.
- the ketone (3) and ester (4) may be synthesized by known methods.
- the Grignard reagents (5), (6), and (7) may be ones prepared by a known method from corresponding halogen compounds on the market or from halogen compounds synthesized by a known method.
- an alcohol compound (8) is obtained by a) a method comprising the reaction of a diaryl ketone (3) with a Grignard reagent (5), or by b) a method comprising the raction of an ester (4) with a Grignard reagent (6) and/or another Grignard reagent, an ordinary Grignard reaction can be used.
- an alcohol compound (8) can be obtained by the reaction of a diaryl ketone (3) with a Grignard reagent (5).
- the amount of the Grignard reagent (5) to be used is preferably about from 0.5 to 10 mol, more preferably about from 0.8 to 3.0 mol, per mol of the diaryl ketone (3).
- reaction solvents include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran. Such a solvent may be used in an amount of preferably about from 1.0 to 80 times by volume, more preferably about from 2.0 to 30 times by volume, the amount of the diaryl ketone (3).
- ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran.
- Such a solvent may be used in an amount of preferably about from 1.0 to 80 times by volume, more preferably about from 2.0 to 30 times by volume, the amount of the diaryl ketone (3).
- Appropriate additives may be added in conducting in this reaction in order to accelerate the reaction.
- the additives include cesium trichloride, zinc chloride, zinc bromide, copper chloride, copper bromide, copper iodide, aluminum trichloride, and titanium tetrachloride. Preferred of these are cesium trichloride, copper chloride, copper bromide, and copper iodide.
- the amount of such additives to be used is preferably about from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol, per mol of the diaryl ketone (3).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas.
- the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 12 hours
- the reaction temperature is generally about from ⁇ 20 to 100° C., preferably about from 0 to 70° C.
- such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the diaryl ketone (3) and Grignard reagent (5) to be used, etc.
- an alcohol compound (8) can be obtained by the reaction of an ester (4) with a Grignard reagent (6) and/or another Grignard reagent.
- the amount of the Grignard reagents (6) and (7) to be used is preferably about from 1.0 to 10 mol, more preferably about from 1.6 to 4.8 mol, per mol of the ester (4).
- reaction solvents include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran. Such a solvent may be used in an amount of preferably about from 1.0 to 50 times by volume, more preferably about from 4.0 to 10 times by volume, the amount of the ester (4).
- ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran.
- Such a solvent may be used in an amount of preferably about from 1.0 to 50 times by volume, more preferably about from 4.0 to 10 times by volume, the amount of the ester (4).
- Appropriate additives may be added in conducting the reaction in order to accelerate the reaction.
- the additives include cesium trichloride, zinc chloride, zinc bromide, copper chloride, copper bromide, copper iodide, aluminum trichloride, and titanium tetrachloride. Preferred of these are cesium trichloride, copper chloride, copper bromide, and copper iodide.
- the amount of such additives to be used is preferably about from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol, per mol of the ester (4).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas.
- the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 8 hours
- the reaction temperature is generally about from ⁇ 20 to 100° C., preferably about from 0 to 70° C.
- such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the ester (4) and Grignard reagents (6) and (7) to be used, etc.
- Examples of the acid catalyst include hydrochloric acid, sulfuric acid, camphorsulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Preferred of these is p-toluenesulfonic acid.
- the amount of the acid catalyst to be used is preferably about from 0.0001 to 0.2 mol, more preferably about from 0.005 to 0.05 mol, per mol of the alcohol compound (8).
- reaction solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are benzene, toluene, and xylene.
- Such a solvent may be used in an amount of preferably about from 1.0 to 50 times by volume, more preferably about from 2.0 to 20 times by volume, the amount of the alcohol compound (8).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas.
- the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 8 hours
- the reaction temperature is generally about from 20 to 180° C., preferably about from 70 to 140° C.
- such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the alcohol compound (8) and acid catalyst to be used, etc.
- halogen examples include chlorine, bromine, and iodine, and bromine is preferred.
- the amount of the halogen to be used is preferably about from 0.5 to 2.0 mol, more preferably about from 0.8 to 1.2 mol, per mol of the vinyl compound (9).
- reaction solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane; and halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dibromomethane, and dibromoethane. Preferred of these are halogenated solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride.
- a solvent may be used in an amount of preferably about from 0.2 to 50 times by volume, more preferably about from 0.5 to 20 times by volume, the amount of the vinyl compound (9).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas.
- the reaction time is generally about from 10 minutes to 24 hours, preferably about from 30 minutes to 8 hours
- the reaction temperature is generally about from ⁇ 60 to 100° C., preferably about from ⁇ 30 to 50° C.
- such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the vinyl compound (9) and halogen to be used, etc.
- Examples of the base include triethylamine, dimethylaniline, diethylaniline, pyridine, picoline, lutidine, ethylpyridine, quinoline, and isoquinoline. Preferred of these is pyridine.
- Such a base may be used in an amount of preferably about from 0.5 to 30 mol, more preferably about from 1.0 to 10 mol, per mol of the dihalide compound (10).
- reaction solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are benzene, toluene, and xylene.
- Such a solvent may be used in an amount of preferably about from 0.2 to 30 times by volume, more preferably about from 0.5 to 10 times by volume, the amount of the dihalide compound (10).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas.
- the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 16 hours
- the reaction temperature is generally about from 20 to 140° C., preferably about from 60 to 110° C.
- such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the dihalide compound (10) and base to be used, etc.
- the amount of the lithium metal, alkyllithium, or magnesium metal to be used is preferably about from 0.5 to 3.0 mol, more preferably about from 0.8 to 1.5 mol, per mol of the vinyl halide compound (11).
- the amount of the halogenated phosphorus compound (12) to be used is preferably about from 0.5 to 3.0 mol, more preferably about from 0.7 to 1.5 mol, per mol of the vinyl halide compound (11).
- reaction solvents include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran. Such a solvent may be used in an amount of preferably about from 1.0 to 50 times by volume, more preferably about from 4.0 to 30 times by volume, the amount of the vinyl halide compound (11).
- Appropriate additives may be added in conducting in this reaction in order to accelerate the reaction.
- the additives include copper chloride, copper bromide, copper iodide, copper triflate, copper cyanide, a copper iodide-dimethyl sulfide complex, a copper iodide-triphenylphosphine complex, and a copper iodide-tributylphosphine complex.
- Preferred of these are copper chloride, copper bromide, and copper iodide.
- the amount of such additives to be used is preferably about from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol, per mol of the vinyl halide compound (11).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas.
- the reaction time is generally about from 10 minutes to 40 hours, preferably about from 30 minutes to 24 hours
- the reaction temperature is generally about from ⁇ 100 to 120° C., preferably about from ⁇ 80 to 80° C.
- such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the vinyl halide compound (11) and phosphorus halide compound (12) to be used, etc.
- the compound (1) of the invention serves as a ligand to form a palladium-phosphine catalyst in cooperation with a palladium compound.
- the palladium compound to be used as a catalyst precursor for forming the palladium-phosphine catalyst is not particularly limited. However, salts or complexes of palladium having a valence of 4, 2, or 0 are mainly used.
- the palladium compound include compounds of tetravalent palladium, such as sodium hexachloropalladate(IV) tetrahydrate and potassium hexachloropalladate(IV), compounds of bivalent palladium, such as palladium(II) chloride, palladium(II) bromide, palladium(II) acetate, palladium(II) acetylacetonate, dichlorobis(benzonitrile)palladium(II), dichlorobis(acetonitrile)palladium(II), dichlorobis(triphenylphosphine)palladium(II), dichlorotetraamminepalladium(II), dichloro(cycloocta-1,5-diene)palladium(II), palladium(II) trifluoroacetate, and ⁇ -allylpalladium(II) chloride diner, and compounds of zero-valent palladium, such as
- the palladium-phosphine catalyst obtained by causing a palladium compound to act on the novel 2,2-(diaryl)vinylphosphine compound (1) can be prepared, for example, by reacting the 2,2-(diaryl)vinylphosphine compound (1) with ⁇ -allylpalladium(II) chloride dimer according to the method described in Y. Uozumi and T. Hayashi, J. Am. Chem. Soc., 1991, Vol. 113, p.9887.
- the palladium-phosphine catalyst thus obtained by causing a palladium compound to act on the novel 2,2-(diaryl)vinylphosphine compound (1) of the invention can be used as a catalyst in the amination reaction or the carbon-carbon bond formation reaction in which an aryl compound having a leaving group is reacted with this reaction substance (an amine compound, an arylboric acid compound, an arylborate ester compound, or an alkyne compound) in the presence of a base.
- Ar is an aryl group which may have one or more substituents or a heteroaryl group which may have one or more substituents; and X 1 is a halogen atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, or a toluenesulfonyloxy group).
- the aryl compound (2) to be used in the invention is not particularly limited. Examples thereof include aryl bromides, aryl chlorides, aryl iodides, aryl fluorides, aryl trifluoromethanesulfonate, aryl methanesulfonate, aryl p-toluenesulfonate, and aryl halides having two or more halogen atoms.
- aryl compound (2) include: aryl bromides such as bromobenzene, o-bromoanisole, m-bromoanisole, p-bromoanisole, o-bromotoluene, m-bromotoluene, p-bromotoluene, o-bromophenol, m-bromophenol, p-bromophenol, 2-bromobenzotrifluoride, 3-bromobenzotrifluoride, 4-bromobenzotrifluoride, 1-bromo-2,4-dimethoxybenzene, 1-bromo-2,5-dimethoxybenzene, 2-bromophenethyl alcohol, 3-bromophenethyl alcohol, 4-bromophenethyl alcohol, 5-bromo-1,2,4-trimethylbenzene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xy
- aryl chlorides such as chlorobenzene, o-chloroanisole, m-chloroanisole, p-chloroanisole, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride, 4-chlorobenzotrifluoride, 1-chloro-2,4-dimethoxybenzene, 1-chloro-2,5-dimethoxybenzene, 2-chlorophenethyl alcohol, 3-chlorophenethyl alcohol, 4-chlorophenethyl alcohol, 5-chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-
- aryl iodides such as iodobenzene, o-iodoanisole, m-iodoanisole, p-iodoanisole, o-iodotoluene, m-iodotoluene, p-iodotoluene, o-iodophenol, m-iodophenol, p-iodophenol, 2-iodobenzotrifluoride, 3-iodobenzotrifluoride, 4-iodobenzotrifluoride, 1-iodo-2,4-dimethoxybenzene, 1-iodo-2,5-dimethoxybenzene, 2-iodophenethyl alcohol, 3-iodophenethyl alcohol, 4-iodophenethyl alcohol, 5-iodo-1,2,4-trimethylbenzene, 2-iodo-m-xylene, 2-iodo
- aryl fluorides such as fluorobenzene, o-fluoroanisole, m-fluoroanisole, p-fluoroanisole, o-fluorotoluene, m-fluorotoluene, p-fluorotoluene, o-fluorophenol, m-fluorophenol, p-fluorophenol, 2-fluorobenzotrifluoride, 3-fluorobenzotrifluoride, 4-fluorobenzotrifluoride, 1-fluoro-2,4-dimethoxybenzene, 1-fluoro-2,5-dimethoxybenzene, 2-fluorophenethyl alcohol, 3-fluorophenethyl alcohol, 4-fluorophenethyl alcohol, 5-fluoro-1,2,4-trimethylbenzene, 2-fluoro-m-xylene, 2-fluoro-p-xylene, 3-fluoro-o-xylene, 4-fluoro-o-o
- aryl trifluoromethanesulfonate such as trifluoromethanesulfonyloxybenzene, o-trifluoromethanesulfonyloxyanisole, m-trifluoromethanesulfonyloxyanisole, p-trifluoromethanesulfonyloxyanisole, o-trifluoromethanesulfonyloxytoluene, m-trifluoromethanesulfonyloxytoluene, p-trifluoromethanesulfonyloxytoluene, p-trifluoromethanesulfonyloxyphenol, o-trifluoromethanesulfonyloxyphenol, p-trifluoromethanesulfonyloxyphenol, 2-trifluoromethanesulfonyloxybenzotrifluoride, 3-trifluoromethanesulfonyloxybenzotrifluoride
- aryl methanesulfonate such as methanesulfonyloxybenzene, o-methanesulfonyloxyanisole, m-methanesulfonyloxyanisole, p-methanesulfonyloxyanisole, o-methanesulfonyloxytoluene, m-methanesulfonyloxytoluene, p-methanesulfonyloxytoluene, o-methanesulfonyloxyphenol, m-methanesulfonyloxyphenol, p-methanesulfonyloxyphenol, 2-methanesulfonyloxybenzotrifluoride, 3-methanesulfonyloxybenzotrifluoride, 4-methanesulfonyloxybenzotrifluoride, 1-methanesulfonyloxy-2,4-dimethoxybenz
- aryl p-toluenesulfonate such as p-toluenesulfonyloxybenzene, o-(p-toluenesulfonyloxy)anisole, m-(p-toluenesulfonyloxy)anisole, p-(p-toluenesulfonyloxy)anisole, o-(p-toluenesulfonyloxy)toluene, m-(p-toluenesulfonyloxy)toluene, p-(p-toluenesulfonyloxy)toluene, o-(p-toluenesulfonyloxy)phenol, m-(p-toluenesulfonyloxy)phenol, p-(p-toluenesulfonyloxy)phenol, 2-(p-toluenesulfon
- Examples of the amine compound to be used in the invention include primary amines, secondary amines, imines, and amides.
- the primary amines are not particularly limited. Examples thereof include aliphatic primary amines such as ethylamine, propylamine, butylamine, isobutylamine, tert-butylamine, pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, and octylamine; and aromatic primary amines such as aniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-anisidine, m-anisidine, p-anisidine, o-toluidine, m-toluidine, p-toluidine, 2-naphthylamine, 2-aminobiphenyl, 4-aminobiphenyl, 3,4-methylenedioxyaniline, m-xylidine, and p-xylidine.
- aliphatic primary amines such as ethy
- the secondary amines are not particularly limited. Examples thereof include cyclic secondary amines such as piperazine, 2-methylpiperazine, homopiperazine, N-methylhomopiperazine, 2,6-dimethylpiperazine, N-methylpiperazine, N-ethylpiperazine, N-ethoxycarbonylpiperazine, N-benzylpiperazine, morpholine, 2,6-dimethylmorpholine, piperidine, 2,6-dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 4-piperidone, pyrrolidine, 2,5-dimethylpyrrolidine, carbazole, indole, and indoline; and noncyclic secondary amines such as dimethylamine, diethylamine, and other noncyclic secondary amines which may have one or more substituents on the aromatic ring(s), such as N-methylaniline, N-ethylaniline, N-
- the imines are not particularly limited. Examples thereof include benzophenonimine and 4,4′-dimethoxybenzophenoneimine.
- the amides are not particularly limited. Examples thereof include 2-azetidinone ( ⁇ -propiolactam), ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, acetamide, propionamide, cyclohexanecarboxamide, benzamide, N-methylformamide, N-methylacetamide, N-ethylacetamide, N-methylcyclohexanecarboxamide, and N-methylbenzamide.
- 2-azetidinone ⁇ -propiolactam
- ⁇ -butyrolactam ⁇ -valerolactam
- ⁇ -caprolactam acetamide
- propionamide cyclohexanecarboxamide
- benzamide N-methylformamide
- N-methylacetamide N-ethylacetamide
- N-methylcyclohexanecarboxamide N-methylbenzamide
- arylboric acid compounds and the arylborate ester compounds to be used in the invention are not particularly limited. Examples thereof include phenylboric acid, 4-methylphenylboric acid, 2-thienylboric acid, 2-furylboric acid, 2,3,4,5,6-pentafluorophenylboric acid, 2-fluorophenylboric acid, 3-fluorophnylboric acid, 4-fluorophenylboric acid, 2-chlorophenylboric acid, 3-chlorophenylboric acid, 4-chlorophenylboric acid, 2-bromophenylboric acid, 3-bromophenylboric acid, 4-bromophenylboric acid, 2-iodophenylboric acid, 3-iodophenylboric acid, 4-iodophenylboric acid, 2,4-difluorophenylboric acid, 2,5-difluorophenylboric acid, 2,
- the arylalkyne compounds to be used in the invention are not particularly limited. Examples thereof include acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, phenylacetylene, 2-propyn-1-ol, 3-butyn-1-ol, 2-methyl-3-butyn-2-ol, 1-ethynyl-cyclohexanol, and trimethylsilylacetylene.
- the amine compound may be used so as to be present in the reaction system in an amount of from 0.1 to 50 mol per mol of the aryl compound (2) or in an amount of from 0.1 to 50 mol per mol of the leaving group on the ring structure of the aryl compound (2).
- the amine compound is preferably used so as to be present in the reaction system in an amount of from 0.2 to 30 mol per mol of the aryl compound (2) or in an amount of from 0.2 to 60 mol per mol of the leaving group on the ring structure of the aryl compound (2).
- the aryl boric acid compound or aryl borate ester compound may be used so as to be present in the reaction system in an amount of from 0.1 to 50 mol per mol of the aryl compound (2) or in an amount of from 0.1 to 50 mol per of the leaving group on the ring structure of the aryl compound (2).
- the aryl boric acid compound or aryl borate ester compound is preferably used so as to be present in the reaction system in an amount of from 0.2 to 30 mol per mol of the aryl compound (2) or in an amount of from 0.2 to 60 mol per mol of the leaving group on the ring structure of the aryl compound (2).
- the alkyne compound may be used so as to be present in the reaction system in an amount of from 0.1 to 50 mol per mol of the aryl compound (2) or in an amount of from 0.1 to 50 mol per of the leaving group on the ring structure of the aryl compound (2).
- the aryl boric acid compound or aryl borate ester compound is preferably used so as to be present in the reaction system in an amount of from 0.2 to 30 mol per mol of the aryl compound (2) or in an amount of from 0.2 to 60 mol per mol of the leaving group on the ring structure of the aryl compound (2).
- the base to be used in the invention is not particularly limited, and may be selected from inorganic bases and/or organic bases.
- Preferred examples thereof include alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride; alkali metal or alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, potassium phenoxide, lithium phenoxide, lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide; alkali metal phosphates such as lithium phosphate, potassium phosphate, and sodium phosphate; and tertiary amines such as triethylamine, triprop
- such as a base may be supplied to the reaction system by in situ preparing it from an alkali metal, alkali metal hydride, alkali metal hydroxide, or alkali metal phosphate and an alcohol.
- the amount of the base to be used is preferably at least 0.5 mol per mol of the leaving group of the aryl compound (2). If the amount of the base is smaller than 0.5 mol, there are cases where the yield of an arylamine, a diaryl and an arylalkyne is reduced. Even when the base is added in large excess, the yield of an arylamine, a diaryl and an arylalkyne remains unchanged, resulting only in a complicated post-treatment after completion of the reaction. Consequently, the amount of the base to be added is more preferably in the range of from 1 to 5 mol.
- the reaction according to the invention is usually conducted in the presence of an inert solvent.
- the solvent to be used is not particularly limited as long as it does not considerably inhibit the reaction. Examples thereof include aliphatic organic solvents such as pentane, hexane, heptane, and octane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; aromatic organic solvents such as benzene, toluene, and xylene; ether type organic solvents such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, and dioxolane; and acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric triamide.
- aromatic organic solvents such as benzene, toluene, and xylene and ether type organic solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane.
- the catalyst produces the same results when used by any of the following methods: a) a method in which a palladium compound; a base; an amine compound, an arylboric acid compound, an arylborate ester compound, or an alkyne compound; an aryl compound havng a leaving group; and the 2,2-(diaryl)vinylphosphine compound (1), which each has been described above, are charged into a reactor simultaneously; b) a method in which a palladium compound, the reaction substrate, and the 2,2-(diaryl)vinylphosphine compound (1) are separately charged into a reactor in the presence of a base; c) a method in which a palladium compound is mixed beforehand with the 2,2-(diaryl)vinylphosphine compound (1) in a reaction system to prepare a catalyst, and an aryl compound having a leaving group is then added to the reaction system in the presence of a base; and d) a method in which a palladium
- the amount of the palladium compound to be used for the amination reaction or the carbon-carbon bond formation reaction is generally from 0.001 to 20 mol %, preferably from 0.01 to 5 mol %, based on this reaction substance (the amine compound, the arylboric acid compound, the arylborate ester compound, or the alkyne compound).
- the amount of the 2,2-(diaryl)vinylphosphine compound to be used for this reaction is generally from 0.1 to 10 times by mol, preferably from 1 to 5 times by mol, the amount of the palladium compound.
- a palladium compound and the 2,2-(diaryl)vinylphosphine compound (1) are indispensable.
- the amination reaction or the carbon-carbon bond formation reaction according to the invention may be conducted at ordinary pressure under an inert gas atmosphere such as nitrogen or argon, or may be conducted at an elevated pressure.
- the reaction according to the invention may be conducted at a temperature of generally from 10 to 300° C, preferably from 20 to 200° C.
- reaction time in the invention varies depending on the amounts of the aryl compound (2), this reaction substance (the amine compound, the arylboric acid compound, the arylborate ester compound, or the alkyne compound), base, palladium compound, and 2,2-(diaryl)vinylphosphine compound (1) and on the reaction temperature, it may be selected in the range of from several minutes to 72 hours.
- the reaction mixture is treated in an ordinary way, whereby the target compound can be obtained.
- the novel 2,2-(diaryl)vinylphosphine compound of the invention when used together with a palladium compound, serves as the catalyst of an amination reaction or a carbon-carbon bond formation reaction to show excellent performances.
- this catalyst is used in the amination reaction or the carbon-carbon formation reaction of an aryl compound having a leaving group, an arylamine, a diaryl or an arylalkyne can be efficiently produced in a shorter time period than in the amination reaction or the carbon-carbon bond formation reaction with any conventional amination catalyst or any conventional carbon-carbon bond formation reaction catalyst. It is hence an excellent catalyst for industrial use.
- Mass spectrometer M-80 Ionization voltage, 20 eV (manufactured by Hitachi Ltd.)
- the organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure.
- the concentrate was recrystallized from ethanol to obtain 1.08 g (60%) of the target compound as white crystals.
- the organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure.
- the concentrate was recrystallized from ethanol to obtain 8.80 g (72%) of the target compound as white crystals.
- the concentrate was dissolved in 150 mL of toluene, and 0.1 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. This concentrate was purified by column chromatography to obtain 13.6 g (65%) of light-yellow crystals.
- the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure.
- the concentrate was purified by column chromatography and then crystallized from methanol to obtain 12.0 g (69%) of the target compound as green-yellow crystals.
- the resultant mixture was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure.
- the concentrate was recrystallized twice from hexane/ethanol to obtain 1.9 g (60%) of the target compound as white crystals.
- the resultant solution was subjected to azeotropic dehydration for 2 hours with toluene refluxing. After being cooled, the reaction mixture was washed with 2% aqueous sodium carbonate solution and water and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by distillation to obtain 174 g (97%) of the target compound.
- the reaction mixture was washed with 5% hydrochloric acid and water, subsequently dried with anhydrous sodium sulfate, and then concentrated under reduced pressure.
- the resultant concentrate was distilled and then recrystallized from methanol to obtain 126 g (81%) of the target compound as white crystals.
- Example 1 (3) The same procedure as in Example 1 (3) was conducted, except that 1.30 g (5.00 mmol) of 2-bromo-1,1-diphenylethylene was used in place of 2-bromo-1,1-diphenylpropene. Thus, 1.03 g (57%) of the target compound was obtained as white crystals.
- the resultant reaction mixture was washed with 0.1 M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure.
- the concentrate was dissolved in 50 mL of toluene, and 0.05 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted for 2 hours with toluene refluxing.
- reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 8.81 g (79%) of a transparent oily substance.
- the organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure.
- the concentrate was recrystallized from ethanol and toluene to obtain 0.72 g (43%) of the target compound as white crystals.
- the concentrate was dissolved in 46 mL of toluene, and 0.18 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted for 2 hours with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 12.5 g (98%) of a transparent oily substance.
- the crystals yielded were taken out by filtration and dissolved in 40 mL of ethyl acetate.
- the resultant solution was washed with 28% ammonia water and an aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure.
- the concentrate was recrystallized from ethanol to obtain 1.34 g (59%) of the target compound as white crystals.
- the resultant mixture was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure.
- the concentrate was recrystallized from ethanol to obtain 1.45 g (66%) of the target compound as white crystals.
- the mixture was extracted with ethyl acetate, and the resultant organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure.
- the concentrate was purified by column chromatography to obtain 3.12 g (78%) of the target compound as a light-yellow oily substance.
- Example 12 The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 2.3 mg (0.25 mol % based on the amine) of ( ⁇ -allyl)palladium chloride.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- Example 12 The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 4.8 mg (0.25 mol % based on the amine) of dichlorobis(benzonitrile)palladium.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- Example 12 The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 3.8 mg (0.25 mol % based on the amine) of palladium acetylacetonate.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- Example 12 The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 14.4 mg (0.25 mol % based on the amine) of tetrakis(triphenylphosphine)palladium.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- Example 12 The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 5.7 mg (0.25 mol % based on the amine) of tris(dibenzylideneacetone)dipalladium.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 20.7 mg (1.0 mol % based on the amine) of the 1,1-bis(4-dimethylaminophenyl)-2-(diphenylphosphino)propene obtained in Example 4.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 18.9 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(diphenylphosphino)propene obtained in Example 1.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 19.5 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2 and that the reaction time was changed to 3 hours.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine and palladium acetate were replaced with 19.5 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(di-t-butylphosphino)propene obtained in Example 3 and 2.3 mg (1.0 mol % based on the amine) of ( ⁇ -allyl)palladium chloride, respectively, and that the reaction time was changed to 3 hours.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 18.2 mg (1.0 mol % based on the amine) of the 2,2-diphenyl-1-(diphenylphosphino)ethylene obtained in Example 7.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 23.8 mg (1.0 mol % based on the amine) of the 1,1-bis(4-dimethylaminophenyl)-2-(dicyclohexylphosphino)propene obtained in Example 5 and that the reaction time was changed to 3 hours.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 21.2 mg (1.0 mol % based on the amine) of the 1,1-bis(4-dimethylaminophenyl)-2-(di-t-butylphosphino)propene obtained in Example 6.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 20.9 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)-3-methylbutene obtained in Example 8.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 22.6 mg (1.0 mol % based on the amine) of the 1,2,2-triphenyl-1-(dicyclohexylphosphino)ethylene obtained in Example 9.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 15.2 mg (1.0 mol % based on the amine) of tris(o-tolyl)phosphine.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Example 12 The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 14.0 mg (1.0 mol % based on the amine) of triscyclohexylphosphine.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- Table 19 shows that when the 2,2-(diaryl)vinylphosphine compounds according to the invention (Examples 18 to 26) were used to conduct an amination reaction, the target arylamine could be obtained in high yield.
- triphenylphosphine Comparative Example 1
- tris(o-tolyl)phosphine Comparative Example 2
- BINAP Comparative Example 3
- triscyclohexylphosphine Comparative Example 4
- vinyldiphenylphosphine Comparative Example 5
- the yield of the target arylamine was as low as 37% at the most.
- Example 27 The same procedure as in Example 27 was conducted, except that the phosphine was replaced with 4.2 mg (1.0 mol % based on the amine) of vinyldiphenylphosphine.
- the amount of N-p-methoxyphenyl-N-p-tolylamine as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield was found to be 5%. The results obtained are shown in Table 20.
- Example 28 The same procedure as in Example 28 was conducted, except that the phosphine was replaced with 4.2 mg (1.0 mol % based on the amine) of vinyldiphenylphosphine.
- the amount of N-p-methoxyphenyl-N-p-tolylamine as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield was found to be 5%.
- the results obtained are shown in Table 20. TABLE 20 Aryl Yield Example compound Amine Product (%) Example 27 82 Comparative Example 6 5 Example 28 89 Comparative Example 7 5 Example 29 61 Example 30 81 Example 31 65 Example 32 50
- Table 20 shows that when the 2,2-(diaryl)vinylphosphine compound according to the invention (Examples 27 to 32) was used to conduct amination reactions, the target arylamines could be obtained in high yields. In contrast, when vinyldiphenylphosphine (Comparative Examples 6 and 7) was used as a phosphine in place of the 2,2-(diaryl)vinylphosphine compound of the invention to conduct amination reactions, the yield of the target arylamines was as low as 5%.
- 2,2-(diaryl)vinylphosphine compound according the invention is an exceedingly useful phosphine in completing the amination reaction of the invention.
- Example 33 The same procedure as in Example 12 was conducted, except that the palladium compound and phosphine were replaced with the [1,1-diphenyl-2-(di-tert-butylphosphino)propene]( ⁇ -allyl)palladium chloride (palladium-phosphine catalyst) obtained in Example 33.
- the amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield of the target compound was 90%.
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Abstract
Description
- The present invention relates to a novel 2,2-(diaryl)vinylphosphine compound and a palladium-phosphine catalyst obtained by causing a palladium compound to act on the 2,2-(diaryl)vinylphosphine compound. The invention further relates to a process for obtaining an arylamine, a diaryl and an arylalkyne in the presence of the palladium-phosphine catalyst.
- Many transition metal complexes have conventionally been used as catalysts for organic synthesis reactions. Phosphine compounds play an extremely important role as ligands required of these catalysts. For example, in Tsuji-Trost reaction, in which an allyl compound reacts with a nucleating agent with the aid of a palladium catalyst, phosphine compounds including triphenylphosphine function to stabilize the catalyst and accelerate the reaction (see Jiro Tsuji,Palladium Reagents and Catalysts, JOHN WILEY & SONS, 1995, pp. 125-188, pp. 290-340).
- In recent years, S. L. Buchwald et al. disclosed a method for synthesizing an arylamine by the amination reaction of an aryl compound having a leaving group (see U.S. Pat. No. 5,576,460, International Publication 2000/02887, and S. L. Buchwald et al.,J. Org. Chem., 2000, 65, pp. 1158-1174). Also disclosed is a process for arylamine production which is characterized by using a catalyst comprising a trialkylphosphine and a palladium compound (see JP-A-10-139742). (The term “JP-A” as used herein means an “unexamined published Japanese patent application”.)
- Also disclosed is a method for synthesizing a diaryl compound by the carbon-carbon bond formation reaction of an aryl compound having a leaving group with an arylboric acid compound or an arylborate ester compound (see A. F. Littke et al.,J. Am. Chem. Soc., 2000, 122, pp. 4020-4028, D. Z. Adriano et al., Tetrahedron Letters, 2000, 41, pp. 8199-8202, and N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, pp. 2457-2483).
- Furthermore disclosed is a method for synthesizing an arylalkyne by the carbon-carbon bond formation reaction of an aryl compound having a leaving group with an alkyne compound (see H-F. Chow et al.,J. Org. Chem., 2001, 66, pp. 1910-1913, Y. Nishihara et al., J. Org. Chem., 2000, 65, pp. 1780-1787, J-F. Nguefack et al., Tetrahedron Letters, 1996, 37, pp. 5527-5530, and N. A. Bumagin et al., Tetrahedron Letters, 1996, 37, pp. 897-900).
- Although it is important to constitute an optimal catalyst according to the intended reaction or the substrate to be reacted, there can be a variety of complicated combinations of catalyst components, i.e., a metal and a phosphine ligand. Consequently, there are cases where even when phosphine ligands which have been developed so far are used, the catalysts are insufficient in catalytic activity, etc. and hence pose a problem when subjected to practical use in industrial reactions. It is therefore important to develop a novel phosphine ligand.
- An object of the invention is to provide a novel ligand useful in various catalytic reactions. Another object of the invention is to provide a process for producing an arylamine, a diaryl and an arylalkyne important as an intermediate for medicines and agricultural chemicals and as an organic electronic material using a catalyst containing the ligand.
- In order to achieve the above objects, the present inventors made extensive studies. As a result, it has been found that a novel 2,2-(diaryl)vinylphosphine compound. Furthermore, it has been found that a catalyst prepared from this 2,2-(diaryl)vinylphosphine compound and a palladium compound is effective in the amination reaction of an aryl compound having a leaving group, the carbon-carbon bond formation reaction of an aryl compound having a leaving group with an arylboric acid compound or an arylborate ester compound, and the carbon-carbon bond formation reaction of an aryl compound having a leaving group with an alkyne compound, and enables an arylamine, a diaryl and an arylalkyne to be produced efficiently in a short time period. The invention has been completed based on this finding.
- The invention includes the following.
-
- (wherein R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents; R2 and R3 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents; R4, R5, R6, and R7 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, a phenyl group which may have one or more substituents, an alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom, a benzyl group, a naphthyl group, or a halogen-substituted lower alkyl group having 1 or 2 carbon atoms, provided that R4 and R5 taken together and/or R6 and R7 taken together may represent a fused benzene ring, a substituted fused benzene ring, a trimethylene group, a tetramethylene group, or a methylenedioxy group; and p, q, r, and s each is 0 to 5, provided that p+q and r+s each is in the range of from 0 to 5).
- 2. A palladium-phosphine catalyst obtained by causing a palladium compound to act on the 2,2-(diaryl)vinylphosphine compound described in 1 above.
- 3. The palladium-phosphine catalyst described in 2 above wherein the palladium compound is a salt or complex of palladium having a valence of 4, 2, or 0.
- 4. A process for producing an arylamine which comprises using the palladium-phosphine catalyst described in 2 or 3 above in the amination reaction of an aryl compound represented by the following general formula (2):
- ArX1 (2)
- (wherein Ar is an aryl group which may have one or more substituents, or a heteroaryl group which may have one or more substituents; and X1 is a halogen atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, or a toluenesulfonyloxy group) with an amine compound in the presence of a base.
- 5. A process for producing a diaryl which comprises using the palladium-phosphine catalyst described in 2 or 3 above in the carbon-carbon bond formation reaction of an aryl compound represented by the following general formula (2)
- ArX1 (2)
- (wherein Ar and X1 have the same meanings as defined above with an arylboric acid compound or an arylborate ester compound in the presence of a base).
- 6. A process for producing an arylalkyne which comprises using the palladium-phosphine catalyst described in 2 or 3 above in the carbon-carbon bond formation reaction of an aryl compound represented by the following general formula (2)
- ArX1 (2)
- (wherein Ar and X1 have the same meanings as defined above with an alkyne compound in the presence of a base).
- The invention will be explained below in detail.
- In the compound (1) of the invention, R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents. R1 is preferably a hydrogen atom, a lower alkyl group having 1 to 3 carbon atoms, an alicyclic group having 6 carbon atoms, or a phenyl group.
- Specific examples of R1 include a hydrogen atom; an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, pentyl, or hexyl; an alicyclic group having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may have one or more substitutents, for example, a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a lower alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a di(lower alkyl)amino group in which each alkyl has 1 to 3 carbon atoms, such as dimethylamino, diethylamino or dipropylamino, or a halogen atom such as fluorine, chlorine, bromine or iodine.
- R2 and R3 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, or a phenyl group which may have one or more substituents. Preferably, R2 and R3 may be the same and different and each is a lower alkyl group having 1 to 4 carbon atoms, an alicyclic group having 6 carbon atoms, or a phenyl group.
- Specific examples of R2 and R3 include an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, pentyl or hexyl; an alicyclic group having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may have one or more substitutents, for example, a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a lower alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a di(lower alkyl)amino group in which each alkyl has 1 to 3 carbon atoms, such as dimethylamino, diethylamino or dipropylamino, or a halogen atom such as fluorine, chlorine, bromine or iodine.
- R4, R5, R6, and R7 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, a phenyl group which may have one or more substituents, an alkoxy group having 1 to 6 carbon atoms, a dialkylamino group in which each alkyl has 1 to 3 carbon atoms, a halogen atom, a benzyl group, a naphthyl group, or a halogen-substituted lower alkyl group having 1 or 2 carbon atoms, provided that R4 and R5 taken together and/or R6 and R7 taken together represent a fused benzene ring, a substituted fused benzene ring, a trimethylene group, a tetramethylene group, or a methylenedioxy group; and p, q, r, and s each is 0 to 5, provided that p+q and r+s each is in the range of from 0 to 5. Preferably, R4, R5, R6, and R7 may be the same or different and each is a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a di(lower alkyl)amino group in which each alkyl has 1 or 2 carbon atoms, or a halogen atom, provided that R4 and R5 may and R6 and R7 may together represent a fused benzene ring or a methylenedioxy group. Furthermore, p, q, r, and s each preferably is 0 to 2.
- Specific examples of R4, R5, R6, and R7 include a hydrogen atom; a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl; an alicyclic group having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may have one or more substitutents, for example, a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a lower alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a di(lower alkyl)amino group in which each alkyl has 1 to 3 carbon atoms, such as dimethylamino, diethylamino or dipropylamino, or a halogen atom such as fluorine, chlorine, bromine or iodine; a lower alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, or butoxy; a di(lower alkyl)amino group in which each alkyl has 1 to 3 carbon atoms, such as dimethylamino, diethylamino or dipropylamino; a halogen atom such as fluorine, chlorine, bromine or iodine; a benzyl group; a naphthyl group; or a halogen-substituted lower alkyl group having 1 or 2 carbon atoms, such as trifluoromethyl, trichloromethyl, or tribromomethyl.
- Furthermore, R4 and R5 taken together and/or R6 and R7 taken together represent a fused benzene ring, a substituted fused benzene ring, a trimethylene group, a tetramethylene group, or a methylenedioxy group.
- Preferred examples of the 2,2-(diaryl)vinylphosphine compound of the invention, which is represented by general formula (1) described above, include the compounds shown in Tables 1 to 17 given below. However, the compound of the invention should not be construed as being limited to these examples.
- The abbreviations used in Tables 1 to 17 have the following meanings, respectively. The abbreviations used in compound names appearing hereinafter have the same meanings. The numeral preceding the abbreviation or symbol for a substituent indicates the position of the substituent on the phenyl group (for example, 4-Me means a methyl substituent bonded to the 4-position carbon atom of the phenyl group).
- Me methyl
- Et ethyl
- nPr n-propyl
- iPr isopropyl
- nBu n-butyl
- iBu isobutyl
- tBu tert-butyl
- MeO methoxy
- EtO ethoxy
- F fluorine atom
- Cl chlorine atom
- Br bromine atom
- Me2N dimethylamino
- Et2N diethylamino
- CyPe cyclopentyl
- CyHx cyclohexyl
- Ph phenyl
- p-Tol p-tolyl
- Xy 2,4-xylyl
- 2,3-benzene means that the substituents fuse with the benzene ring to form an α-naphthyl group.
- 3,4-benzene means that the substituents fuse with the benzene ring to form a β-naphthyl group.
TABLE 1 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 1 H Me Me 0 — 0 — 0 — 0 — 2 H Et Et 0 — 0 — 0 — 0 — 3 H nPr nPr 0 — 0 — 0 — 0 — 4 H iPr iPr 0 — 0 — 0 — 0 — 5 H nBu nBu 0 — 0 — 0 — 0 — 6 H iBu iBu 0 — 0 — 0 — 0 — 7 H tBu tBu 0 — 0 — 0 — 0 — 8 H CyPe CyPe 0 — 0 — 0 — 0 — 9 H CyHx CyHx 0 — 0 — 0 — 0 — 10 H Ph Ph 0 — 0 — 0 — 0 — 11 Me Me Me 0 — 0 — 0 — 0 — 12 Me Et Et 0 — 0 — 0 — 0 — 13 Me nPr nPr 0 — 0 — 0 — 0 — 14 Me iPr iPr 0 — 0 — 0 — 0 — 15 Me nBu nBu 0 — 0 — 0 — 0 — 16 Me iBu iBu 0 — 0 — 0 — 0 — 17 Me tBu tBu 0 — 0 — 0 — 0 — 18 Me CyPe CyPe 0 — 0 — 0 — 0 — 19 Me CyHx CyHx 0 — 0 — 0 — 0 — 20 Me Ph Ph 0 — 0 — 0 — 0 — -
TABLE 2 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 21 Et Me Me 0 — 0 — 0 — 0 — 22 Et Et Et 0 — 0 — 0 — 0 — 23 Et nPr nPr 0 — 0 — 0 — 0 — 24 Et iPr iPr 0 — 0 — 0 — 0 — 25 Et nBu nBu 0 — 0 — 0 — 0 — 26 Et iBu iBu 0 — 0 — 0 — 0 — 27 Et tBu tBu 0 — 0 — 0 — 0 — 28 Et CyPe CyPe 0 — 0 — 0 — 0 — 29 Et CyHx CyHx 0 — 0 — 0 — 0 — 30 Et Ph Ph 0 — 0 — 0 — 0 — 31 nPr Me Me 0 — 0 — 0 — 0 — 32 nPr Et Et 0 — 0 — 0 — 0 — 33 nPr nPr nPr 0 — 0 — 0 — 0 — 34 nPr iPr iPr 0 — 0 — 0 — 0 — 35 nPr nBu nBu 0 — 0 — 0 — 0 — 36 nPr iBu iBu 0 — 0 — 0 — 0 — 37 nPr tBu tBu 0 — 0 — 0 — 0 — 38 nPr CyPe CyPe 0 — 0 — 0 — 0 — 39 nPr CyHx CyHx 0 — 0 — 0 — 0 — 40 nPr Ph Ph 0 — 0 — 0 — 0 — -
TABLE 3 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 41 iPr Me Me 0 — 0 — 0 — 0 — 42 iPr Et Et 0 — 0 — 0 — 0 — 43 iPr nPr nPr 0 — 0 — 0 — 0 — 44 iPr iPr iPr 0 — 0 — 0 — 0 — 45 iPr nBu nBu 0 — 0 — 0 — 0 — 46 iPr iBu iBu 0 — 0 — 0 — 0 — 47 iPr tBu tBu 0 — 0 — 0 — 0 — 48 iPr CyPe CyPe 0 — 0 — 0 — 0 — 49 iPr CyHx CyHx 0 — 0 — 0 — 0 — 50 iPr Ph Ph 0 — 0 — 0 — 0 — 51 nBu Me Me 0 — 0 — 0 — 0 — 52 nBu Et Et 0 — 0 — 0 — 0 — 53 nBu nPr nPr 0 — 0 — 0 — 0 — 54 nBu iPr iPr 0 — 0 — 0 — 0 — 55 nBu nBu nBu 0 — 0 — 0 — 0 — 56 nBu iBu iBu 0 — 0 — 0 — 0 — 57 nBu tBu tBu 0 — 0 — 0 — 0 — 58 nBu CyPe CyPe 0 — 0 — 0 — 0 — 59 nBu CyHx CyHx 0 — 0 — 0 — 0 — 60 nBu Ph Ph 0 — 0 — 0 — 0 — -
TABLE 4 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 61 iBu Me Me 0 — 0 — 0 — 0 — 62 iBu Et Et 0 — 0 — 0 — 0 — 63 iBu nPr nPr 0 — 0 — 0 — 0 — 64 iBu iPr iPr 0 — 0 — 0 — 0 — 65 iBu nBu nBu 0 — 0 — 0 — 0 — 66 iBu iBu iBu 0 — 0 — 0 — 0 — 67 iBu tBu tBu 0 — 0 — 0 — 0 — 68 iBu CyPe CyPe 0 — 0 — 0 — 0 — 69 iBu CyHx CyHx 0 — 0 — 0 — 0 — 70 iBu Ph Ph 0 — 0 — 0 — 0 — 71 tBu Me Me 0 — 0 — 0 — 0 — 72 tBu Et Et 0 — 0 — 0 — 0 — 73 tBu nPr nPr 0 — 0 — 0 — 0 — 74 tBu iPr iPr 0 — 0 — 0 — 0 — 75 tBu nBu nBu 0 — 0 — 0 — 0 — 76 tBu iBu iBu 0 — 0 — 0 — 0 — 77 tBu tBu tBu 0 — 0 — 0 — 0 — 78 tBu CyPe CyPe 0 — 0 — 0 — 0 — 79 tBu CyHx CyHx 0 — 0 — 0 — 0 — 80 tBu Ph Ph 0 — 0 — 0 — 0 — -
TABLE 5 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 81 CyEx Me Me 0 — 0 — 0 — 0 — 82 CyHx Et Et 0 — 0 — 0 — 0 — 83 CyHx nPr nPr 0 — 0 — 0 — 0 — 84 CyHx iPr iPr 0 — 0 — 0 — 0 — 85 CyHx nBu nBu 0 — 0 — 0 — 0 — 86 CyHx iBu iBu 0 — 0 — 0 — 0 — 87 CyHx tBu tBu 0 — 0 — 0 — 0 — 88 CyHx CyPe CyPe 0 — 0 — 0 — 0 — 89 CyHx CyHx CyHx 0 — 0 — 0 — 0 — 90 CyHx Ph Ph 0 — 0 — 0 — 0 — 91 Ph Me Me 0 — 0 — 0 — 0 — 92 Ph Et Et 0 — 0 — 0 — 0 — 93 Ph nPr nPr 0 — 0 — 0 — 0 — 94 Ph iPr iPr 0 — 0 — 0 — 0 — 95 Ph nBu nBu 0 — 0 — 0 — 0 — 96 Ph iBu iBu 0 — 0 — 0 — 0 — 97 Ph tBu tBu 0 — 0 — 0 — 0 — 98 Ph CyPe CyPe 0 — 0 — 0 — 0 — 99 Ph CyHx CyHx 0 — 0 — 0 — 0 — 100 Ph Ph Ph 0 — 0 — 0 — 0 — -
TABLE 6 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 101 Me Ph Ph 1 4-Me 0 — 1 4-Me 0 — 102 Me Ph Ph 1 4-Et 0 — 1 4-Et 0 — 103 Me Ph Ph 1 4-MeO 0 — 1 4-MeO 0 — 104 Me Ph Ph 1 4-EtO 0 — 1 4-EtO 0 — 105 Me Ph Ph 1 4-Me2N 0 — 1 4-Me2N 0 — 106 Me Ph Ph 1 4-Et2N 0 — 1 4-Et2N 0 — 107 Me Ph Ph 1 4-F 0 — 1 4-F 0 — 108 Me Ph Ph 1 4-Cl 0 — 1 4-Cl 0 — 109 Me Ph Ph 1 4-Br 0 — 1 4-Br 0 — 110 Me Ph Ph 1 3-Me 1 5-Me 1 3-Me 1 5-Me 111 Me Ph Ph 3,4-OCH2O— 3,4-OCH2O— 112 Me Ph Ph 5 Me 0 — 5 Me 0 — 113 Me Ph Ph 1 3-MeO 1 4-MeO 1 3-MeO 1 4-MeO 114 Me nPr nPr 1 4-Me2N 0 — 1 4-Me2N 0 — 115 Me iPr iPr 1 4-Me2N 0 — 1 4-Me2N 0 — 116 Me nBu nBu 1 4-Me2N 0 — 1 4-Me2N 0 — 117 Me iBu iBu 1 4-Me2N 0 — 1 4-Me2N 0 — 118 Me tBu tBu 1 4-Me2N 0 — 1 4-Me2N 0 — 119 Me CyPe CyPe 1 4-Me2N 0 — 1 4-Me2N 0 — 120 Me CyHx CyHx 1 4-Me2N 0 — 1 4-Me2N 0 — -
TABLE 7 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 121 Ph Ph Ph 1 4-Me 0 — 1 4-Me 0 — 122 Ph Ph Ph 1 4-Et 0 — 1 4-Et 0 — 123 Ph Ph Ph 1 4-MeO 0 — 1 4-MeO 0 — 124 Ph Ph Ph 1 4-EtO 0 — 1 4-EtO 0 — 125 Ph Ph Ph 1 4-Me2N 0 — 1 4-Me2N 0 — 126 Ph Ph Ph 1 4-Et2N 0 — 1 4-Et2N 0 — 127 Ph Ph Ph 1 4-F 0 — 1 4-F 0 — 128 Ph Ph Ph 1 4-Cl 0 — 1 4-Cl 0 — 129 Ph Ph Ph 1 4-Br 0 — 1 4-Br 0 — 130 Ph Ph Ph 1 3-Me 1 5-Me 1 3-Me 1 5-Me 131 Ph Ph Ph 3,4-OCH2O— 3,4-OCH2O— 132 Ph Ph Ph 5 Me 0 — 5 Me 0 — 133 Ph Ph Ph 1 3-MeO 1 4-MeO 1 3-MeO 1 4-MeO 134 Ph nPr nPr 1 4-Me2N 0 — 1 4-Me2N 0 — 135 Ph iPr iPr 1 4-Me2N 0 — 1 4-Me2N 0 — 136 Ph nBu nBu 1 4-Me2N 0 — 1 4-Me2N 0 — 137 Ph iBu iBu 1 4-Me2N 0 — 1 4-Me2N 0 — 138 Ph tBu tBu 1 4-Me2N 0 — 1 4-Me2N 0 — 139 Ph CyPe CyPe 1 4-Me2N 0 — 1 4-Me2N 0 — 140 Ph CyHx CyHx 1 4-Me2N 0 — 1 4-Me2N 0 — -
TABLE 8 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 141 Me Ph Ph 1 4-Ph 0 — 1 4-Ph 0 — 142 Me Ph Ph 0 — 0 — 1 4-Me 1 2-Me 143 Me iPr iPr 1 4-Me 0 — 0 — 0 — 144 Me iPr iPr 1 4-Me 0 — 1 4-Me 0 — 145 Me iPr iPr 1 4-tBu 0 — 1 4-tBu 0 — 146 Me iPr iPr 1 4-MeO 0 — 1 4-MeO 0 — 147 Me iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me 148 Me ipr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 149 Me iPr iPr 1 4-Ph 0 — 1 4-Ph 0 — 150 Me CyHx CyHx 1 4-Me 0 — 1 4-Me 0 — 151 Me CyHx CyEx 1 4-MeO 0 — 1 4-MeO 0 — 152 Me CyHx CyHx 1 2-Me 1 4-Me 1 2-Me 1 4-Me 153 Me CyHx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1 4-Me0 154 Me CyHx CyHx 1 4-F 0 — 1 4-F 0 — 155 Me CyHx CyHx 1 4-tBu 0 — 1 4-tBu 0 — 156 Me CyHx CyHx 1 4-Cl 0 — 1 4-Cl 0 — 157 Me CyHx CyHx 2,3-benzene 2,3-benzene 158 Me CyHx CyHx 3,4-benzene 3,4-benzene 159 Me CyHx CyHx 3,4-OCH2O— 3,4-OCH2O— 160 Me CyHx CyHx 2,3-(CH2)4— 2,3-(CH2)4— -
TABLE 9 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 161 Me CyHx CyHx 2,3-(CH2)3— 2,3-(CH2)3— 162 Me tBu tBu 1 4-Me 0 — 0 — 0 — 163 Me tBu tBu 1 4-Me2N 1 2-Me 1 4-Me2N 1 2-Me 164 Me tBu tBu 1 4-MeO 0 — 1 4-MeO 0 — 165 Me tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 166 Me tBu tBu 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 167 Me tBu tBu 1 4-F 0 — 1 4-F 0 — 168 Me tBu tBu 1 4-tBu 0 — 1 4-tBu 0 — 169 Me tBu tBu 1 4-Cl 0 — 1 4-Cl 0 — 170 Me tBu tBu 1 4-Me2N 1 2-Me 1 4-Me2N 1 2-Me 171 Me tBu tBu 2,3-benzene 3,4-benzene 172 Me tBu tBu 3,4-benzene 3,4-benzene 173 Me tBu tBu 3,4-OCH2O— 3,4-OCH2O— 174 Me tBu tBu 2,3-(CH2)4— 2,3-(CH2)4— 175 Me tBn tBu 2,3-(CH2)3— 2,3-(CH2)3— 176 Me p-Tol p-Tol 0 — 0 — 0 — 0 — 177 Me p-Tol p-Tol 1 4-Me 0 — 1 4-Me 0 — 178 Me p-Tol p-Tol 1 4-Me2N 0 — 1 4-Me2N 0 — 179 Me Xy Xy 0 — 0 — 1 — 0 — 180 Me Xy Xy 1 4-Me2N 0 — 1 4-Me2N 0 — -
TABLE 10 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 181 iPr Ph Ph 1 4-Ph 0 — 1 4-Ph 0 — 182 iPr Ph Ph 0 — 0 — 1 4-Me 1 2-Me 183 iPr iPr iPr 1 4-Me 0 — 0 — 0 — 184 iPr iPr iPr 1 4-Me 0 — 1 4-Me 0 — 185 iPr iPr iPr 1 4-tBu 0 — 1 4-tBu 0 — 186 iPr iPr iPr 1 4-MeO 0 — 1 4-MeO 0 — 187 iPr iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me 188 iPr iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 189 iPr iPr iPr 1 4-Ph 0 — 1 4-Ph 0 — 190 iPr CyHx CyHx 1 4-Me 0 — 1 4-Me 0 — 191 iPr CyHx CyHx 1 4-MeO 0 — 1 4-MeO 0 — 192 iPr CyHx CyHx 1 2-Me 1 4-Me 1 2-Me 1 4-Me 193 iPr CyEx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 194 iPr CyHx CyHx 1 4-F 0 — 1 4-F 0 — 195 iPr CyHx CyHx 1 4-tBu 0 — 1 4-tBu 0 — 196 iPr CyHx CyHx 1 4-Cl 0 — 1 4-Cl 0 — 197 iPr CyHx CyHx 2,3-benzene 2,3-benzene 198 iPr CyHx CyHx 3,4-benzene 3,4-benzene 199 iPr CyHx CyHx 3,4-OCH2O— 3,4-OCH2O— 200 iPr CyHx CyHx 2,3-(CH2)4— 2,3-(CH2)4— -
TABLE 11 General Formula (1) Exemplified Compound R1 R2 R3 P R4 q R5 r R6 s R7 201 iPr CyHx CyHx 2,3-(CH2)3— 2,3-(CH2)3— 202 iPr tBu tBu 1 4-Me 0 — 0 — 0 — 203 iPr tBu tBu 1 4-Me2N 0 — 1 4-Me2N 0 — 204 iPr tBu tBu 1 4-MeO 0 — 1 4-MeO 0 — 205 iPr tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 206 iPr tBu tBu 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 207 iPr tBu tBu 1 4-F 0 — 1 4-F 0 — 208 iPr tBu tBu 1 4-tBu 0 — 1 4-tBu 0 — 209 iPr tBu tBu 1 4-Cl 0 — 1 4-Cl 0 210 iPr tBu tBu 1 4-Me2N 1 2-Me 1 4-Me2N 1 2-Me 211 iPr tBu tBu 2,3-benzene 2,3-benzene 212 iPr tBu tBu 3,4-benzene 3,4-benzene 213 iPr tBu tBu 3,4-OCH2O— 3,4-OCH2O— 214 iPr tBu tBu 2,3-(CH2)4— 2,3-(CH2)4— 215 iPr tBu tBu 2,3-(CH2)3— 2,3-(CH2)3— 216 iPr p-Tol p-Tol 0 — 0 — 0 — 0 — 217 iPr p-Tol p-Tol 1 4-Me 0 — 1 4-Me 0 — 218 iPr p-Tol p-Tol 1 4-Me2N 0 — 1 4-Me2N 0 — 219 iPr Xy Xy 0 — 0 — 1 — 0 — 220 iPr Xy Xy 1 4-Me2N 0 — 1 4-Me2N 0 — -
TABLE 12 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 221 CyHx Ph Ph 1 4-Ph 0 — 1 4-Ph 0 — 222 CyHx Ph Ph 0 — 0 — 1 4-Me 1 2-Me 223 CyHx iPr iPr 1 4-Me 0 — 0 — 0 — 224 CyHx iPr iPr 1 4-Me 0 — 1 4-Me 0 — 225 CyHx iPr iPr 1 4-tBu 0 — 1 4-tBu 0 — 226 CyHx iPr iPr 1 4-MeO 0 — 1 4-MeO 0 — 227 CyHx iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me 228 CyHx iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 229 CyHx iPr iPr 1 4-Ph 0 — 1 4-Ph 0 — 230 CyHx CyHx CyHx 1 4-Me 0 — 1 4-Me 0 — 231 CyHx CyHx CyHx 1 4-MeO 0 — 1 4-MeO 0 — 232 CyHx CyHx CyHx 1 2-Me 1 4-Me 1 2-Me 1 4-Me 233 CyHx CyHx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 234 CyHx CyHx CyHx 1 4-F 0 — 1 4-F 0 — 235 CyHx CyHx CyHx 1 4-tBu 0 — 1 4-tBu 0 — 236 CyHx CyHx CyHx 1 4-Cl 0 — 1 4-Cl 0 — 237 CyHx CyHx CyHx 2,3-benzene 2,3-benzene 238 CyHx CyHx CyHx 3,4-benzene 3,4-benzene 239 CyHx CyHx CyHx 3,4-OCH2O— 3,4-OCH2O— 240 CyHx CyHx CyHx 2,3-(CH2)4— 2,3-(CH2)4— -
TABLE 13 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 241 CyHx CyHx CyHx 2,3-(CH2)3— 2,3-(CH2)3— 242 CyHx tBu tBu 1 4-Me 0 — 0 — 0 — 243 CyHx tBu tBu 1 4-Me2N 0 — 1 4-Me2N 0 — 244 CyHx tBu tBu 1 4-MeO 0 — 1 4-MeO 0 — 245 CyHx tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 246 CyHx tBu tBu 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 247 CyHx tBu tBu 1 4-F 0 — 1 4-F 0 — 248 CyHx tBu tBu 1 4-tBu 0 — 1 4-tBu 0 — 249 CyHx tBu tBu 1 4-Cl 0 — 1 4-Cl 0 — 250 CyHx tBu tBu 1 4-Me2N 1 2-Me 1 4-Me2N 1 2-Me 251 CyHx tBu tBu 2,3-benzene 2,3-benzene 252 CyHx tBu tBu 3,4-benzene 3,4-benzene 253 CyHx tBu tBu 3,4-OCH2O— 3,4-OCH2O— 254 CyHx tBu tBu 2,3-(CH2)4— 2,3-(CH2)4— 255 CyHx tBu tBu 2,3-(CH2)3— 2,3-(CH2)3— 256 CyHx p-Tol p-Tol 0 — 0 — 0 — 0 — 257 CyHx p-Tol p-Tol 1 4-Me 0 — 1 4-Me 0 — 258 CyHx p-Tol p-Tol 1 4-Me2N 0 — 1 4-Me2N 0 — 259 CyHx Xy Xy 0 — 0 — 1 — 0 — 260 CyHx Xy Xy 1 4-Me2N 0 — 1 4-Me2H 0 — -
TABLE 14 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 261 tBu Ph Ph 1 4-Ph 0 — 1 4-Ph 0 — 262 tBu Ph Ph 0 — 0 — 1 4-Me 1 2-Me 263 tBu iPr iPr 1 4-Me 0 — 0 — 0 — 264 tBu iPr iPr 1 4-Me 0 — 1 4-Me 0 — 265 tBu iPr iPr 1 4-tBu 0 — 1 4-tBu 0 — 266 tBu iPr iPr I 4-MeO 0 — 1 4-MeO 0 — 267 tBu iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me 268 tBu iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 269 tBu iPr iPr 1 4-Ph 0 — 1 4-Ph 0 — 270 tBu CyHx CyHx 1 4-Me 0 — 1 4-Me 0 — 271 tBu CyHx CyHx 1 4-MeO 0 — 1 4-MeO 0 — 272 tBu CyHx CyHx 1 2-Me 1 4-Me 1 2-Me 1 4-Me 273 tBu CyHx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 274 tBu CyHx CyHx 1 4-F 0 — 1 4-F 0 — 275 tBu CyHx CyHx 1 4-tBu 0 — 1 4-tBu 0 — 276 tBu CyHx CyHx 1 4-Cl 0 — 1 4-Cl 0 — 277 tBu CyHx CyHx 2,3-benzene 2,3-benzene 278 tBu CyHx CyHx 3,4-benzene 3,4-benzene 279 tBu CyHx CyHx 3,4-OCH2O— 3,4-OCH2O— 280 tBu CyHx CyHx 2,3-(CH2)4— 2,3-(CH2)4— -
TABLE 15 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 281 tBu CyHx CyHx 2,3-(CH2)3— 2,3-(CH2)3— 282 tBu tBu tBu 1 4-Me 0 — 0 — 0 — 283 tBu tBu tBu 1 4-Me2N 0 — 1 4-Me2N 0 — 284 tBu tBu tBu 1 4-MeO 0 — 1 4-MeO 0 — 285 tBu tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 286 tBu tBu tBu 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 287 tBu tBu tBu 1 4-F 0 — 1 4-F 0 — 288 tBu tBu tBu 1 4-tBu 0 — 1 4-tBu 0 — 289 tBu tBu tBu 1 4-Cl 0 — 1 4-Cl 0 — 290 tBu tBu tBu 1 4-Me2N 1 2-Me 1 4-Me2N 1 2-Me 291 tBu tBu tBu 2,3-benzene 2,3-benzene 292 tBu tBu tBu 3,4-benzene 3,4-benzene 293 tBu tBu tBu 3,4-OCH2O— 3,4-OCH2O— 294 tBu tBu tBu 2,3-(CH2)4— 2,3-(CH2)4— 295 tBu tBu tBu 2,3-(CH2)3— 2,3-(CH2)3— 296 tBu p-Tol p-Tol 0 — 0 — 0 — 0 — 297 tBu p-Tol p-Tol 1 4-Me 0 — 1 4-Me 0 — 298 tBu p-Tol p-Tol 1 4-Me2N 0 — 1 4-Me2N 0 — 299 tBu Xy Xy 0 — 0 — 1 — 0 — 300 tBu Xy Xy 1 4-Me2N 0 — 1 4-Me2N 0 — -
TABLE 16 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 301 Ph Ph Ph 1 4-Ph 0 — 1 4-Ph 0 — 302 Ph Ph Ph 0 — 0 — 1 4-Me 1 2-Me 303 Ph iPr iPr 1 4-Me 0 — 0 — 0 — 304 Ph iPr iPr 1 4-Me 0 — 1 4-Me 0 — 305 Ph iPr iPr 1 4-tBu 0 — 1 4-tBu 0 — 306 Ph iPr iPr 1 4-MeO 0 — 1 4-MeO 0 — 307 Ph iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me 308 Ph iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 309 Ph iPr iPr 1 4-Ph 0 — 1 4-Ph 0 — 310 Ph CyHx CyHx 1 4-Me 0 — 1 4-Me 0 — 311 Ph CyHx CyHx 1 4-MeO 0 — 1 4-MeO 0 — 312 Ph CyHx CyHx 1 2-Me 1 4-Me 1 2-Me 1 4-Me 313 Ph CyHx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 314 Ph CyHx CyHx 1 4-F 0 — 1 4-F 0 — 315 Ph CyHx CyHx 1 4-tBu 0 — 1 4-tBu 0 — 316 Ph CyHx CyHx 1 4-Cl 0 — 1 4-Cl 0 — 317 Ph CyHx CyHx 2,3-benzene 2,3-benzene 318 Ph CyHx CyHx 3,4-benzene 3,4-benzene 319 Ph CyHx CyHx 3,4-OCH2O— 3,4-OCH2O— 320 Ph CyHx CyHx 2,3-(CH2)4— 2,3-(CH2)4— -
TABLE 17 General Formula (1) Exemplified Compound R1 R2 R3 p R4 q R5 r R6 s R7 321 Ph CyHx CyHx 2,3-(CH2)3— 2,3-(CH2)3— 322 Ph tBu tBu 1 4-Me 0 — 0 — 0 — 323 Ph tBu tBu 1 4-Me2N 0 — 1 4-Me2N 0 — 324 Ph tBu tBu 1 4-MeO 0 — 1 4-MeO 0 — 325 Ph tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 326 Ph tBu tBu 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 327 Ph tBu tBu 1 4-F 0 — 1 4-F 0 — 328 Ph tBu tBu 1 4-tBu 0 — 1 4-tBu 0 — 329 Ph tBu tBu 1 4-Cl 0 — 1 4-Cl 0 — 330 Ph tBu tBu 1 4-Me2N 1 2-Me 1 4-Me2N 1 2-Me 331 Ph tBu tBu 2,3-benzene 2,3-benzene 332 Ph tBu tBu 3,4-benzene 3,4-benzene 333 Ph tBu tBu 3,4-OCH2O— 3,4-OCH2O— 334 Ph tBu tBu 2,3-(CH2)4— 2,3-(CH2)4— 335 Ph tBu tBu 2,3-(CH2)3— 2,3-(CH2)3— 336 Ph p-Tol p-Tol 0 — 0 — 0 — 0 — 337 Ph p-Tol p-Tol 1 4-Me 0 — 1 4-Me 0 338 Ph p-Tol p-Tol 1 4-Me2N 0 — 1 4-Me2N 0 — 339 Ph Xy Xy 0 — 0 — 1 — 0 — 340 Ph Xy Xy 1 4-Me2N 0 — 1 4-Me2N 0 — -
- (In the formula, R1, R2, R3, R4, R5, R6, R7, p, q, r, and s have the same meanings as defined above; X is a halogen atom; and R is a lower alkyl group having 1 to 4 carbon atoms.)
- Specifically, the process comprises the following five steps as shown above.
- First Step: A step in which an alcohol compound (8) is obtained by a) a method comprising the reaction of a diaryl ketone (3) with a Grignard reagent (5), or by b) a method comprising the reaction of an ester (4) with a Grignard reagent (6) and/or another Grignard reagent.
- Second Step: A step in which the alcohol compound (8) is dehydrated with an acid catalyst (e.g., p-toluenesulfonic acid) to obtain a vinyl compound (9).
- Third Step: A step in which the vinyl compound (9) is caused to addition reaction of a halogen to thereby obtain a dihalide compound (10).
- Fourth Step: A step in which the dihalide compound (10) is subjected to dehydrohalogenation optionally in the presence of a base (e.g., pyridine) to obtain a vinyl halide compound (11).
- Fifth Step: A step in which lithium metal, an alkyllithium, or magnesium metal is caused to act on the vinyl halide compound (11) to prepare a vinyllithium compound or vinyl Grignard reagent and this reaction product is subjected to coupling reaction with a phosphorus halide compound (12) to obtain a 2,2-(diaryl)vinylphosphine compound (1) of the invention.
- In the compound (3) to compound (10) in the formula shown above, R1, R2, R3, R4, R5, R6, R7, p, q, r, and s have the same meanings as defined above; X is a halogen atom; and R in the compound (4) is a lower alkyl group having 1 to 4 carbon atoms.
- Examples of R1, R2, R3, R4, R5, R6, and R7 include the same groups and atoms as enumerated above.
- Examples of X include a halogen atom such as fluorine, chlorine, bromine or iodine.
- Examples of R include a lower alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl.
- As the diaryl ketone (3) and the ester (4) may be used a commercial diaryl ketone compound and a commercial ester compound (e.g., ones manufactured by Tokyo Kasei Kogyo Co., Ltd. and Nacalai Tesque, Inc.) without any treatment. Alternatively, the ketone (3) and ester (4) may be synthesized by known methods.
- The Grignard reagents (5), (6), and (7) may be ones prepared by a known method from corresponding halogen compounds on the market or from halogen compounds synthesized by a known method.
- For conducting the first step, in which an alcohol compound (8) is obtained by a) a method comprising the reaction of a diaryl ketone (3) with a Grignard reagent (5), or by b) a method comprising the raction of an ester (4) with a Grignard reagent (6) and/or another Grignard reagent, an ordinary Grignard reaction can be used.
- In the Grignard reaction by method a), an alcohol compound (8) can be obtained by the reaction of a diaryl ketone (3) with a Grignard reagent (5).
- The amount of the Grignard reagent (5) to be used is preferably about from 0.5 to 10 mol, more preferably about from 0.8 to 3.0 mol, per mol of the diaryl ketone (3).
- Examples of reaction solvents include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran. Such a solvent may be used in an amount of preferably about from 1.0 to 80 times by volume, more preferably about from 2.0 to 30 times by volume, the amount of the diaryl ketone (3).
- Appropriate additives may be added in conducting in this reaction in order to accelerate the reaction. Examples of the additives include cesium trichloride, zinc chloride, zinc bromide, copper chloride, copper bromide, copper iodide, aluminum trichloride, and titanium tetrachloride. Preferred of these are cesium trichloride, copper chloride, copper bromide, and copper iodide. The amount of such additives to be used is preferably about from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol, per mol of the diaryl ketone (3).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas. In this reaction, the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 12 hours, and the reaction temperature is generally about from −20 to 100° C., preferably about from 0 to 70° C. Although such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the diaryl ketone (3) and Grignard reagent (5) to be used, etc.
- In the Grignard reaction by method b), an alcohol compound (8) can be obtained by the reaction of an ester (4) with a Grignard reagent (6) and/or another Grignard reagent.
- The amount of the Grignard reagents (6) and (7) to be used is preferably about from 1.0 to 10 mol, more preferably about from 1.6 to 4.8 mol, per mol of the ester (4).
- Examples of reaction solvents include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran. Such a solvent may be used in an amount of preferably about from 1.0 to 50 times by volume, more preferably about from 4.0 to 10 times by volume, the amount of the ester (4).
- Appropriate additives may be added in conducting the reaction in order to accelerate the reaction. Examples of the additives include cesium trichloride, zinc chloride, zinc bromide, copper chloride, copper bromide, copper iodide, aluminum trichloride, and titanium tetrachloride. Preferred of these are cesium trichloride, copper chloride, copper bromide, and copper iodide. The amount of such additives to be used is preferably about from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol, per mol of the ester (4).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas. In this reaction, the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 8 hours, and the reaction temperature is generally about from −20 to 100° C., preferably about from 0 to 70° C. Although such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the ester (4) and Grignard reagents (6) and (7) to be used, etc.
- In each of a) and b) described above, an ordinary post-treatment is conducted after completion of the reaction, whereby the target compound can be obtained.
- For conducting the second step, in which the alcohol compound (8) is dehydrated with an acid catalyst (e.g., p-toluenesulfonic acid) to obtain a vinyl compound (9), an ordinary dehydration reaction can be used.
- Examples of the acid catalyst include hydrochloric acid, sulfuric acid, camphorsulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Preferred of these is p-toluenesulfonic acid. The amount of the acid catalyst to be used is preferably about from 0.0001 to 0.2 mol, more preferably about from 0.005 to 0.05 mol, per mol of the alcohol compound (8).
- Examples of reaction solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are benzene, toluene, and xylene. Such a solvent may be used in an amount of preferably about from 1.0 to 50 times by volume, more preferably about from 2.0 to 20 times by volume, the amount of the alcohol compound (8).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas. In this reaction, the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 8 hours, and the reaction temperature is generally about from 20 to 180° C., preferably about from 70 to 140° C. Although such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the alcohol compound (8) and acid catalyst to be used, etc.
- After completion of the reaction, an ordinary post-treatment is conducted, whereby the target compound can be obtained.
- For conducting the third step, in which the vinyl compound (9) is caused to add a halogen to thereby obtain a dihalide compound (10), the ordinary halogen addition reaction to an olefin can be used.
- Examples of the halogen include chlorine, bromine, and iodine, and bromine is preferred. The amount of the halogen to be used is preferably about from 0.5 to 2.0 mol, more preferably about from 0.8 to 1.2 mol, per mol of the vinyl compound (9).
- Examples of reaction solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane; and halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dibromomethane, and dibromoethane. Preferred of these are halogenated solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. Such a solvent may be used in an amount of preferably about from 0.2 to 50 times by volume, more preferably about from 0.5 to 20 times by volume, the amount of the vinyl compound (9).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas. In this reaction, the reaction time is generally about from 10 minutes to 24 hours, preferably about from 30 minutes to 8 hours, and the reaction temperature is generally about from −60 to 100° C., preferably about from −30 to 50° C. Although such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the vinyl compound (9) and halogen to be used, etc.
- After completion of the reaction, an ordinary post-treatment is conducted, whereby the target compound can be obtained.
- For conducting the fourth step, in which the dihalide compound (10) is subjected to dehydrohalogenation optionally in the presence of a base to obtain a vinyl halide compound (11), an ordinary dehydrohalogenation reaction can be used.
- Examples of the base include triethylamine, dimethylaniline, diethylaniline, pyridine, picoline, lutidine, ethylpyridine, quinoline, and isoquinoline. Preferred of these is pyridine. Such a base may be used in an amount of preferably about from 0.5 to 30 mol, more preferably about from 1.0 to 10 mol, per mol of the dihalide compound (10).
- Examples of reaction solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are benzene, toluene, and xylene. Such a solvent may be used in an amount of preferably about from 0.2 to 30 times by volume, more preferably about from 0.5 to 10 times by volume, the amount of the dihalide compound (10).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas. In this reaction, the reaction time is generally about from 10 minutes to 30 hours, preferably about from 30 minutes to 16 hours, and the reaction temperature is generally about from 20 to 140° C., preferably about from 60 to 110° C. Although such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the dihalide compound (10) and base to be used, etc.
- After completion of the reaction, an ordinary post-treatment is conducted, whereby the target compound can be obtained.
- For conducting the fifth step, in which lithium metal, an alkyllithium, or magnesium metal is caused to act on the vinyl halide compound (11) to prepare a vinyllithium compound or vinyl Grignard reagent and this reaction product is subjected to coupling reaction with a phosphorus halide compound (12) to obtain a 2,2-(diaryl)vinylphosphine compound (1) of the invention, use can be made of the ordinary coupling reaction of a lithium reagent or Grignard reagent with a phosphorus halide compound.
- The amount of the lithium metal, alkyllithium, or magnesium metal to be used is preferably about from 0.5 to 3.0 mol, more preferably about from 0.8 to 1.5 mol, per mol of the vinyl halide compound (11).
- The amount of the halogenated phosphorus compound (12) to be used is preferably about from 0.5 to 3.0 mol, more preferably about from 0.7 to 1.5 mol, per mol of the vinyl halide compound (11).
- Examples of reaction solvents include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether and tetrahydrofuran. Such a solvent may be used in an amount of preferably about from 1.0 to 50 times by volume, more preferably about from 4.0 to 30 times by volume, the amount of the vinyl halide compound (11).
- Appropriate additives may be added in conducting in this reaction in order to accelerate the reaction. Examples of the additives include copper chloride, copper bromide, copper iodide, copper triflate, copper cyanide, a copper iodide-dimethyl sulfide complex, a copper iodide-triphenylphosphine complex, and a copper iodide-tributylphosphine complex. Preferred of these are copper chloride, copper bromide, and copper iodide. The amount of such additives to be used is preferably about from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol, per mol of the vinyl halide compound (11).
- This reaction is usually conducted under an inert gas atmosphere such as nitrogen gas or argon gas. In this reaction, the reaction time is generally about from 10 minutes to 40 hours, preferably about from 30 minutes to 24 hours, and the reaction temperature is generally about from −100 to 120° C., preferably about from −80 to 80° C. Although such conditions can be used to carry out the reaction, they may be suitably varied according to the kinds and amounts of the vinyl halide compound (11) and phosphorus halide compound (12) to be used, etc.
- After completion of the reaction, an ordinary post-treatment is conducted, whereby the target compound can be obtained.
- The compound (1) of the invention thus obtained serves as a ligand to form a palladium-phosphine catalyst in cooperation with a palladium compound.
- The palladium compound to be used as a catalyst precursor for forming the palladium-phosphine catalyst is not particularly limited. However, salts or complexes of palladium having a valence of 4, 2, or 0 are mainly used.
- Specific examples of the palladium compound include compounds of tetravalent palladium, such as sodium hexachloropalladate(IV) tetrahydrate and potassium hexachloropalladate(IV), compounds of bivalent palladium, such as palladium(II) chloride, palladium(II) bromide, palladium(II) acetate, palladium(II) acetylacetonate, dichlorobis(benzonitrile)palladium(II), dichlorobis(acetonitrile)palladium(II), dichlorobis(triphenylphosphine)palladium(II), dichlorotetraamminepalladium(II), dichloro(cycloocta-1,5-diene)palladium(II), palladium(II) trifluoroacetate, and π-allylpalladium(II) chloride diner, and compounds of zero-valent palladium, such as tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)dipalladium(0)-chloroform complex, and tetrakis(triphenylphosphine)palladium(0).
- The palladium-phosphine catalyst obtained by causing a palladium compound to act on the novel 2,2-(diaryl)vinylphosphine compound (1) can be prepared, for example, by reacting the 2,2-(diaryl)vinylphosphine compound (1) with π-allylpalladium(II) chloride dimer according to the method described in Y. Uozumi and T. Hayashi,J. Am. Chem. Soc., 1991, Vol. 113, p.9887.
- The palladium-phosphine catalyst thus obtained by causing a palladium compound to act on the novel 2,2-(diaryl)vinylphosphine compound (1) of the invention can be used as a catalyst in the amination reaction or the carbon-carbon bond formation reaction in which an aryl compound having a leaving group is reacted with this reaction substance (an amine compound, an arylboric acid compound, an arylborate ester compound, or an alkyne compound) in the presence of a base.
- The aryl compound having a leaving group in the invention is represented by general formula (2):
- ArX1 (2)
- (wherein Ar is an aryl group which may have one or more substituents or a heteroaryl group which may have one or more substituents; and X1 is a halogen atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, or a toluenesulfonyloxy group).
- The aryl compound (2) to be used in the invention is not particularly limited. Examples thereof include aryl bromides, aryl chlorides, aryl iodides, aryl fluorides, aryl trifluoromethanesulfonate, aryl methanesulfonate, aryl p-toluenesulfonate, and aryl halides having two or more halogen atoms.
- Specific examples of the aryl compound (2) include: aryl bromides such as bromobenzene, o-bromoanisole, m-bromoanisole, p-bromoanisole, o-bromotoluene, m-bromotoluene, p-bromotoluene, o-bromophenol, m-bromophenol, p-bromophenol, 2-bromobenzotrifluoride, 3-bromobenzotrifluoride, 4-bromobenzotrifluoride, 1-bromo-2,4-dimethoxybenzene, 1-bromo-2,5-dimethoxybenzene, 2-bromophenethyl alcohol, 3-bromophenethyl alcohol, 4-bromophenethyl alcohol, 5-bromo-1,2,4-trimethylbenzene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene, 5-bromo-m-xylene, 1-bromo-3-(trifluoromethoxy)benzene, 1-bromo-4-(trifluoromethoxy)benzene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 4-bromo-1,2-(methylenedioxy)benzene, 1-bromonaphthalene, 2-bromonaphthalene, 1-bromo-2-methylnaphthalene, 1-bromo-4-methylnaphthalene, 1,4-dibromonaphthalene, 4,4′-dibromobiphenyl, 2-bromothiophene, 3-bromothiophene, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 9-bromophenanthrene, 2-bromofuran, and 3-bromofuran;
- aryl chlorides such as chlorobenzene, o-chloroanisole, m-chloroanisole, p-chloroanisole, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride, 4-chlorobenzotrifluoride, 1-chloro-2,4-dimethoxybenzene, 1-chloro-2,5-dimethoxybenzene, 2-chlorophenethyl alcohol, 3-chlorophenethyl alcohol, 4-chlorophenethyl alcohol, 5-chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xylene, 1-chloro-3-(trifluoromethoxy)benzene, 1-chloro-4-(trifluoromethoxy)benzene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 3-chloronaphthalene, 2-chloronaphthalene, 1-chloro-2-methylnaphthalene, 2-chloro-4-methylnaphthalene, 1,4-dichloronaphthalene, 4,4′-dichlorobiphenyl, 2-chlorothiophene, 3-chlorothiophene, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 9-chlorophenanthrene, 2-chlorofuran, and 3-chlorofuran;
- aryl iodides such as iodobenzene, o-iodoanisole, m-iodoanisole, p-iodoanisole, o-iodotoluene, m-iodotoluene, p-iodotoluene, o-iodophenol, m-iodophenol, p-iodophenol, 2-iodobenzotrifluoride, 3-iodobenzotrifluoride, 4-iodobenzotrifluoride, 1-iodo-2,4-dimethoxybenzene, 1-iodo-2,5-dimethoxybenzene, 2-iodophenethyl alcohol, 3-iodophenethyl alcohol, 4-iodophenethyl alcohol, 5-iodo-1,2,4-trimethylbenzene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene, 5-iodo-m-xylene, 1-iodo-3-(trifluoromethoxy)benzene, 1-iodo-4-(trifluoromethoxy)benzene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 1-iodonaphthalene, 2-iodonaphthalene, 1-iodo-2-methylnaphthalene, 1-iodo-4-methylnaphthalene, 1,4-diiodonaphthalene, 4,4′-diiodobiphenyl, 2-iodothiophene, 3-iodothiophene, 2-iodopyridine, 3-iodopyridine, 4-iodopyridine, 9-iodophenanthrene, 2-iodofuran, and 3-iodofuran;
- aryl fluorides such as fluorobenzene, o-fluoroanisole, m-fluoroanisole, p-fluoroanisole, o-fluorotoluene, m-fluorotoluene, p-fluorotoluene, o-fluorophenol, m-fluorophenol, p-fluorophenol, 2-fluorobenzotrifluoride, 3-fluorobenzotrifluoride, 4-fluorobenzotrifluoride, 1-fluoro-2,4-dimethoxybenzene, 1-fluoro-2,5-dimethoxybenzene, 2-fluorophenethyl alcohol, 3-fluorophenethyl alcohol, 4-fluorophenethyl alcohol, 5-fluoro-1,2,4-trimethylbenzene, 2-fluoro-m-xylene, 2-fluoro-p-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene, 4-fluoro-m-xylene, 5-fluoro-m-xylene, 1-fluoro-3-(trifluoromethoxy)benzene, 1-fluoro-4-(trifluoromethoxy)benzene, 2-fluorobiphenyl, 3-fluorobiphenyl, 4-fluorobiphenyl, 4-fluoro-1,2-(methylenedioxy)benzene, 1-fluoronaphthalene, 2-fluoronaphthalene, 1-fluoro-2-methylnaphthalene, 1-fluoro-4-methylnaphthalene, 1,4-difluoronaphthalene, 4,4′-difluorobiphenyl, 2-fluorothiophene, 3-fluorothiophene, 2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine, 9-fluorophenanthrene, 2-fluorofuran, and 3-fluorofuran;
- aryl trifluoromethanesulfonate such as trifluoromethanesulfonyloxybenzene, o-trifluoromethanesulfonyloxyanisole, m-trifluoromethanesulfonyloxyanisole, p-trifluoromethanesulfonyloxyanisole, o-trifluoromethanesulfonyloxytoluene, m-trifluoromethanesulfonyloxytoluene, p-trifluoromethanesulfonyloxytoluene, p-trifluoromethanesulfonyloxyphenol, o-trifluoromethanesulfonyloxyphenol, p-trifluoromethanesulfonyloxyphenol, 2-trifluoromethanesulfonyloxybenzotrifluoride, 3-trifluoromethanesulfonyloxybenzotrifluoride, 4-trifluoromethanesulfonyloxybenzotrifluoride, 1-trifluoromethanesulfonyloxy-2,4-dimethoxybenzene, 1-trifluoromethanesulfonyloxy-2,5-dimethoxybenzene, 2-trifluoromethanesulfonyloxyphenethyl alcohol, 3-trifluoromethanesulfonyloxyphenethyl alcohol, 4-trifluoromethanesulfonyloxyphenethyl alcohol, 5-trifluoromethanesulfonyloxy-1,2,4-trimethylbenzene, 2-trifluoromethanesulfonyloxy-m-xylene, 2-trifluoromethanesulfonyloxy-p-xylene, 3-trifluoromethanesulfonyloxy-o-xylene, 4-trifluoromethanesulfonyloxy-o-xylene, 4-trifluoromethanesulfonyloxy-m-xylene, 5-trifluoromethanesulfonyloxy-m-xylene, 1-trifluoromethanesulfonyloxy-3-(trifluoromethoxy)benzene, 1-trifluoromethanesulfonyloxy-4-(trifluoromethoxy)benzene, 2-trifluoromethanesulfonyloxybiphenyl, 3-trifluoromethanesulfonyloxybiphenyl, 4-trifluoromethanesulfonyloxybiphenyl, 4-trifluoromethanesulfonyloxy-1,2-(methylenedioxy)benzene, 1-trifluoromethanesulfonyloxynaphthalene, 2-trifluoromethanesulfonyloxynaphthalene, 1-trifluoromethanesulfonyloxy-2-methylnaphthalene, 1-trifluoromethanesulfonyloxy-4-methylnaphthalene, 1,4-ditrifluoromethanesulfonyloxynaphthalene, 4,4′-ditrifluoromethanesulfonyloxybiphenyl, 2-trifluoromethanesulfonyloxythiophene, 3-trifluoromethanesulfonyloxythiophene, 2-trifluoromethanesulfonyloxypyridine, 3-trifluoromethanesulfonyloxypyridine, 4-trifluoromethanesulfonyloxypyridine, 9-trifluoromethanesulfonyloxyphenanthrene, 2-trifluoromethanesulfonyloxyfuran, and 3-trifluoromethanesulfonyloxyfuran;
- aryl methanesulfonate such as methanesulfonyloxybenzene, o-methanesulfonyloxyanisole, m-methanesulfonyloxyanisole, p-methanesulfonyloxyanisole, o-methanesulfonyloxytoluene, m-methanesulfonyloxytoluene, p-methanesulfonyloxytoluene, o-methanesulfonyloxyphenol, m-methanesulfonyloxyphenol, p-methanesulfonyloxyphenol, 2-methanesulfonyloxybenzotrifluoride, 3-methanesulfonyloxybenzotrifluoride, 4-methanesulfonyloxybenzotrifluoride, 1-methanesulfonyloxy-2,4-dimethoxybenzene, 1-methanesulfonyloxy-2,5-dimethoxybenzene, 2-methanesulfonyloxyphenethyl alcohol, 3-methanesulfonyloxyphenethyl alcohol, 4-methanesulfonyloxyphenethyl alcohol, 5-methanesulfonyloxy-1,2,4-trimethylbenzene, 2-methanesulfonyloxy-m-xylene, 2-methanesulfonyloxy-p-xylene, 3-methanesulfonyloxy-o-xylene, 4-methanesulfonyloxy-o-xylene, 4-methanesulfonyloxy-m-xylene, 5-methanesulfonyloxy-m-xylene, 1-methanesulfonyloxy-3-(trifluoromethoxy)benzene, 1-methanesulfonyloxy-4-(trifluoromethoxy)benzene, 2-methanesulfonyloxybiphenyl, 3-methanesulfonyloxybiphenyl, 4-methanesulfonyloxybiphenyl, 4-methanesulfonyloxy-1,2-(methylenedioxy)benzene, 1-methanesulfonyloxynaphthalene, 2-methanesulfonyloxynaphthalene, 1-methanesulfonyloxy-2-methylnaphthalene, 1-methanesulfonyloxy-4-methylnaphthalene, 1,4-dimethanesulfonyloxynaphthalene, 4,4′-dimethanesulfonyloxybiphenyl, 2-methanesulfonyloxythiophene, 3-methanesulfonyloxythiophene, 2-methanesulfonyloxypyridine, 3-methanesulfonyloxypyridine, 4-methanesulfonyloxypyridine, 9-methanesulfonyloxyphenanthrene, 2-methanesulfonyloxyfuran, and 3-methanesulfonyloxyfuran; and
- aryl p-toluenesulfonate such as p-toluenesulfonyloxybenzene, o-(p-toluenesulfonyloxy)anisole, m-(p-toluenesulfonyloxy)anisole, p-(p-toluenesulfonyloxy)anisole, o-(p-toluenesulfonyloxy)toluene, m-(p-toluenesulfonyloxy)toluene, p-(p-toluenesulfonyloxy)toluene, o-(p-toluenesulfonyloxy)phenol, m-(p-toluenesulfonyloxy)phenol, p-(p-toluenesulfonyloxy)phenol, 2-(p-toluenesulfonyloxy)benzotrifluoride, 3-(p-toluenesulfonyloxy)benzotrifluoride, 4-(p-toluenesulfonyloxy)benzotrifluoride, 1-(p-toluenesulfonyloxy)-2,4-dimethoxybenzene, 1-(p-toluenesulfonyloxy)-2,5-dimethoxybenzene, 2-(p-toluenesulfonyloxy)phenethyl alcohol, 3-(p-toluenesulfonyloxy)phenethyl alcohol, 4-(p-toluenesulfonyloxy)phenethyl alcohol, 5-(p-toluenesulfonyloxy)-1,2,4-trimethylbenzene, 2-(p-toluenesulfonyloxy)-m-xylene, 2-(p-toluenesulfonyloxy)-p-xylene, 3-(p-toluenesulfonyloxy)-o-xylene, 4-(p-toluenesulfonyloxy)-o-xylene, 4-(p-toluenesulfonyloxy)-m-xylene, 5-(p-toluenesulfonyloxy)-m-xylene, 1-(p-toluenesulfonyloxy)-3-(trifluoromethoxy)benzene, 1-(p-toluenesulfonyloxy)-4-(trifluoromethoxy)benzene, 2-(p-toluenesulfonyloxy)biphenyl, 3-(p-toluenesulfonyloxy)biphenyl, 4-(p-toluenesulfonyloxy)biphenyl, 4-(p-toluenesulfonyloxy)-1,2-(methylenedioxy)benzene, 1-(p-toluenesulfonyloxy)naphthalene, 2-(p-toluenesulfonyloxy)naphthalene, 1-(p-toluenesulfonyloxy)-2-methylnaphthalene, 1-(p-toluenesulfonyloxy)-4-methylnaphthalene, 1,4-di(p-toluenesulfonyloxy)naphthalene, 4,4′-di(p-toluenesulfonyloxy)biphenyl, 2-(p-toluenesulfonyloxy)thiophene, 3-(p-toluenesulfonyloxy)thiophene, 2-(p-toluenesulfonyloxy)pyridine, 3-(p-toluenesulfonyloxy)pyridine, 4-(p-toluenesulfonyloxy)pyridine, 9-(p-toluenesulfonyloxy)phenanthrene, 2-(p-toluenesulfonyloxy)furan, and 3-(p-toluenesulfonyloxy)furan.
- Other examples of aryl halides which can be used in the invention include aryl halides having two or more halogen atoms, such as 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 9,10-dibromoanthracene, 9,10-dichloroanthracene, 1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene, 1-bromo-4-fluorobenzene, 2-bromochlorobenzene, 3-bromochlorobenzene, 4-bromochlorobenzene, 2-bromo-5-chlorotoluene, 3-bromo-4-chlorobenzotrifluoride, 5-bromo-2-chlorobenzotrifluoride, 1-bromo-2,3-dichlorobenzene, 1-bromo-2,6-dichlorobenzene, 1-bromo-3,5-dichlorobenzene, 2-bromo-4-fluorotoluene, 2-bromo-5-fluorotoluene, 3-bromo-4-fluorotoluene, 4-bromo-2-fluorotoluene, and 4-bromo-3-fluorotoluene.
- Examples of the amine compound to be used in the invention include primary amines, secondary amines, imines, and amides.
- The primary amines are not particularly limited. Examples thereof include aliphatic primary amines such as ethylamine, propylamine, butylamine, isobutylamine, tert-butylamine, pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, and octylamine; and aromatic primary amines such as aniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-anisidine, m-anisidine, p-anisidine, o-toluidine, m-toluidine, p-toluidine, 2-naphthylamine, 2-aminobiphenyl, 4-aminobiphenyl, 3,4-methylenedioxyaniline, m-xylidine, and p-xylidine.
- The secondary amines are not particularly limited. Examples thereof include cyclic secondary amines such as piperazine, 2-methylpiperazine, homopiperazine, N-methylhomopiperazine, 2,6-dimethylpiperazine, N-methylpiperazine, N-ethylpiperazine, N-ethoxycarbonylpiperazine, N-benzylpiperazine, morpholine, 2,6-dimethylmorpholine, piperidine, 2,6-dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 4-piperidone, pyrrolidine, 2,5-dimethylpyrrolidine, carbazole, indole, and indoline; and noncyclic secondary amines such as dimethylamine, diethylamine, and other noncyclic secondary amines which may have one or more substituents on the aromatic ring(s), such as N-methylaniline, N-ethylaniline, N-methylbenzylamine, N-methylphenethylamine, and diphenylamine derivatives.
- The imines are not particularly limited. Examples thereof include benzophenonimine and 4,4′-dimethoxybenzophenoneimine.
- The amides are not particularly limited. Examples thereof include 2-azetidinone (β-propiolactam), γ-butyrolactam, δ-valerolactam, ε-caprolactam, acetamide, propionamide, cyclohexanecarboxamide, benzamide, N-methylformamide, N-methylacetamide, N-ethylacetamide, N-methylcyclohexanecarboxamide, and N-methylbenzamide.
- The arylboric acid compounds and the arylborate ester compounds to be used in the invention are not particularly limited. Examples thereof include phenylboric acid, 4-methylphenylboric acid, 2-thienylboric acid, 2-furylboric acid, 2,3,4,5,6-pentafluorophenylboric acid, 2-fluorophenylboric acid, 3-fluorophnylboric acid, 4-fluorophenylboric acid, 2-chlorophenylboric acid, 3-chlorophenylboric acid, 4-chlorophenylboric acid, 2-bromophenylboric acid, 3-bromophenylboric acid, 4-bromophenylboric acid, 2-iodophenylboric acid, 3-iodophenylboric acid, 4-iodophenylboric acid, 2,4-difluorophenylboric acid, 2,5-difluorophenylboric acid, 2,6-difluorophenylboric acid, 3,4-difluorophenylboric acid, 3,5-difluorophenylboric acid, 4-trifluoromethylphenylboric acid, 3,5-bis(trifluoromethyl)phenylboric acid, 3-cyanophenylboric acid, 4-formylphenylboric acid, 4-methoxyphenylboric acid, 1-naphthylboric acid, 2-naphthylboric acid, ferrocenylboric acid, 4-hydroxyphenylboric acid, and the aryl borate ester compound (such as dimethyl, diethyl, dipropyl, diisoprpyl and pinacol ester) of the arylboric acid compound as defined above.
- The arylalkyne compounds to be used in the invention are not particularly limited. Examples thereof include acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, phenylacetylene, 2-propyn-1-ol, 3-butyn-1-ol, 2-methyl-3-butyn-2-ol, 1-ethynyl-cyclohexanol, and trimethylsilylacetylene.
- In the invention, the amine compound may be used so as to be present in the reaction system in an amount of from 0.1 to 50 mol per mol of the aryl compound (2) or in an amount of from 0.1 to 50 mol per mol of the leaving group on the ring structure of the aryl compound (2). However, from the standpoint of facilitating the recovery of the amine compound remaining unreacted, the amine compound is preferably used so as to be present in the reaction system in an amount of from 0.2 to 30 mol per mol of the aryl compound (2) or in an amount of from 0.2 to 60 mol per mol of the leaving group on the ring structure of the aryl compound (2).
- In the invention, the aryl boric acid compound or aryl borate ester compound may be used so as to be present in the reaction system in an amount of from 0.1 to 50 mol per mol of the aryl compound (2) or in an amount of from 0.1 to 50 mol per of the leaving group on the ring structure of the aryl compound (2). However, from the standpoint of facilitating the recovery of the aryl boric acid compound or aryl borate ester compound remaining unreacted, the aryl boric acid compound or aryl borate ester compound is preferably used so as to be present in the reaction system in an amount of from 0.2 to 30 mol per mol of the aryl compound (2) or in an amount of from 0.2 to 60 mol per mol of the leaving group on the ring structure of the aryl compound (2).
- In the invention, the alkyne compound may be used so as to be present in the reaction system in an amount of from 0.1 to 50 mol per mol of the aryl compound (2) or in an amount of from 0.1 to 50 mol per of the leaving group on the ring structure of the aryl compound (2). However, from the standpoint of facilitating the recovery of the alkyne compound remaining unreacted, the aryl boric acid compound or aryl borate ester compound is preferably used so as to be present in the reaction system in an amount of from 0.2 to 30 mol per mol of the aryl compound (2) or in an amount of from 0.2 to 60 mol per mol of the leaving group on the ring structure of the aryl compound (2).
- The base to be used in the invention is not particularly limited, and may be selected from inorganic bases and/or organic bases. Preferred examples thereof include alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride; alkali metal or alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, potassium phenoxide, lithium phenoxide, lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide; alkali metal phosphates such as lithium phosphate, potassium phosphate, and sodium phosphate; and tertiary amines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, tricyclohexylamine; and secondary amines such as diethylamine, dipropylamine, diisopropylamine, dibutylamine, and dicyclohexylamine. Besides being added as it is to the reaction system, such as a base may be supplied to the reaction system by in situ preparing it from an alkali metal, alkali metal hydride, alkali metal hydroxide, or alkali metal phosphate and an alcohol.
- The amount of the base to be used is preferably at least 0.5 mol per mol of the leaving group of the aryl compound (2). If the amount of the base is smaller than 0.5 mol, there are cases where the yield of an arylamine, a diaryl and an arylalkyne is reduced. Even when the base is added in large excess, the yield of an arylamine, a diaryl and an arylalkyne remains unchanged, resulting only in a complicated post-treatment after completion of the reaction. Consequently, the amount of the base to be added is more preferably in the range of from 1 to 5 mol.
- The reaction according to the invention is usually conducted in the presence of an inert solvent. The solvent to be used is not particularly limited as long as it does not considerably inhibit the reaction. Examples thereof include aliphatic organic solvents such as pentane, hexane, heptane, and octane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; aromatic organic solvents such as benzene, toluene, and xylene; ether type organic solvents such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, and dioxolane; and acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. Preferred of these are aromatic organic solvents such as benzene, toluene, and xylene and ether type organic solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane.
- In this reaction, the catalyst produces the same results when used by any of the following methods: a) a method in which a palladium compound; a base; an amine compound, an arylboric acid compound, an arylborate ester compound, or an alkyne compound; an aryl compound havng a leaving group; and the 2,2-(diaryl)vinylphosphine compound (1), which each has been described above, are charged into a reactor simultaneously; b) a method in which a palladium compound, the reaction substrate, and the 2,2-(diaryl)vinylphosphine compound (1) are separately charged into a reactor in the presence of a base; c) a method in which a palladium compound is mixed beforehand with the 2,2-(diaryl)vinylphosphine compound (1) in a reaction system to prepare a catalyst, and an aryl compound having a leaving group is then added to the reaction system in the presence of a base; and d) a method in which a palladium compound is mixed beforehand with the 2,2-(diaryl)vinylphosphine compound (1) to prepare a catalyst, and this catalyst and an aryl compound having a leaving group and this reaction substance are separately charged into a reactor.
- The amount of the palladium compound to be used for the amination reaction or the carbon-carbon bond formation reaction is generally from 0.001 to 20 mol %, preferably from 0.01 to 5 mol %, based on this reaction substance (the amine compound, the arylboric acid compound, the arylborate ester compound, or the alkyne compound). The amount of the 2,2-(diaryl)vinylphosphine compound to be used for this reaction is generally from 0.1 to 10 times by mol, preferably from 1 to 5 times by mol, the amount of the palladium compound.
- In the invention, a palladium compound and the 2,2-(diaryl)vinylphosphine compound (1) are indispensable.
- The amination reaction or the carbon-carbon bond formation reaction according to the invention may be conducted at ordinary pressure under an inert gas atmosphere such as nitrogen or argon, or may be conducted at an elevated pressure.
- The reaction according to the invention may be conducted at a temperature of generally from 10 to 300° C, preferably from 20 to 200° C.
- Although the reaction time in the invention varies depending on the amounts of the aryl compound (2), this reaction substance (the amine compound, the arylboric acid compound, the arylborate ester compound, or the alkyne compound), base, palladium compound, and 2,2-(diaryl)vinylphosphine compound (1) and on the reaction temperature, it may be selected in the range of from several minutes to 72 hours.
- After completion of the reaction, the reaction mixture is treated in an ordinary way, whereby the target compound can be obtained.
- The novel 2,2-(diaryl)vinylphosphine compound of the invention, when used together with a palladium compound, serves as the catalyst of an amination reaction or a carbon-carbon bond formation reaction to show excellent performances. When this catalyst is used in the amination reaction or the carbon-carbon formation reaction of an aryl compound having a leaving group, an arylamine, a diaryl or an arylalkyne can be efficiently produced in a shorter time period than in the amination reaction or the carbon-carbon bond formation reaction with any conventional amination catalyst or any conventional carbon-carbon bond formation reaction catalyst. It is hence an excellent catalyst for industrial use.
- The invention will be explained below in more detail by reference to Examples. However, the invention should not be construed as being limited by these Examples in any way.
- In the Examples, properties were determined using the following apparatus.
- 1)1H-NMR Spectrometry: Apparatus Type GEMINI 2000 (manufactured by Varian) or apparatus Type DRX-500 (manufactured by Varian).
- Internal standard substance: tetramethylsilane
- 2)31P-NMR Spectrometry: Apparatus Type DRX-500 (manufactured by Bruker)
- External standard substance: 85% phosphoric acid
- 3)19F-NMR Spectrometry: Apparatus Type DRX-500 (manufactured by Bruker)
- Internal standard substance: trifluoroacetic acid
- 4) Melting Point: Yanaco MP-500D (manufactured by Yanagimoto Shoji K. K.)
- 5) Gas Chromatograph: GC 353 (manufactured by GL Science)
- Column: NB-1 (30 m×0.25 mm) (manufactured by GL Science)
- Internal standard substance: o-terphenyl or tridecane
- 6) Mass Spectrometry (MS):
- Mass spectrometer M-80: Ionization voltage, 20 eV (manufactured by Hitachi Ltd.)
- (1) Synthesis of 1-Diphenylpropene
- Into a reactor were introduced 96.0 g (3.95 mol) of magnesium and 500 mL of tetrahydrofuran (hereinafter abbreviated as THF) under a nitrogen atmosphere. Iodine and bromobenzene were added to the mixture in a slight amount to ascertain initiation of a reaction. Thereafter, a mixture of 677 g (4.31 mol) of bromobenzene and 1,500 mL of THF was gradually added dropwise thereto while keeping the temperature of the system at about 40° C., and this mixture was refluxed for 1 hour. Thereto was gradually added dropwise 140 g (1.59 mol) of methyl propionate while keeping the temperature of the system at about 40° C. This mixture was stirred at 60° C. for 3 hours. The resultant reaction mixture was washed with 0.1 M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was dissolved in 800 mL of toluene, and 3.8 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted for 1.5 hours with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The resultant concentrate was recrystallized from methanol to obtain 230 g (75%) of the target compound as white crystals.
- Melting point: 48-49° C.1H-NMR (CDCl3) δ 1.76 (d, J=7.1 Hz, 3H), 6.17 (q, J=7.1 Hz, 1H), 7.08-7.44 (m, 10H)
- (2) Synthesis of 2-Bromo-1,1-diphenylpropene
- Into a reactor were introduced 19.4 g (100 mmol) of the 1,1-diphenylpropene and 78 mL of 1,2-dichloroethane under a nitrogen atmosphere. The contents were cooled to 0° C., and 15.9 g (100 mmol) of bromine was gradually added dropwise thereto. The resultant mixture was stirred at room temperature for 1 hour. Thereafter, 32.4 mL (400 mmol) of pyridine and 156 mL of toluene were added thereto and this mixture was stirred at 80° C. for 3 hours. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography and then recrystallized from methanol to obtain 14.5 g (53%) of the target compound as white crystals.
- Melting point: 46-47° C.1H-NMR (CDCl3) δ 2.43 (s, 3H), 7.14-7.38 (m, 10H)
- (3) Synthesis of 1,1-Diphenyl-2-(diphenylphosphino)propene (Exemplified Compound 20)
- Into a reactor were introduced 1.37 g (5.00 mmol) of the 2-bromo-1,1-diphenylpropene and 14 mL of THF under a nitrogen atmosphere. The contents were cooled to −70° C,. and 3.4 mL (5.5 mmol; 1.6 M hexane solution) of butyllithium was gradually added dropwise thereto. The resultant mixture was stirred for 30 minutes. Thereafter, 1.1 mL (6.0 mmol) of chlorodiphenylphosphine was added, and this mixture was heated to room temperature and then stirred for 13 hours. Water was added to the reaction mixture. The organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 1.08 g (60%) of the target compound as white crystals.
- Melting point: 128-130° C.1H-NMR (CDCl3) δ 1.70 (d, J=2.8 Hz, 3H), 7.12-7.47 (m, 20H) 31P-NMR (CDCl3) δ −4.68
- Into a reactor were introduced 8.50 g (31.1 mmol) of the 2-bromo-1,1-diphenylpropene obtained in Example 1 (2) and 85 mL of THF under a nitrogen atmosphere. The contents were cooled to −70° C. Thereto was gradually added dropwise 21.4 mL (34.2 mmol; 1.6 M hexane solution) of butyllithium. The resultant mixture was stirred for 30 minutes. Thereafter, 8.25 ml (37.3 mmol) of chlorodicyclohexylphosphine was added, and this mixture was stirred for 75 minutes, subsequently heated to room temperature, and then further stirred for 15.5 hours. Water was added to the reaction mixture. The organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 8.80 g (72%) of the target compound as white crystals.
- Melting point: 128-130° C.1H-NMR (CDCl3) δ 1.06-1.94 (m, 25H), 7.04-7.36 (m, 10H) 31P-NMR (CDCl3) δ −3.68
- Into a reactor were introduced 1.37 g (5.0 mmol) of the 2-bromo-1,1-diphenylpropene obtained in Example 1 (2), 0.134 g (5.5 mmol) of magnesium, and 11 mL of THF under a nitrogen atmosphere. Iodine and bromobenzene were added to the mixture in a slight amount to ascertain initiation of a reaction. Thereafter, the reaction mixture was refluxed for 2 hours and then cooled. Thereto were added 0.520 g (5.3 mmol) of copper chloride and 1.1 mL (5.5 mmol) of chlorodi-t-butylphosphine. This reaction mixture was refluxed for 18 hours and then cooled to room temperature. Thereto was added 14 mL of heptane. The crystals yielded were taken out by filtration and dissolved in 40 mL of ethyl acetate. The resultant solution was washed with 28% ammonia water and an aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 0.736 g (43%) of the target compound as white crystals.
- Melting point: 130-133° C.1H-NMR (CDCl3) δ 1.21 (s, 9H), 1.26 (s, 9H), 2.06 (d, J=1.4 Hz, 3H), 7.08-7.36 (m, 10H) 31 P-NMR (CDCl3) δ 30.13
- (1) Synthesis of 1,1-Bis(4-dimethylaminophenyl)propene
- Into a reactor was introduced 102 ml (82.0 mmol; 0.80 M THF solution) of ethylmagnesium bromide under a nitrogen atmosphere. The contents were cooled to 0° C. Thereto was gradually added dropwise a solution prepared by mixing 20.0 g (74.5 mmol) of 4,4′-bis(dimethylamino)benzophenone and 40 mL of THF. This mixture was stirred at room temperature for 5 hours. Saturated aqueous ammonium chloride solution was added to the resultant reaction mixture, and the metal salt yielded was removed by Celite filtration. The organic layer was separated from the filtrate and then extracted with toluene. Thereafter, the solvent was removed under reduced pressure. The concentrate was dissolved in 150 mL of toluene, and 0.1 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. This concentrate was purified by column chromatography to obtain 13.6 g (65%) of light-yellow crystals.
-
- (2) Synthesis of 1,1-Bis(4-dimethylaminophenyl)-2-bromopropene
- Into a reactor were introduced 13.6 g (48.5 mmol) of the 1,1-bis(4-dimethylaminophenyl)propene and 54 mL of 1,2-dichloroethane under a nitrogen atmosphere. The contents were cooled to 0° C. Thereto was gradually added dropwise 7.76 g (48.5 mmol) of bromine. The resultant mixture was stirred at room temperature for 2.5 hours. Thereafter, 15.7 mL (194 mmol) of pyridine and 109 mL of toluene were added thereto and this mixture was stirred at 80° C. for 3 hours. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. The concentrate was purified by column chromatography and then crystallized from methanol to obtain 12.0 g (69%) of the target compound as green-yellow crystals.
- Melting point: 119-122° C.1H-NMR (CDCl3) δ 2.46 (s, 3H) , 2.94 (s, 12H) , 6.58-6.70 (m, 4H), 6.96-7.20 (m, 4H)
- (3) Synthesis of 1,1-Bis(4-dimethylaminophenyl)-2-(diphenylphosphino)propene (Exemplified Compound 105)
- Into a reactor were introduced 3.0 g (8.3 mmol) of the 1,1-bis(4-dimethylaminophenyl)-2-bromopropene and 10 mL of THF under a nitrogen atmosphere. The contents were cooled to −60° C. Thereto was gradually added dropwise 5.2 mL (8.3 mmol; 1.6 M hexane solution) of butyllithium. The resultant mixture was stirred for 30 minutes. Thereafter, 1.1 mL (6.0 mmol) of chlorodiphenylphosphine was added thereto and this mixture was heated to room temperature and stirred for 16 hours. Water was added to the reaction mixture. The resultant mixture was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized twice from hexane/ethanol to obtain 1.9 g (60%) of the target compound as white crystals.
- Melting point: 95-97° C.1H-NMR (CDCl3) δ 1.73 (d, J=2.8 Hz, 3H) 2.91 (s, 6H), 2.95 (s, 6H), 6.52-6.69 (m, 4H), 6.97-7.10 (m, 4H), 7.18-7.49 (m, 10H) 31P-NMR (CDCl3) δ −2.79
- Into a reactor were introduced 1.44 g (4.00 mmol) of the 1,1-bis(4-dimethylaminophenyl)-2-bromopropene obtained in Example 4 (2) and 14 mL of THF under a nitrogen atmosphere. The contents were cooled to −60° C. Thereto was gradually added dropwise 2.8 mL (4.4 mmol; 1.6 M hexane solution) of butyllithium. The resultant mixture was stirred at that temperature for 1 hour. Thereafter, 0.97 mL (4.4 mmol) of chlorodicyclohexylphosphine was added thereto, and this mixture was stirred for 30 minutes, subsequently heated to room temperature, and then further stirred for 17 hours. Water was added to the reaction mixture. The organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol and hexane to obtain 0.44 g (23%) of the target compound as white crystals.
- Melting point: 159-164° C.1H-NMR (CDCl3) δ 1.04-2.15 (m, 25H), 2.91 (s, 6H), 2.92 (s, 6H), 6.50-6.75 (m, 4H), 6.85-7.08 (m, 4H) 31P-NMR (CDCl3) δ −2.19
- Into a reactor were introduced 1.44 g (4.00 mmol) of the 1,1-bis(4-dimethylaminophenyl)-2-bromopropene obtained in Example 4 (2), 0.107 g (4.4 mmol) of magnesium, and 11.5 mL of THF under a nitrogen atmosphere. A slight amount of iodine was added to the mixture to ascertain initiation of a reaction. Thereafter, the reaction mixture was refluxed for 2 hours and then cooled. Thereto were added 0.416 g (4.2 mmol) of copper chloride and 0.91 mL (4.4 mmol) of chlorodi-tert-butylphosphine. The reaction mixture was refluxed for 18 hours and then cooled to room temperature. Thereto were added 22.5 mL of heptane and 7.5 ml of diethyl ether. The crystals yielded were taken out by filtration and dissolved in 30 mL of ethyl acetate. The resultant solution was washed with 28% ammonia water and an aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 0.34 g (20%) of the target compound as white crystals.
- Melting point: 133-135° C.1H-NMR (CDCl3) δ 1.21 (s, 9H), 1.26 (s, 9H), 2.21 (d, J=1.6 Hz, 3H), 2.91 (s, 6H), 2.92 (s, 6H), 6.50-6.69 (m, 4H), 6.91-7.04 (m, 4H) 31P-NMR (CDCl3) δ 31.68
- (1) Synthesis of 1,1-Diphenylethylene
- Into a reactor were introduced 31.6 g (1.30 mol) of magnesium and 50 mL of THF under a nitrogen atmosphere. Iodine and ethyl bromide were added to the mixture in a slight amount to ascertain initiation of a reaction. Thereafter, 600 mL of THF was added thereto, and methyl chloride gas having a regulated temperature was bubbled into the resultant mixture at a regulated rate so as to keep the mixture at 30 to 40° C. After heat generation ended and the magnesium metal was ascertained to have disappeared, the reaction mixture was stirred at that temperature for 1 hour. Subsequently, a mixture of 182 g (1.10 mol) of benzophenone and 364 mL of THF was gradually added dropwise thereto at 35 to 40° C. and this mixture was stirred for 15 hours. This reaction mixture was cooled and then poured into 10% aqueous ammonium chloride solution. The resultant mixture was stirred for 30 minutes. After liquid separation, the organic layer was washed with an aqueous sodium chloride solution and water, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. To the concentrate were added 400 mL of toluene and 1 g of p-toluenesulfonic acid monohydrate. The resultant solution was subjected to azeotropic dehydration for 2 hours with toluene refluxing. After being cooled, the reaction mixture was washed with 2% aqueous sodium carbonate solution and water and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by distillation to obtain 174 g (97%) of the target compound.
- Melting point: 103° C./134 Pa (1 mmHg)
- (2) Synthesis of 1-Bromo-2,2-diphenylethylene
- Into a reactor were introduced 110 g (0.60 mol) of the 1,1-diphenylethylene and 1,098 g of carbon tetrachloride under a nitrogen atmosphere. A solution prepared by mixing 95.9 g (0.60 mol) of bromine with 288 g of carbon tetrachloride was added dropwise thereto over 1 hour with cooling with ice. After completion of the addition, the reaction mixture was stirred at that temperature for 7 hours and then concentrated. To the residue were added 119 g of pyridine and 500 mL of toluene. This mixture was refluxed for 3 hours. After being cooled, the reaction mixture was washed with 5% hydrochloric acid and water, subsequently dried with anhydrous sodium sulfate, and then concentrated under reduced pressure. The resultant concentrate was distilled and then recrystallized from methanol to obtain 126 g (81%) of the target compound as white crystals.
- Melting point: 45° C.1H-NMR (CDCl3) δ 6.77 (s, 1H), 7.15-7.47 (m, 10H)
- (3) Synthesis of 2,2-Diphenyl-1-(diphenylphosphino)ethylene (Exemplified Compound 10)
- The same procedure as in Example 1 (3) was conducted, except that 1.30 g (5.00 mmol) of 2-bromo-1,1-diphenylethylene was used in place of 2-bromo-1,1-diphenylpropene. Thus, 1.03 g (57%) of the target compound was obtained as white crystals.
- Melting point: 116-118° C.1H-NMR (CDCl3) δ 6.85 (d, J=3.4 Hz, 1H), 7.16-7.50 (m, 20H) 31P-NMR (CDCl3) δ −23.01
- (1) Synthesis of 1,1-Diphenyl-3-methylbutene
- Into a reactor were introduced 2.92 g (120 mmol) of magnesium and 100 mL of THF under a nitrogen atmosphere. Iodine and bromobenzene were added to the mixture in a slight amount to ascertain initiation of a reaction. Thereafter, 17.3 g (110 mmol) of bromobenzene was gradually added dropwise thereto and the resultant mixture was refluxed for 10 minutes. Subsequently, 6.51 g (50.0 mmol) of ethyl isovalerate was gradually added dropwise to the reaction mixture while keeping the temperature of the system at about 40° C., and this mixture was refluxed for 3 hours. The resultant reaction mixture was washed with 0.1 M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was dissolved in 50 mL of toluene, and 0.05 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted for 2 hours with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 8.81 g (79%) of a transparent oily substance.
-
- (2) Synthesis of 2-Bromo-1,1-diphenyl-3-methylbutene
- Into a reactor were introduced 8.81 g (39.6 mmol) of the 1,1-diphenyl-3-methylbutene and 35 mL of 1,2-dichloroethane under a nitrogen atmosphere. The contents were cooled to 0° C., and 6.33 g (39.6 mmol) of bromine was gradually added dropwise thereto. This mixture was stirred at room temperature for 1 hour. The resultant reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol and ethyl acetate to obtain 8.64 g (72%) of the target compound as white crystals.
- Melting point: 112-114° C.1H-NMR (CDCl3) δ 1.11 (d, J=6.6 Hz, 6H), 2.87 (septet, J=6.6 Hz, 1H), 7.13-7.38 (m, 10H)
- (3) Synthesis of 1,1-Diphenyl-2-(dicyclohexylphosphino)-3-methylbutene (Exemplified Compound 49)
- Into a reactor were introduced 1.20 g (4.00 mmol) of the 2-bromo-1,1-diphenyl-3-methylbutene and 12 mL of THF under a nitrogen atmosphere. The contents were cooled to −70° C., and 2.8 mL (4.4 mmol; 1.6 M hexane solution) of butyllithium was gradually added dropwise thereto. The resultant mixture was stirred at that temperature for 30 minutes. Thereafter, 1.1 mL (4.8 mmol) of chlorodicyclohexylphosphine was added thereto, and this mixture was stirred at that temperature for 3 hours and then heated to room temperature over 13 hours. Water was added to the reaction mixture. The organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol and toluene to obtain 0.72 g (43%) of the target compound as white crystals.
- Melting point: 162-163° C.1H-NMR (CDCl3) δ 0.86-2.18 (m, 22H), 1.23 (d, J=7.0 Hz, 6H), 2.63-2.92 (m, 1H), 7.05-7.33 (m, 10H) 31P-NMR (CDCl3) δ −1.46
- (1) Synthesis of 1,1,2-Triphenylethylene
- Into a reactor was introduced 47 mL (55 mmol; 1.06 M THF solution) of benzylmagnesium chloride under a nitrogen atmosphere. The contents were cooled to 0° C. Thereafter, a solution prepared by mixing 9.11 g (50.0 mmol) of benzophenone with 18 mL of THF was gradually added dropwise thereto, and this mixture was stirred at room temperature for 1 hour. The resultant reaction mixture was washed with 0.1 M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was dissolved in 46 mL of toluene, and 0.18 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted for 2 hours with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 12.5 g (98%) of a transparent oily substance.
-
- (2) Synthesis of 1-Bromo-1,2,2-triphenylethylene
- Into a reactor were introduced 12.5 g (48.8 mmol) of the 1,1,2-triphenylethylene and 50 mL of 1,2-dichloroethane under a nitrogen atmosphere. The contents were cooled to 0° C., and 7.80 g (48.8 mmol) of bromine was gradually added dropwise thereto. This mixture was stirred at room temperature for 1 hour. The resultant reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution, saturated aqueous sodium thiosulfate solution, and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The resultant concentrate was recrystallized from ethanol and ethyl acetate to obtain 11.3 g (69%) of the target compound as white crystals.
- Melting point: 116-118° C.1H-NMR (CDCl3) δ 6.91-7.42 (m, 15H)
- (3) Synthesis of 1,2,2-Triphenyl-1-(dicyclohexylphosphino)ethylene (Exemplified Compound 99)
- Into a reactor were introduced 1.68 g (5.0 mmol) of the 1-bromo-1,2,2-triphenylethylene, 0.134 g (5.5 mmol) of magnesium, and 13 mL of THF under a nitrogen atmosphere. Iodine and bromobenzene were added to the mixture in a slight amount to ascertain initiation of a reaction. Thereafter, the reaction mixture was refluxed for 2 hours and then cooled. Thereto were added 0.520 g (5.3 mmol) of copper chloride and 1.2 mL (5.5 mmol) of chlorodicyclohexylphosphine. This reaction mixture was refluxed for 17 hours and then cooled to room temperature. Thereto was added 17 mL of heptane. The crystals yielded were taken out by filtration and dissolved in 40 mL of ethyl acetate. The resultant solution was washed with 28% ammonia water and an aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 1.34 g (59%) of the target compound as white crystals.
- Melting point: 121-123° C.1H-NMR (CDCl3) δ 0.94-2.00 (m, 22H), 6.84-7.40 (m, 15H) 31P-NMR (CDCl3) δ −0.979
- (1) Synthesis of 1,1-Bis(4-methoxyphenyl)propanol
- Into a reactor were introduced 31.9 mL (30.9 mmol; 0.97 M THF solution) of ethylmagnesium chloride and 20 mL of THF under a nitrogen atmosphere. The contents were cooled to 4° C. Thereafter, a solution prepared by mixing 5.00 g (20.6 mmol) of 4,4′-dimethoxybenzophenone with 20 mL of THF was gradually added dropwise thereto, and this mixture was stirred at room temperature for 1 hour. Saturated aqueous ammonium chloride solution was added to the reaction mixture. The organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate and then concentrated under reduced pressure. The concentrate was purified by column chromatography to obtain 3.06 g (55%) of the target compound as a light-yellow oily substance.
-
- (2) Synthesis of 1,1-Bis(4-methoxyphenyl)propene
- Into a reactor were introduced 2.86 g (10.5 mmol) of the 1,1-bis(4-methoxyphenyl)propanol, 40 mL of toluene, and 28 mg of p-toluenesulfonic acid monohydrate under a nitrogen atmosphere. Azeotropic dehydration was conducted for 2 hours with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 2.60 g (97%) of the target compound as light-yellow crystals.
- Melting point: 99-100° C.1H-NMR (CDCl3) δ 1.75 (d, J=7.0 Hz, 3H), 3.79 (s, 3H) 3.84 (s, 3H), 6.03 (q, J=7.0 Hz, 1H), 6.78-6.81 (m, 2H), 6.90-6.92 (m, 2H), 7.09-7.11 (m, 2H), 7.13-7.16 (m, 2H)
- (3) Synthesis of 1,1-Bis(4-methoxyphenyl)-2-bromopropene
- Into a reactor were introduced 2.50 g (9.82 mmol) of the 1,1-bis(4-methoxyphenyl)propene and 25 ml of 1,2-dichloroethane under a nitrogen atmosphere. The contents were cooled to −20° C. A mixture of 1.57 g (9.82 mmol) of bromine and 13 mL of 1,2-dichloroethane was gradually added dropwise thereto, and the resultant mixture was stirred overnight at room temperature. This reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure to obtain 3.26 g (100%) of the target compound as a light-yellow oily substance.
-
- (4) Synthesis of 1,1-Bis(4-methoxyphenyl)-2-(diphenylphosphino)propene (Exemplified Compound 103)
- Into a reactor were introduced 2.00 g (6.00 mmol) of the 1,1-bis(4-methoxyphenyl)-2-bromopropene and 30 mL of THF under a nitrogen atmosphere. The contents were cooled to −65° C., and 4.0 mL (6.0 mmol; 1.5 M hexane solution) of butyllithium was gradually added dropwise thereto. The resultant mixture was stirred for 30 minutes. Thereafter, 0.90 mL (5.0 mmol) of chlorodiphenylphosphine was added, and this mixture was stirred at that temperature for 1 hour and then at room temperature for 1 hour. Saturated aqueous ammonium chloride solution was added to the reaction mixture. The resultant mixture was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 1.45 g (66%) of the target compound as white crystals.
- Melting point: 123-125° C.1H-NMR (CDCl3) δ 1.71 (d, J=2.9 Hz, 3H) , 3.76 (s, 3H) 3.79 (s, 3H), 6.74-6.77 (m, 2H), 6.82-6.85 (m, 2H), 7.05-7.10 (m, 4H), 7.32-7.40 (m, 10H) 31P-NMR (CDCl3) δ −3.73
- (1) Synthesis of 1,1-Bis(4-fluorophenyl)propanol
- Into a reactor were introduced 10.0 g (40.6 mmol) of cerium chloride and 80 mL of THF under a nitrogen atmosphere. This mixture was stirred at room temperature for 20 hours and then cooled to 0° C. Thereto was added dropwise 25.1 mL (24.3 mmol; 0.97 M THF solution) of ethylmagnesium chloride over 30 minutes. Subsequently, a solution prepared by mixing 3.54 g (16.2 mmol) of 4,4′-difluorobenzophenone with 20 mL of THF was added dropwise thereto over 40 minutes, and this mixture was stirred for 1 hour. To the resultant reaction mixture was added 10% aqueous acetic acid solution. Thereafter, the mixture was extracted with ethyl acetate, and the resultant organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. The concentrate was purified by column chromatography to obtain 3.12 g (78%) of the target compound as a light-yellow oily substance.
-
- (2) Synthesis of 1,1-Bis(4-fluorophenyl)propene
- Into a reactor were introduced 2.80 g (11.3 mmol) of the 1,1-bis(4-fluorophenyl)propanol, 60 mL of toluene, and 14 mg of p-toluenesulfonic acid monohydrate under a nitrogen atmosphere. Azeotropic dehydration was conducted for 1 hour with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 2.39 g (92%) of the target compound as white crystals.
- Melting point: 43-44° C.1H-NMR (CDCl3) δ 1.74 (d, J=7.0 Hz, 3H), 6.09 (q, J=7.0 Hz, 1H), 6.91-6.96 (m, 2H), 7.04-7.08 (m, 2H), 7.10-7.17 (m, 4H)
- (3) Synthesis of 1,1-Bis(4-fluorophenyl)-2-bromopropene
- Into a reactor were introduced 2.00 g (8.69 mmol) of the 1,1-bis(4-fluorophenyl)propene and 25 mL of 1,2-dichloroethane under a nitrogen atmosphere. The contents were cooled to −20° C. A mixture of 1.39 g (8.69 mmol) of bromine and 12 mL of 1,2-dichloroethane was added dropwise thereto over 1 hour, and the resultant mixture was stirred at that temperature for 1 hour and then at room temperature for 16 hours. Subsequently, a solution prepared by mixing 0.703 mL (8.69 mmol) of pyridine with 20 mL of toluene was added dropwise thereto over 15 minutes, and this mixture was stirred at 100° C. for 2 hours and then cooled. Saturated aqueous sodium hydrogen carbonate solution was added to the resultant reaction mixture, which was then extracted with toluene. The resultant organic layer was washed with saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 1.21 g (45%) of the target compound as white crystals.
- Melting point: 53-54° C.1H-NMR (CDCl3) δ 2.42 (s, 3H), 6.98-7.03 (m, 4H), 7.11-7.13 (m, 2H), 7.19-7.23 (m, 2H)
- (4) Synthesis of 1,1-Bis(4-fluorophenyl)-2-(diphenylphosphino)propene (Exemplified Compound 107)
- Into a reactor were introduced 0.907 g (2.93 mmol) of the 1,1-bis(4-fluorophenyl)-2-bromopropene and 20 mL of THF under a nitrogen atmosphere. The contents were cooled to −65° C., and 2.0 mL (2.9 mmol; 1.5 M hexane solution) of butyllithium was gradually added dropwise thereto. The resultant mixture was stirred for 40 minutes. Thereafter, a mixture of 0.58 mL (3.2 mmol) of chlorodiphenylphosphine and 5 mL of THF was added thereto, and the resultant mixture was stirred at that temperature for 2 hours and then heated to room temperature. Saturated aqueous ammonium chloride solution was added to the reaction mixture, which was then extracted with ethyl acetate. The resultant organic layer was washed with water and saturated aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from methanol to obtain 0.687 g (57%) of the target compound as white crystals.
- Melting point: 88-90° C.1H-NMR (CDCl3) δ 1.63 (d, J=2.8 Hz, 3H) , 6.81-6.87 (m, 2H), 6.90-6.96 (m, 2H), 7.00-7.08 (m, 4H), 7.25-7.32 (m, 10H) 31P-NMR (CDCl3) δ −4.40 19F-NMR (CDCl3) δ−115.0, −114.9
- Into a reactor were introduced 0.85 g (5.0 mmol) of diphenylamine and 0.76 g of o-terphenyl as an internal standard substance under a nitrogen atmosphere. Thereto was added 10 mL of toluene to dissolve those ingredients. To this solution were added 0.53 g (5.5 mmol) of sodium t-butoxide, 0.95 mL (5.5 mmol) of 1-bromo-4-tert-butylbenzene, 2.8 mg (0.25 mol % based on the amine) of palladium acetate, and 23.2 mg (1.0 mol % based on the amine) of the 1,1-bis(4-dimethylaminophenyl)-2-(diphenylphosphino)propene obtained in Example 4. This mixture was stirred at 100° C. for 8 hours and then cooled. The resultant reaction mixture was analyzed by gas chromatography to determine the amount of diphenyl(4-tert-butylphenyl)amine as the target compound by the internal-standard determination method. The results obtained are shown in Table 18.
-
- The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 2.3 mg (0.25 mol % based on the amine) of (π-allyl)palladium chloride. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 4.8 mg (0.25 mol % based on the amine) of dichlorobis(benzonitrile)palladium. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 3.8 mg (0.25 mol % based on the amine) of palladium acetylacetonate. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 14.4 mg (0.25 mol % based on the amine) of tetrakis(triphenylphosphine)palladium. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
- The same procedure as in Example 12 was conducted, except that the palladium compound was replaced with 5.7 mg (0.25 mol % based on the amine) of tris(dibenzylideneacetone)dipalladium. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 18.
TABLE 18 Example Palladium Yield (%) Example 12 Pd(OAc)2 85 Example 13 [(n-allyl)PdCl]2 83 Example 14 (C6H5CN)2PdCl2 86 Example 15 Pd(acac)2 78 Example 16 Pd(PPh3)4 83 Example 17 Pd2(dba)3 78 - The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 20.7 mg (1.0 mol % based on the amine) of the 1,1-bis(4-dimethylaminophenyl)-2-(diphenylphosphino)propene obtained in Example 4. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 18.9 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(diphenylphosphino)propene obtained in Example 1. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 19.5 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2 and that the reaction time was changed to 3 hours. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine and palladium acetate were replaced with 19.5 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(di-t-butylphosphino)propene obtained in Example 3 and 2.3 mg (1.0 mol % based on the amine) of (π-allyl)palladium chloride, respectively, and that the reaction time was changed to 3 hours. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 18.2 mg (1.0 mol % based on the amine) of the 2,2-diphenyl-1-(diphenylphosphino)ethylene obtained in Example 7. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 23.8 mg (1.0 mol % based on the amine) of the 1,1-bis(4-dimethylaminophenyl)-2-(dicyclohexylphosphino)propene obtained in Example 5 and that the reaction time was changed to 3 hours. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 21.2 mg (1.0 mol % based on the amine) of the 1,1-bis(4-dimethylaminophenyl)-2-(di-t-butylphosphino)propene obtained in Example 6. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 20.9 mg (1.0 mol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)-3-methylbutene obtained in Example 8. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 22.6 mg (1.0 mol % based on the amine) of the 1,2,2-triphenyl-1-(dicyclohexylphosphino)ethylene obtained in Example 9. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 13.1 mg (1.0 mol % based on the amine) of triphenylphosphine. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 15.2 mg (1.0 mol % based on the amine) of tris(o-tolyl)phosphine. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 11.7 mg (1.0 mol % based on the amine) of BINAP (2,2-bis(diphenylphosphino)-1,1′-binaphthyl). The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 14.0 mg (1.0 mol % based on the amine) of triscyclohexylphosphine. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
- The same procedure as in Example 12 was conducted, except that the phosphine was replaced with 10.6 mg (1.0 mol % based on the amine) of vinyldiphenylphosphine. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. The results obtained are shown in Table 19.
TABLE 19 Time Yield Phosphine (hr) (%) Example 18 (4-Me2N—C6H4)2C═C(Me)PPh2 8 85 Example 19 Ph2C═C(Me)PPh2 8 88 Example 20 Ph2C═C(Me)PCy2 3 96 Example 21 Ph2C═C(Me)P—tBu2 3 89 Example 22 Ph2C═C(H)PPh2 8 45 Example 23 (4-Me2N—C6H4)2C═C(Me)PCy2 3 87 Example 24 (4-Me2N—C6H4)2C═C(Me)P—tBu2 8 88 Example 25 Ph2C═C(iPr)PCy2 8 45 Example 26 Ph2C═C(Ph)PCy2 8 40 Comparative Ph3P 8 10 Example 1 Comparative (o-tolyl)3P 8 30 Example 2 Comparative BINAP 8 22 Example 3 Comparative Cy3P 8 37 Example 4 Comparative Vinyl-PPh2 8 1 Example 5 - Table 19 shows that when the 2,2-(diaryl)vinylphosphine compounds according to the invention (Examples 18 to 26) were used to conduct an amination reaction, the target arylamine could be obtained in high yield. In contrast, when triphenylphosphine (Comparative Example 1), tris(o-tolyl)phosphine (Comparative Example 2), BINAP (Comparative Example 3), triscyclohexylphosphine (Comparative Example 4), and vinyldiphenylphosphine (Comparative Example 5) were used as phosphines in place of the 2,2-(diaryl)vinylphosphine compounds of the invention to conduct the reaction, the yield of the target arylamine was as low as 37% at the most.
- As demonstrated above, those 2,2-(diaryl)vinylphosphine compounds according the invention are exceedingly useful phosphines in completing the amination reaction of the invention.
- Into a reactor were introduced 0.214 g (2.00 mmol) of p-toluidine and 4 mL of dioxane under a nitrogen atmosphere. The amine was dissolved in the solvent. To this solution were added 0.515 g (2.2 mmol) of p-iodoanisole, 0.231 g (2.4 mmol) of sodium t-butoxide, 4.5 mg (1 mol % based on the amine) of palladium acetate, and 15.6 mg (2 mmol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2. The resultant reaction mixture was stirred at 100° C. for 8 hours and then cooled. Saturated aqueous ammonium chloride solution was added thereto, and this mixture was extracted with toluene. The extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography to obtain 0.351 g (82%) of N-p-methoxyphenyl-N-p-tolylamine as yellow crystals. The results obtained are shown in Table 20.
- Melting point: 81-82° C.1H-NMR (CDCl3) δ 2.74 (s, 3H) , 3.79 (s, 3H), 5.38 (br-s, 1H), 6.78-6.91 (m, 4H), 6.96-7.09 (m, 4H)
- Into a reactor were introduced 0.330 g (1.93 mmol) of p-tolyl bromide and 4 mL of toluene under a nitrogen atmosphere. The bromide was dissolved in the solvent. To this solution were added 0.266 g (2.16 mmol) of p-anisidine, 0.226 g (2.35 mmol) of sodium t-butoxide, 8.5 mg (1 mol % based on the amine) of tris(dibenzylidene)dipalladium, and 32.3 mg (2 mmol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2. The resultant reaction mixture was stirred at 100° C. for 5 hours and then cooled. Saturated aqueous ammonium chloride solution was added thereto, and this mixture was extracted with toluene. The extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography to obtain 0.366 g (89%) of N-p-methoxyphenyl-N-p-tolylamine. The results obtained are shown in Table 20.
- Into a reactor were introduced 0.466 g (2.00 mmol) of 4-bromobiphenyl and 4 mL of toluene under a nitrogen atmosphere. The bromobiphenyl was dissolved in the solvent. To this solution were added 0.399 g (2.2 mmol) of benzophenonimine, 0.231 g (2.4 mmol) of sodium t-butoxide, 13.5 mg (3 mol % based on the amine) of palladium acetate, and 46.9 mg (6 mmol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2. The resultant reaction mixture was stirred at 100° C. for 16 hours and then cooled. Saturated aqueous ammonium chloride solution was added thereto, and this mixture was extracted with toluene. The extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography to obtain 0.409 g (61%) of N-(diphenylmethylene)-4-aminobiphenyl as a yellow oily substance. The results obtained are shown in Table 20.
-
- Into a reactor were introduced 0.275 g (2.00 mmol) of 4-chlorobenzonitrile and 4 mL of toluene under a nitrogen atmosphere. The nitrile was dissolved in the solvent. To this solution were added 0.192 g (2.2 mmol) of morpholine, 0.231 g (2.4 mmol) of sodium t-butoxide, 4.5 mg (1 mol % based on the amine) of palladium acetate, and 15.6 mg (2 mmol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2. The resultant reaction mixture was stirred at 100° C. for 14 hours and then cooled. Saturated aqueous ammonium chloride solution was added thereto, and this mixture was extracted with toluene. The extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography to obtain 0.304 g (81%) of N-(4-cyanophenyl)morpholine as light-yellow crystals. The results obtained are shown in Table 20.
- Melting point: 80-81° C.1H-NMR (CDCl3) δ 3.23-3.33 (m, 4H), 3.80-3.90 (m, 4H), 6.81-6.92 (m, 2H), 7.47-7.57 (m, 2H)
- Into a reactor were introduced 0.503 g (2.10 mmol) of p-tolyl triflate and 4 mL of dioxane under a nitrogen atmosphere. The triflate was dissolved in the solvent. To this solution were added 0.246 g (2.29 mmol) of p-toluidine, 0.658 g (3.10 mmol) of potassium phosphate, 19.9 mg (2.1 mol % based on the triflate) of tris(dibenzylideneacetone)dipalladium, and 58.7 mg (7.2 mmol % based on the triflate) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2. The resultant reaction mixture was stirred at 100° C. for 12 hours and then cooled. Saturated aqueous ammonium chloride solution was added thereto, and this mixture was extracted with toluene. The extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography to obtain 0.268 g (65%) of ditolylamine. The results obtained are shown in Table 20.
- Melting point: 78-82° C.1H-NMR (CDCl3) δ 2.32 (s, 6H), 5.51 (br-s, 1H), 6.88-7.17 (m, 8H)
- Into a reactor were introduced 0.358 g (2.20 mmol) of 3-bromothiophene and 4 mL of toluene under a nitrogen atmosphere. The bromothiophene was dissolved in the solvent. To this solution were added 0.343 g (2.03 mmol) of diphenylamine, 0.229 g (2.39 mmol) of sodium t-butoxide, 4.4 mg (1 mol % based on the amine) of palladium acetate, and 30.6 mg (2 mmol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2. The resultant reaction mixture was stirred at 100° C. for 10 hours and then cooled. Saturated aqueous ammonium chloride solution was added thereto, and this mixture was extracted with toluene. The extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography to obtain 0.257 g (50%) of N-(3-thiophenyl)-N,N-diphenylamine. The results obtained are shown in Table 20.
- Melting point: 79-82° C.1H-NMR (CDCl3) δ 6.66 (d/d, J=1.4, 3.1 Hz, 1H), 6.88 (d/d, J=1.4, 5.1 Hz, 1H), 6.94-7.36 (m, 11H)
- The same procedure as in Example 27 was conducted, except that the phosphine was replaced with 4.2 mg (1.0 mol % based on the amine) of vinyldiphenylphosphine. The amount of N-p-methoxyphenyl-N-p-tolylamine as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield was found to be 5%. The results obtained are shown in Table 20.
- The same procedure as in Example 28 was conducted, except that the phosphine was replaced with 4.2 mg (1.0 mol % based on the amine) of vinyldiphenylphosphine. The amount of N-p-methoxyphenyl-N-p-tolylamine as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield was found to be 5%. The results obtained are shown in Table 20.
TABLE 20 Aryl Yield Example compound Amine Product (%) Example 27 82 Comparative Example 6 5 Example 28 89 Comparative Example 7 5 Example 29 61 Example 30 81 Example 31 65 Example 32 50 - Table 20 shows that when the 2,2-(diaryl)vinylphosphine compound according to the invention (Examples 27 to 32) was used to conduct amination reactions, the target arylamines could be obtained in high yields. In contrast, when vinyldiphenylphosphine (Comparative Examples 6 and 7) was used as a phosphine in place of the 2,2-(diaryl)vinylphosphine compound of the invention to conduct amination reactions, the yield of the target arylamines was as low as 5%.
- As demonstrated above, that 2,2-(diaryl)vinylphosphine compound according the invention is an exceedingly useful phosphine in completing the amination reaction of the invention.
- Into a reactor were introduced 0.183 g (0.5 mmol) of (π-allyl)palladium chloride dimer, 0.338 g (1.0 mmol) of the 1,1-diphenyl-2-(di-t-butylphosphino)propene obtained in Example 3, and 3 mL of toluene under a nitrogen atmosphere. The contents were stirred at room temperature for 62 hours. To the resultant reaction mixture was added 3 mL of heptane. This mixture was stirred for 30 minutes. The crystals yielded were taken out by filtration and dried to obtain 0.25 g (48%) of the target compound.
-
- The same procedure as in Example 12 was conducted, except that the palladium compound and phosphine were replaced with the [1,1-diphenyl-2-(di-tert-butylphosphino)propene](π-allyl)palladium chloride (palladium-phosphine catalyst) obtained in Example 33. The amount of diphenyl(4-tert-butylphenyl)amine as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield of the target compound was 90%.
- Into a reactor were introduced 0.123 ml (1.0 mmol) of 1-bromotoluene, 0.1829 g (1.5 mmol) of phenylboric acid, 87.2 mg (1.5 mmol) of potassium fluoride, 4.5 mg (0.02 mmol) of palladium acetate, 11.7 mg (0.03 mmol) of the 1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example 2, and 3.0 ml of dioxane under a nitrogen atmosphere. The resultant reaction mixture was stirred at room temperature for 20 hours. The amount of 4-methylbiphenyl as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield was found to be 70%.
-
- Into a reactor were introduced 0.123 ml (1.0 mmol) of 1-bromotoluene, 0.1829 g (1.5 mmol) of phenylboric acid, 87.2 mg (1.5 mmol) of potassium fluoride, 4.5 mg (0.02 mmol) of palladium acetate, 11.7 mg (0.03 mmol) of the 1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example 2, and 3.0 ml of dioxane under a nitrogen atmosphere. The resultant reaction mixture was stirred at 80° C. for 4 hours. The amount of 4-methylbiphenyl as the target compound was determined by the internal-standard determination method by gas chromatography. As a result, the yield was found to be 95%.
- Into a reactor were introduced 0.79 g (5.0 mmol) of 2-bromo-pyridine, 0.73 g (6.0 mmol) of phenylboric acid, 1.38 g (10.0 mmol) of potassium carbonate, 11.2 mg (0.05 mmol) of palladium acetate, 39.1 mg (0.1 mmol) of the 1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example 2, 5.0 ml of water, and 15.0 ml of toluene under a nitrogen atmosphere. The resultant reaction mixture was stirred at 80° C. for 4 hours and then cooled. Thereafter, the solvent was removed under pressure. The concentrate was purified by column chromatography to obtain 0.66 g (85%) of 2-phenylpyridine as the target compound.
-
- Into a reactor were introduced 1.38 g (10.0 mmol) of 4-chlorobenzonitrile, 1.68 g (20.0 mmol) of 2-methyl-3-butyne-2-ol, 2.7 mg (0.015 mmol) of palladium, 1.4 mg (0.0075 mmol) of copper iodide, 17.6 mg (0.045 mmol) of the 1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example 2, 4.0 mL (0.055 mmol) of diisopropylamine, and 4.0 ml of N,N-dimethylformamide under a nitrogen atmosphere. The resultant reaction mixture was stirred at 100° C. for 23 hours and then cooled. Thereafter, the solvent was removed under pressure. The concentrate was purified by column clromatography to obtain 1.56 g (84%) of 4-(4-cyanophenyl)-2-methyl-3-butyne-2-ol as white crystals.
-
- While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
- This application is based on Japanese patent application No. 2000-194690 filed on Jun. 28, 2000, the entire contents thereof being hereby incorporated by reference.
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2000194690 | 2000-06-28 | ||
JP2000-194690 | 2000-06-28 |
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US20020058837A1 true US20020058837A1 (en) | 2002-05-16 |
US6455720B1 US6455720B1 (en) | 2002-09-24 |
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US09/891,304 Expired - Lifetime US6455720B1 (en) | 2000-06-28 | 2001-06-27 | 2,2(diarlyl)vinylphosphine compound, palladium catalyst thereof, and process for producing arylamine, diaryl, or arylalkyne with the catalyst |
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US (1) | US6455720B1 (en) |
EP (1) | EP1167372B1 (en) |
KR (1) | KR100641597B1 (en) |
DE (1) | DE60101423T2 (en) |
TW (1) | TW591034B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100298569A1 (en) * | 2007-09-28 | 2010-11-25 | Marc Taillefer | Use of cyclovinyl phosphine/copper complexes as arylation catalysts |
CN103739421A (en) * | 2013-12-17 | 2014-04-23 | 大连世慕化学有限公司 | 1,1-stilbene derivative and preparation method |
CN111423369A (en) * | 2018-12-21 | 2020-07-17 | 陕西师范大学 | Esterase activated aggregation-induced emission type anticancer prodrug and preparation method thereof |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10250901A1 (en) * | 2002-10-31 | 2004-05-19 | Umicore Ag & Co.Kg | Process for the preparation of palladium (0) -containing compounds |
JP4784402B2 (en) * | 2006-06-06 | 2011-10-05 | 東ソー株式会社 | Catalyst for producing arylamines and method for producing arylamines using the same |
KR101294236B1 (en) | 2009-07-10 | 2013-08-07 | 엘지디스플레이 주식회사 | Blue color fluorescent material and Organic electroluminescent device using the same |
KR102052070B1 (en) | 2012-11-19 | 2019-12-05 | 삼성디스플레이 주식회사 | Amine-based compound and organic light emitting diode comprising the same |
CN104058910B (en) * | 2014-06-17 | 2015-06-17 | 陕西师范大学 | Method for synthesizing triphenylethylene compounds under synergic catalytic action of chlorobenzene and palladium |
CN105669356B (en) * | 2016-03-10 | 2018-09-14 | 北京颖泰嘉和生物科技股份有限公司 | A method of preparing 1,1- talan |
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2001
- 2001-06-27 US US09/891,304 patent/US6455720B1/en not_active Expired - Lifetime
- 2001-06-28 KR KR1020010037503A patent/KR100641597B1/en active IP Right Grant
- 2001-06-28 EP EP01114826A patent/EP1167372B1/en not_active Expired - Lifetime
- 2001-06-28 DE DE60101423T patent/DE60101423T2/en not_active Expired - Fee Related
- 2001-06-28 TW TW090115733A patent/TW591034B/en not_active IP Right Cessation
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US111961A (en) * | 1871-02-21 | Improvement in pumps | ||
US3157042A (en) * | 1963-03-29 | 1964-11-17 | Folger Adam | Motor-driven or operated locks, and the like |
US3355439A (en) * | 1963-10-30 | 1967-11-28 | Union Carbide Corp | Polymers of coordination complexes of vinylphosphines and metal salts, and process for preparing same |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20100298569A1 (en) * | 2007-09-28 | 2010-11-25 | Marc Taillefer | Use of cyclovinyl phosphine/copper complexes as arylation catalysts |
US8604201B2 (en) | 2007-09-28 | 2013-12-10 | Centre National De Recherche Scientifique (C.N.R.S.) | Use of cyclovinyl phosphine/copper complexes as arylation catalysts |
CN103739421A (en) * | 2013-12-17 | 2014-04-23 | 大连世慕化学有限公司 | 1,1-stilbene derivative and preparation method |
CN111423369A (en) * | 2018-12-21 | 2020-07-17 | 陕西师范大学 | Esterase activated aggregation-induced emission type anticancer prodrug and preparation method thereof |
Also Published As
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TW591034B (en) | 2004-06-11 |
EP1167372A1 (en) | 2002-01-02 |
US6455720B1 (en) | 2002-09-24 |
DE60101423D1 (en) | 2004-01-22 |
KR100641597B1 (en) | 2006-11-06 |
EP1167372B1 (en) | 2003-12-10 |
KR20020001652A (en) | 2002-01-09 |
DE60101423T2 (en) | 2004-10-14 |
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