CN108380245A - 一种新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂及其制备方法和合成应用 - Google Patents
一种新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂及其制备方法和合成应用 Download PDFInfo
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- CN108380245A CN108380245A CN201810115048.5A CN201810115048A CN108380245A CN 108380245 A CN108380245 A CN 108380245A CN 201810115048 A CN201810115048 A CN 201810115048A CN 108380245 A CN108380245 A CN 108380245A
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- China
- Prior art keywords
- cymene
- azepine
- ruthenium complexes
- diphenylphosphino
- complexes agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 150000003303 ruthenium Chemical class 0.000 title claims abstract description 57
- GCAXZZFHOFRAHM-UHFFFAOYSA-N [P].N1C=CC=CC=C1 Chemical compound [P].N1C=CC=CC=C1 GCAXZZFHOFRAHM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title abstract description 13
- -1 diphenylphosphino azepine imidazoles Chemical class 0.000 claims abstract description 90
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229930007927 cymene Natural products 0.000 claims abstract description 3
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000741 silica gel Substances 0.000 claims abstract description 3
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Chemical group CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XAOXRLOQKPJANZ-UHFFFAOYSA-N OBOC1=CC(=CC(=C1)C(F)(F)F)C(F)(F)F Chemical class OBOC1=CC(=CC(=C1)C(F)(F)F)C(F)(F)F XAOXRLOQKPJANZ-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical group O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012327 Ruthenium complex Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 7
- 239000011574 phosphorus Substances 0.000 claims 7
- 229910052698 phosphorus Inorganic materials 0.000 claims 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims 1
- 239000003863 metallic catalyst Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000011017 operating method Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 78
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 72
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 34
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 31
- 238000010189 synthetic method Methods 0.000 description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 22
- 229910052707 ruthenium Inorganic materials 0.000 description 22
- 239000007787 solid Substances 0.000 description 19
- 238000004679 31P NMR spectroscopy Methods 0.000 description 13
- 239000012230 colorless oil Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- GVGVUNDFQUSHDM-UHFFFAOYSA-N 1-benzyl-2h-pyridine Chemical class C=1C=CC=CC=1CN1CC=CC=C1 GVGVUNDFQUSHDM-UHFFFAOYSA-N 0.000 description 3
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- JPRMBFYOOQJBKR-UHFFFAOYSA-N n-benzyl-n-bromoaniline Chemical class C=1C=CC=CC=1N(Br)CC1=CC=CC=C1 JPRMBFYOOQJBKR-UHFFFAOYSA-N 0.000 description 2
- AINJFPWYQKCVAY-UHFFFAOYSA-N n-benzyl-n-chloroaniline Chemical class C=1C=CC=CC=1N(Cl)CC1=CC=CC=C1 AINJFPWYQKCVAY-UHFFFAOYSA-N 0.000 description 2
- FHWHYVYOMJDEJB-UHFFFAOYSA-N n-benzyl-n-fluoroaniline Chemical class C=1C=CC=CC=1N(F)CC1=CC=CC=C1 FHWHYVYOMJDEJB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CNIIMCXFZSUBJC-UHFFFAOYSA-N (2-phenyl-1h-imidazol-5-yl)methanamine Chemical class NCC1=CNC(C=2C=CC=CC=2)=N1 CNIIMCXFZSUBJC-UHFFFAOYSA-N 0.000 description 1
- GEZMEIHVFSWOCA-UHFFFAOYSA-N (4-fluorophenyl)methanol Chemical class OCC1=CC=C(F)C=C1 GEZMEIHVFSWOCA-UHFFFAOYSA-N 0.000 description 1
- 0 *N(C*1)C=C[N+]1(Cc(cccc1)c1P(c1ccccc1)c1ccccc1)[O-] Chemical compound *N(C*1)C=C[N+]1(Cc(cccc1)c1P(c1ccccc1)c1ccccc1)[O-] 0.000 description 1
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 150000004842 1-phenylimidazoles Chemical class 0.000 description 1
- 150000005004 2-naphthylamines Chemical class 0.000 description 1
- 150000003929 3-aminopyridines Chemical class 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical class NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical class NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical class NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- MOFLDTNKLMFGSU-UHFFFAOYSA-N bromobenzene;methanol Chemical compound OC.BrC1=CC=CC=C1 MOFLDTNKLMFGSU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- AVPVRXORILGHNM-UHFFFAOYSA-N chlorobenzene;methanol Chemical class OC.ClC1=CC=CC=C1 AVPVRXORILGHNM-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- WBKFWQBXFREOFH-UHFFFAOYSA-N dichloromethane;ethyl acetate Chemical compound ClCCl.CCOC(C)=O WBKFWQBXFREOFH-UHFFFAOYSA-N 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical class CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004979 fampridine Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TZHYFNJRLMHJCM-UHFFFAOYSA-N n-(3-phenylpropyl)aniline Chemical compound C=1C=CC=CC=1CCCNC1=CC=CC=C1 TZHYFNJRLMHJCM-UHFFFAOYSA-N 0.000 description 1
- WRDZMZGYHVUYRU-UHFFFAOYSA-N n-[(4-methoxyphenyl)methyl]aniline Chemical compound C1=CC(OC)=CC=C1CNC1=CC=CC=C1 WRDZMZGYHVUYRU-UHFFFAOYSA-N 0.000 description 1
- LFPDICHOBQRBKC-UHFFFAOYSA-N n-[(4-methylphenyl)methyl]aniline Chemical compound C1=CC(C)=CC=C1CNC1=CC=CC=C1 LFPDICHOBQRBKC-UHFFFAOYSA-N 0.000 description 1
- AZLKZLKCCRFAAE-UHFFFAOYSA-N n-benzyl-4-bromoaniline Chemical class C1=CC(Br)=CC=C1NCC1=CC=CC=C1 AZLKZLKCCRFAAE-UHFFFAOYSA-N 0.000 description 1
- MMEIYVXPSXIGET-UHFFFAOYSA-N n-benzyl-4-chloroaniline Chemical class C1=CC(Cl)=CC=C1NCC1=CC=CC=C1 MMEIYVXPSXIGET-UHFFFAOYSA-N 0.000 description 1
- VGUGAUNYDBPMQY-UHFFFAOYSA-N n-benzyl-4-fluoroaniline Chemical class C1=CC(F)=CC=C1NCC1=CC=CC=C1 VGUGAUNYDBPMQY-UHFFFAOYSA-N 0.000 description 1
- LIJJGMDKVVOEFT-UHFFFAOYSA-N n-benzyl-4-methoxyaniline Chemical class C1=CC(OC)=CC=C1NCC1=CC=CC=C1 LIJJGMDKVVOEFT-UHFFFAOYSA-N 0.000 description 1
- KEVOWRWHMCBERP-UHFFFAOYSA-N n-benzyl-4-methylaniline Chemical class C1=CC(C)=CC=C1NCC1=CC=CC=C1 KEVOWRWHMCBERP-UHFFFAOYSA-N 0.000 description 1
- KBOITYDYBXNTMF-UHFFFAOYSA-N n-benzylnaphthalen-2-amine Chemical class C=1C=C2C=CC=CC2=CC=1NCC1=CC=CC=C1 KBOITYDYBXNTMF-UHFFFAOYSA-N 0.000 description 1
- WYHXNQXDQQMTQI-UHFFFAOYSA-N n-benzylpyridin-2-amine Chemical compound C=1C=CC=CC=1CNC1=CC=CC=N1 WYHXNQXDQQMTQI-UHFFFAOYSA-N 0.000 description 1
- SQMRJGGCCLWSQR-UHFFFAOYSA-N n-benzylpyridin-3-amine Chemical compound C=1C=CC=CC=1CNC1=CC=CN=C1 SQMRJGGCCLWSQR-UHFFFAOYSA-N 0.000 description 1
- LCUREJHJUJCKQS-UHFFFAOYSA-N n-benzylpyridin-4-amine Chemical compound C=1C=CC=CC=1CNC1=CC=NC=C1 LCUREJHJUJCKQS-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical class COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical class CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 229950009195 phenylpropanol Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
本发明公开了一种新型双齿磷‑氮杂卡宾对伞花烃型钌配合物催化剂及其制备方法和合成应用,该催化剂通过将氧化银和相应的双齿磷‑氮杂咪唑氯盐配体加入到二氯甲烷溶液中,避光,室温,氮气保护条件下反应12~24h;然后在氮气保护下加入与配体0.5当量的[Ru(p‑cymene)Cl2]2,室温反应12~24h;反应后过滤、重结晶或用二氯甲烷‑甲醇过硅胶柱分离,得到双齿磷‑氮杂卡宾对伞花烃型钌配合物催化剂。本发明的催化剂可在碱性条件下,催化醇与芳香伯胺的“借氢偶联”反应得到一系列有价值的N‑烷基化合物。本发明的双齿磷‑氮杂卡宾对伞花烃型钌配合物催化剂的合成原料简单,操作步骤易行,并且稳定性较好,同时该钌配合物催化剂具有反应底物范围广、条件温和、高效实用等优点,具有重要的应用价值。
Description
技术领域
本发明涉及有机合成技术领域,特别涉及一种新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂及其制备方法和合成应用。
背景技术
N-烷基类化合物在医药、农药、染料和其它精细化工领域有着广泛的用途,其传统合成方法主要是霍夫曼烷基化反应和布赫瓦尔德-哈特维希反应等,但这些方法需要使用毒性大的有机卤试剂,而且反应条件苛刻、环境污染大、产率不高。近年来,以过渡金属络合物催化合成的新方法,可以采用环境友好、便宜易得的醇来代替有机卤试剂,而且反应条件温和,选择性和产率也有较大的提高,是目前最有发展前途的一种方法。其中,钌催化醇和胺的反应,通过氢转移反应(通常也称为“借氢反应”),是制备N-烷基类化合物的一种理想合成方法。但是,这些催化体系常常需要较高的温度(>100℃)或较高的催化剂用量(>2mol%),妨碍了其进一步的工业应用。
发明内容
本发明的目的在于克服现有技术中存在的缺点,提供一种新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,该催化剂合成简单,并且可以在较温和的条件下催化醇与胺反应得到不同的N-烷基类化合物。
本发明的另一目的在于提供一种上述催化剂的制备方法。
本发明的再一目的在于提供一种上述催化剂的合成应用,通过催化醇与胺反应,应用于N-烷基类化合物的合成反应中。
本发明的目的通过下述技术方案实现:
一种新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,具有如式一所示的结构:
其中,R为甲基、异丙基、苯基或均三甲基苯基;X为氯、六氟磷酸基、四氟硼酸基、四苯基硼酸基、三氟甲磺酸基或四(3,5-二(三氟甲基)苯基)硼酸基。
上述新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,是将氧化银和相应的双齿磷-氮杂咪唑氯盐配体加入到二氯甲烷溶液中,避光,室温,氮气保护条件下反应12~24h;然后在氮气保护下加入与配体0.5当量的[Ru(p-cymene)Cl2]2,室温反应12~24h;反应后过滤、重结晶或用二氯甲烷-甲醇过硅胶柱分离,得到双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中阴离子X为Cl。
氧化银和双齿磷-氮杂咪唑氯盐配体的摩尔用量比为(1~2):1。
将阴离子X为Cl的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂和等摩尔量的相应阴离子的银盐(X=PF6,OTf或BF4)或钠盐(X=BArF或BPh4),在二氯甲烷溶液中搅拌2~5h,旋干、过柱,得到不同X阴离子(X=PF6、OTf、BF4、BArF或BPh4)的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂。
新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的制备步骤如式二所示:
所述双齿磷-氮杂咪唑氯盐配体是通过以下三步反应得到,反应过程如式三所示:
所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的用途,是作为金属催化剂催化醇与胺的反应,用于合成制备N-烷基类化合物。
所述N-烷基类化合物的通式为:
所述醇的通式为:
所述胺的通式为:
其中,R1优选吸电子取代基氟、氯、溴,或给电子取代基甲基、甲氧基等;R2优选芳香取代基或脂肪取代基等;所述醇中的R2与N-烷基类化合物中的R2涵义相同,胺中的R1与N-烷基类化合物中的R1涵义相同。
N-烷基类化合物的合成方法,是将所述新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂、醇、胺和碱加入到溶剂中,氮气保护下在50~90℃反应2~12h;反应完毕,降至室温,加水淬灭,用乙酸乙酯萃取,浓缩、纯化、干燥,得到N-烷基类化合物。
所述新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂、醇、胺和碱的摩尔比为(0.001~0.05):1:1:1;所述的碱为叔丁醇钾;所述的溶剂为甲苯。
N-烷基类化合物的合成反应步骤如式四所示:
本发明与现有技术相比具有如下优点和效果:
(1)本发明的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的合成原料简单,操作步骤简单易行,并且对空气稳定。
(2)本发明的催化剂对底物的适应范围广,能够在较温和的条件下催化不同结构的N-烷基化合物的合成。
附图说明
图1为双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6a的单晶结构图。
具体实施方式
下面结合实施例对本发明做进一步详细的描述,但本发明的实施方式不限于此。
为了在实施例中简明清楚地表述配体和配合物,说明如下:
配体5a为式5所示的双齿磷-氮杂咪唑氯盐,其中R为均三甲基苯基;
配体5b为式5所示的双齿磷-氮杂咪唑氯盐,其中R为苯基;
配体5c为式5所示的双齿磷-氮杂咪唑氯盐,其中R为甲基;
配体5d为式5所示的双齿磷-氮杂咪唑氯盐,其中R为异丙基。
配合物6a为式6所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中R为均三甲基苯基;
配合物6b为式6所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中R为苯基;
配合物6c为式6所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中R为甲基;
配合物6d为式6所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中R为异丙基。
配合物6ba为式6b所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中X为六氟磷酸基;
配合物6bb为式6b所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中X为四(3,5-二(三氟甲基)苯基)硼酸基;
配合物6bc为式6b所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中X为三氟甲磺酸基;
配合物6bd为式6b所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中X为四氟硼酸基;
配合物6be为式6b所示的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中X为四苯基硼酸基。
双齿磷-氮杂咪唑氯盐的合成:
双齿磷-氮杂咪唑氯盐的合成根据文献报道的方法合成,以N,N-二甲基苄胺为初始原料,经两步反应得邻二苯基磷苄氯中间体,最后与相应的咪唑反应得到双齿磷-氮杂咪唑氯盐。
实施例1
合成双齿磷-氮杂咪唑氯盐配体5a,具体按照以下步骤进行:将316mg(1.02mmol)邻二苯基磷苄氯和186mg(1.0mmol)1-均三甲基苯基咪唑溶于2ml无水DMF,在氩气保护下,90℃搅拌48h。冷却至室温,旋干溶剂,粗产物用二氯甲烷-乙酸乙酯重结晶,得367mg白色固体,即双齿磷-氮杂咪唑氯盐配体5a,其产率为74%。
1H NMR(400MHz,DMSO-d6)δ9.84(s,1H),7.97(d,J=6.9Hz,2H),7.58–7.49(m,2H),7.42(s,7H),7.24–7.21(m,4H),7.12(s,2H),7.00–6.97(m,1H),5.79(s,2H),2.31(s,3H),1.97(s,6H)。
13C NMR(101MHz,DMSO-d6)δ140.1,138.2,138.2,137.9,136.2,136.1,135.0,134.9,134.2,134.1,133.4,133.2,131.1,130.2,130.0,130.0,129.6,129.3,129.2,129.0,129.0,124.1,123.1,51.1(d,J=24.2Hz),20.6,16.9。
31P NMR(162MHz,DMSO-d6)δ-18.67(s)。
HRMS(ESI,m/z):calcd for C31H30N2P[M-Cl]+461.21411,found461.21352。
实施例2
合成双齿磷-氮杂咪唑氯盐配体5b,具体按照以下步骤进行:
按照实施例1中配体5a的合成方法,用144mg(1.0mmol)1-苯基咪唑代替1-均三甲基苯基咪唑,其他操作条件同实施例1,反应结束后得到390mg白色固体,即双齿磷-氮杂咪唑氯盐配体5b,其产率为86%。
1H NMR(400MHz,DMSO-d6)δ9.91(s,1H),8.17(s,1H),7.78(s,1H),7.73–7.66(m,1H),7.66–7.59(m,4H),7.56(t,J=7.1Hz,2H),7.46(t,J=7.4Hz,1H),7.33(s,6H),7.18–7.04(m,4H),6.95–6.92(m,1H),5.78(s,2H)。
13C NMR(101MHz,DMSO-d6)δ137.7,137.4,136.4,136.2,135.6,134.8,134.7,134.3,134.1,133.3,133.1,131.1,131.0,130.1,129.9,129.7,129.6,129.2,128.8,128.8,123.1,121.6,121.1,51.4(d,J=22.9Hz)。
31P NMR(162MHz,DMSO-d6)δ-18.92(s)。
HRMS(ESI,m/z):calcd for C28H24N2P[M-Cl]+419.16716,found419.16639。
实施例3
合成双齿磷-氮杂咪唑氯盐配体5c,具体按照以下步骤进行:
按照实施例1中配体5a的合成方法,用82mg(1.0mmol)1-甲基咪唑代替1-均三甲基苯基咪唑,其他操作条件同实施例1,反应结束后得到298mg白色固体,即双齿磷-氮杂咪唑氯盐配体5c,其产率为76%。
1H NMR(400MHz,DMSO-d6)δ8.92(s,1H),7.54-7.50(m,1H),7.47-7.43(m,2H),7.37(d,J=8.9Hz,2H),7.34-7.28(m,6H),7.02(t,J=6.7Hz,4H),6.89–6.78(m,1H),5.57(s,2H),3.52(s,3H)。
13C NMR(101MHz,DMSO-d6)δ138.0,137.8,136.9,136.5,136.4,134.8,134.7,134.2,133.4,133.2,131.1,131.0,130.1,129.7,129.3,128.9,128.8,123.6,122.1,51.0(d,J=22.1Hz),35.6。
31P NMR(162MHz,DMSO-d6)δ-18.90(s)。
HRMS(ESI,m/z):calcd for C23H22N2P[M-Cl]+357.15151,found357.15099。
实施例4
合成双齿磷-氮杂咪唑氯盐配体5d,具体按照以下步骤进行:
按照实施例1中配体5a的合成方法,用110mg(1.0mmol)1-异丙基咪唑代替1-均三甲基苯基咪唑,其他操作条件同实施例1,反应结束后得到336mg白色固体,即双齿磷-氮杂咪唑氯盐配体5d,其产率为80%。
1H NMR(400MHz,DMSO-d6)δ9.32(s,0.25H),9.25(s,0.75H),7.76(s,1H),7.62–7.50(m,3H),7.48–7.32(m,7H),7.12(s,4H),6.95(s,1H),5.66(s,2H),4.48(s,1H),1.32(d,J=5.9Hz,6H)。
13C NMR(100MHz,DMSO-d6)δ138.2,137.9,136.3,136.2,135.2,135.0,134.9,134.3,133.3,133.1,130.8,130.7,130.2,129.7,129.3,128.9,128.9,122.5,120.5,52.1,51.0(d,J=23.2Hz),23.4,22.2。
31P NMR(162MHz,DMSO-d6)δ-19.18(s)。
HRMS(ESI,m/z):calcd for C25H26N2P[M-Cl]+385.18281,found385.18221。
双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的合成:
实施例5
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6a,具体按照以下步骤进行:
向带有搅拌子的10ml Schlenk管中,称取100mg(0.2mmol)5a和92mg(0.4mmol)氧化银,加入2ml无水二氯甲烷,氩气保护下,室温避光反应24h。再在氩气保护下,加入61mg(0.1mmol)[(p-cymene)RuCl2)]2和2ml无水二氯甲烷,继续反应24h。反应完全后,过滤,旋干,过柱即得114mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6a,其产率为74%。
1H NMR(400MHz,DMSO-d6)δ8.13(s,1H),7.85-7.81(m,3H),7.73-7.67(m,3H),7.61(t,J=7.4Hz,1H),7.46(s,1H),7.41(t,J=7.6Hz,1H),7.20-7.05(m,4H),6.99(s,1H),6.79(s,1H),6.51–6.46(m,2H),5.85–5.69(m,2H),5.40-5.33(m,2H),5.19(s,1H),4.42(s,1H),2.24(s,4H),1.97(s,3H),1.85(s,3H),1.71(s,3H),0.98(d,J=7.0Hz,3H),0.52(d,J=6.4Hz,3H)。
13C NMR(151MHz,DMSO-d6)δ171.5(d,J=25.7Hz),139.8(d,J=12.6Hz),137.9,137.1,136.8,136.6,136.5,135.3,135.1,135.0,132.6,132.5,131.7,131.5,131.4,131.0,130.7,129.0(d,J=4.5Hz),128.8,128.7,128.6,128.5,128.2(d,J=4.5Hz),128.1,128.0,127.8,127.7(d,J=10.6Hz),126.0,124.0,91.2,89.1,53.7,30.4,23.1,20.4,19.6(d,J=7.2Hz),19.1,17.5,17.4。
31P NMR(162MHz,DMSO-d6)δ23.34(s)。
HRMS(ESI,m/z):calcd for C41H43ClN2PRu[M-Cl]+731.18904,found731.18879。
实施例6
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6b,具体按照以下步骤进行:
按照实施例5中配合物6a的合成方法,用90mg(0.2mmol)5b代替(0.2mmol)5a,其他操作条件同实施例5,反应结束后得到94mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6b,其产率为65%。
1H NMR(400MHz,DMSO-d6)δ8.12(s,1H),7.85(s,1H),7.70-7.65(m,3H),7.60-7.51(m,9H),7.43-7.32(m,4H),7.08(t,J=8.6Hz,2H),6.98(t,J=8.6Hz,1H),5.72(d,J=6.1Hz,1H),5.62-5.56(m,2H),5.50-5.46(m,2H),4.70(d,J=5.9Hz,1H),2.24–2.19(m,1H),1.87(s,3H),0.85(d,J=6.4Hz,3H),0.77(d,J=6.4Hz,3H)。
13C NMR(100MHz,DMSO-d6)δ167.0(d,J=22.2Hz),140.4,139.7(d,J=12.5Hz),137.1,136.7,134.3,134.2,133.8,133.3,132.8(d,J=8.9Hz),131.6,130.6,130.5,130.4,130.2(d,J=2.1Hz),129.5,129.1,129.0,128.8(d,J=9.0Hz),128.6,128.2,128.0,127.9,127.8,126.1,125.3,122.9,108.9,106.7,93.6(d,J=7.1Hz),93.0,93.0,89.2,52.6(d,J=9.6Hz),30.0,22.2,21.5,17.5。
31P NMR(162MHz,DMSO-d6)δ23.99(s)。
HRMS(ESI,m/z):calcd for C38H37ClN2PRu[M-Cl]+689.14209,found689.14183。
实施例7
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6c,具体按照以下步骤进行:
按照实施例5中配合物6a的合成方法,用80mg(0.2mmol)5c代替(0.2mmol)5a,其他操作条件同实施例5,反应结束后得到72mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6c,其产率为54%。
1H NMR(400MHz,DMSO-d6)δ8.02(s,1H),7.90-7.88(m,1H),7.58–7.40(m,12H),7.26(t,J=7.5Hz,1H),6.75(t,J=8.9Hz,1H),6.38(d,J=6.4Hz,1H),6.33(d,J=5.4Hz,1H),5.99(d,J=6.4Hz,1H),5.50(d,J=14.2Hz,1H),5.33(d,J=14.1Hz,1H),5.27(s,1H),3.92(s,3H),2.20(s,3H),2.04-1.97(m,1H),0.84(d,J=6.8Hz,3H),0.62(d,J=6.7Hz,3H)。
13C NMR(100MHz,DMSO-d6)δ165.4(d,J=19.3Hz),141.2(d,J=11.6Hz),137.6,137.1,136.5(d,J=10.0Hz),133.3,132.6,132.3(d,J=9.1Hz),132.1,131.6,130.8,130.4,129.9(d,J=7.3Hz),129.0,128.9,128.8,128.4,127.9,127.8(d,J=10.0Hz),126.3,122.3,107.7,105.8,94.5,94.4,91.7,88.6,52.1(d,J=10.3Hz),38.7,29.9,22.7,20.0,17.6。
31P NMR(162MHz,DMSO-d6)δ25.66(s)。
HRMS(ESI,m/z):calcd for C33H35ClN2PRu[M-Cl]+627.12644,found627.12602。
实施例8
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6d,具体按照以下步骤进行:
按照实施例5中配合物6a的合成方法,用84mg(0.2mmol)5c代替(0.2mmol)5a,其他操作条件同实施例5,反应结束后得到82mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6d,其产率为60%。
1H NMR(400MHz,DMSO-d6)δ8.07(s,1H),7.91(s,1H),7.85–7.79(m,1H),7.80–7.72(m,2H),7.67(s,3H),7.49(t,J=7.3Hz,1H),7.30(t,J=7.5Hz,1H),7.17(t,J=7.1Hz,1H),7.05(d,J=7.5Hz,3H),6.52–6.42(m,2H),5.87(d,J=5.6Hz,1H),5.77(d,J=6.6Hz,1H),5.60(d,J=14.8Hz,1H),5.39-5.34(m,3H),5.31–5.21(m,1H),2.45-2.38(m,1H),1.90(s,3H),1.50(d,J=6.5Hz,3H),1.22(d,J=6.1Hz,3H),1.01(d,J=6.6Hz,3H),0.91(d,J=6.7Hz,3H)。
13C NMR(100MHz,DMSO-d6)δ165.7(d,J=27.3Hz),140.3(d,J=12.4Hz),137.4,137.0,135.6,135.0,134.5,132.4(d,J=8.9Hz),131.8(d,J=8.8Hz),131.4,130.7,130.7,129.1,128.9,128.9,128.8,128.5,127.6(d,J=10.3Hz),124.4,121.5,113.6,103.5,98.1(d,J=4.4Hz),92.7(d,J=5.3Hz),88.1(d,J=3.3Hz),86.3,85.5,52.4(d,J=7.2Hz),51.9,29.9,23.8,23.7,22.0,21.5,17.2。
31P NMR(162MHz,DMSO-d6)δ23.74(s)。
HRMS(ESI,m/z):calcd for C35H39ClN2PRu[M-Cl]+655.15774,found655.15755。
实施例9
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6ba,具体按照以下步骤进行:
向带有搅拌子的10ml Schlenk管中,称取56mg(0.1mmol)6b和25mg(0.1mmol)六氟磷酸银,加入2ml无水二氯甲烷,氩气保护下,室温反应2h。反应完全后,过滤,旋干,过柱即得62mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6ba,其产率为92%。
1H NMR(400MHz,DMSO-d6)δ8.02(s,1H),7.80–7.77(m,1H),7.70–7.68(m,3H),7.60–7.51(m,9H),7.45–7.33(m,4H),7.10–7.05(m,2H),7.00(t,J=8.7Hz,1H),5.72(d,J=6.4Hz,1H),5.63(d,J=14.5Hz,1H),5.55(d,J=5.6Hz,1H),5.50(s,1H),5.40(d,J=14.5Hz,1H),4.71(d,J=6.3Hz,1H),2.25-2.18(m,1H),1.87(s,3H),0.85(d,J=6.7Hz,3H),0.78(d,J=6.8Hz,3H)。
13C NMR(101MHz,DMSO-d6)δ167.1(d,J=22.2Hz),140.4,139.6(d,J=12.5Hz),137.1,136.6,134.3,134.2,133.8,133.3,132.80(d,J=8.9Hz),131.6,130.6,130.4,130.3,130.2,129.5,129.1,129.0,128.9(d,J=9.0Hz),128.5,128.1,127.8,127.7,109.1,106.7,93.6(d,J=7.1Hz),93.0,93.0,89.2,52.8(d,J=9.6Hz),30.0,22.3,21.4,17.4。
31P NMR(162MHz,DMSO-d6)δ23.96,-131.02,-135.41,-139.80,-144.19,-148.58,-152.97,-157.36。
HRMS(ESI,m/z):calcd for C38H37ClN2PRu[M–PF6]+689.14209,found689.14183。
实施例10
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bb,具体按照以下步骤进行:
按照实施例9中配合物6ba的合成方法,用89mg(0.1mmol)四(3,5-二(三氟甲基)苯基)硼酸钠代替(0.1mmol)六氟磷酸银,其他操作条件同实施例9,反应结束后得到108mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bb,其产率为78%。
1H NMR(400MHz,DMSO-d6)δ8.03(s,1H),7.83–7.76(m,1H),7.72–7.64(m,7H),7.61–7.55(m,13H),7.54–7.50(m,4H),7.40–7.35(m,4H),7.12–7.03(m,2H),6.99(t,J=8.7Hz,1H),5.71(d,J=6.4Hz,1H),5.62(d,J=14.4Hz,1H),5.55(d,J=5.6Hz,1H),5.49(s,1H),5.40(d,J=14.5Hz,1H),4.70(d,J=6.2Hz,1H),2.22–2.19(m,1H),1.86(s,3H),0.81(d,J=4.0Hz,3H),0.76(d,J=4.0Hz,3H)。
13C NMR(100MHz,DMSO-d6)δ167.2(d,J=20.0Hz),161.7,161.2,160.7,160.2,140.5,139.7(d,J=12.4Hz),137.1,136.7,134.4–134.1(m),133.8,133.3,132.9,132.8,131.7,130.6,130.4,130.2,129.5,129.1,128.9,128.8,128.7–128.6(m),128.4–128.3(m),128.1,128.1,127.9,127.8,125.4,122.8,122.7,120.0,117.6,108.9,106.8,93.6(d,J=7.1Hz),93.1,93.0,89.2,52.8(d,J=10.0Hz),30.0,22.3,21.5,17.5。
31P NMR(162MHz,DMSO-d6)23.95(s)。
HRMS(ESI,m/z):calcd for C38H37ClN2PRu[M-BArF]+689.14209,found689.14183。
实施例11
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bc,具体按照以下步骤进行:
按照实施例9中配合物6ba的合成方法,用26mg(0.1mmol)三氟甲磺酸银代替(0.1mmol)六氟磷酸银,其他操作条件同实施例9,反应结束后得到85mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bc,其产率为94%。
1H NMR(400MHz,DMSO-d6)δ8.02(s,1H),7.81–7.78(m,1H),7.71–7.68(m,3H),7.62–7.50(m,9H),7.42–7.30(m,4H),7.10–7.05(m,2H),6.99(t,J=8.7Hz,1H),5.72(d,J=6.4Hz,1H),5.63(d,J=14.4Hz,1H),5.55(d,J=5.7Hz,1H),5.50(s,1H),5.40(d,J=14.5Hz,1H),4.70(d,J=6.3Hz,1H),2.24-2.18(m,1H),1.87(s,3H),0.85(d,J=6.7Hz,3H),0.77(d,J=6.8Hz,3H)。
13C NMR(101MHz,DMSO-d6)δ167.1(d,J=22.2Hz),140.4,139.7(d,J=12.5Hz),137.1,136.7,134.4,134.3,133.8,133.3,132.8(d,J=8.9Hz),131.7,130.7,130.4,130.3,130.2,129.5,129.1,129.1,128.8(d,J=9.0Hz),128.6,128.3,128.1,127.9,127.8,126.1,122.8,108.9,106.8,93.7(d,J=7.1Hz),93.1,93.0,89.3,52.8(d,J=9.6Hz),30.0,22.3,21.5,17.5。
31P NMR(162MHz,DMSO-d6)δ23.97。
HRMS(ESI,m/z):calcd for C38H37ClN2PRu[M-CF3SO3]+689.14209,found689.14183。
实施例12
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bd,具体按照以下步骤进行:
按照实施例9中配合物6ba的合成方法,用20mg(0.1mmol)四氟硼酸银代替(0.1mmol)六氟磷酸银,其他操作条件同实施例9,反应结束后得到75mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bd,其产率为90%。
1H NMR(400MHz,DMSO-d6)δ8.03(s,1H),7.81–7.78(m,1H),7.72–7.67(m,3H),7.60–7.50(m,9H),7.41–7.33(m,4H),7.10-7.05(m,2H),6.99(t,J=8.7Hz,1H),5.73(d,J=6.4Hz,1H),5.63(d,J=14.5Hz,1H),5.56(s,1H),5.50(s,1H),5.41(d,J=14.5Hz,1H),4.71(d,J=6.2Hz,1H),2.24-2.18(m,1H),1.87(s,3H),0.85(d,J=6.8Hz,3H),0.77(d,J=6.8Hz,3H)。
13C NMR(101MHz,DMSO-d6)δ167.1(d,J=22.2Hz),140.4,139.7(d,J=12.5Hz),137.1,136.7,134.4,134.3,133.8,133.3,132.8(d,J=8.1Hz),131.7,130.7,130.4,130.3,130.2,129.5,129.1,129.1,128.9(d,J=9.1Hz),128.6,128.3,128.1,127.9,127.8,126.1,125.5,122.8,108.9,106.7,93.7(d,J=7.1Hz),93.1,93.0,89.2,52.8(d,J=10.1Hz),30.0,22.3,21.5,17.5。
31P NMR(162MHz,DMSO-d6)δ23.97。
HRMS(ESI,m/z):calcd for C38H37ClN2PRu[M–BF4]+689.14209,found689.14183。
实施例13
合成双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6be,具体按照以下步骤进行:
按照实施例9中配合物6ba的合成方法,用34mg(0.1mmol)四苯基硼酸钠代替(0.1mmol)六氟磷酸银,其他操作条件同实施例9,反应结束后得到95mg黄色固体,即双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6be,其产率为89%。
1H NMR(400 MHz,DMSO-d6)δ8.01(s,1H),7.81–7.78(m,1H),7.71–7.67(m,3H),7.60–7.50(m,9H),7.41-7.32(m,4H),7.20(s,8H),7.10–7.05(m,2H),7.00(t,J=8.7 Hz,1H),6.93(t,J=7.2 Hz,8H),6.81-6.78(m,4H),5.70(d,J=6.4 Hz,1H),5.63(d,J=14.4Hz,1 H),5.52(d,J=5.5 Hz,1H),5.47(s,1 H),5.39(d,J=8.0 Hz,1H),4.70(d,J=6.3Hz,1 H),2.24-2.18(m,1H),1.85(s,3H),0.85(d,J=6.7 Hz,3H),0.77(d,J=6.7 Hz,3H)。
13C NMR(101 MHz,DMSO-d6)δ167.1(d,J=22.2 Hz),164.1,163.6,163.1,162.6,140.4,139.6(d,J=12.1 Hz),137.1,136.7,135.6,134.5,134.4,134.3,133.8,133.3,132.8(d,J=9.1 Hz),131.6,130.6,130.4(d,J=8.1 Hz),130.2,129.5,129.1,129.0,128.9(d,J=5.1 Hz),128.8,128.6,128.3,128.1,127.9,127.8,127.5,127.4,126.7,125.35-125.26(m),122.7,121.5,108.9,106.7,93.7(d,J=7.1 Hz),93.0,93.0,89.2,30.0,22.3,21.5,17.5。
31P NMR(162 MHz,DMSO-d6)δ23.97。
HRMS(ESI,m/z):calcd for C38H37ClN2PRu[M–BPh4]+689.14209,found689.14183。
双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂在催化醇与苯胺偶联合成N-烷基类化合物的应用,其反应通式如下:
实施例14
合成N-苄基苯胺,具体按照以下步骤进行:
向带有搅拌子的10ml Schlenk管中,称取3.9mg(0.0025mmol)双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6a和112mg(1mmol)叔丁醇钾,108mg(1 mmol)苯甲醇,93mg(1mmol)苯胺,氩气保护下加入2ml无水甲苯,70℃反应12h。反应完全后,过滤,旋干,过柱即得172mg无色油状物,即N-苄基苯胺,其产率为95%。
1H NMR(400MHz,CDCl3)δ7.41-7.35(m,4H),7.34–7.27(m,1H),7.20(t,J=7.5Hz,2H),6.75(t,J=7.3Hz,1H),6.67(d,J=7.8Hz,2H),4.35(s,2H),4.04(s,1H)。
13C NMR(100MHz,CDCl3)δ148.3,139.6,129.4,128.7,127.6,127.3,117.7,113.0,48.4。
MS(ESI)[M+H]+183.65。
实施例15
合成N-4-甲基苄基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6b,122mg(1mmol)4-甲基苯甲醇代替苯甲醇,其他操作条件同实施例14,反应结束后得到176mg无色油状物,即N-4-甲基苄基苯胺,其产率为90%。
1H NMR(400MHz,CDCl3)δ7.26(d,J=8.1Hz,2H),7.17(dd,J=11.3,8.0Hz,4H),6.71(t,J=7.3Hz,1H),6.64(d,J=8.0Hz,2H),4.28(s,2H),3.98(s,1H),2.35(s,3H)。
13C NMR(100MHz,CDCl3)δ148.4,137.0,136.5,129.4,129.4,127.6,117.6,113.0,48.2,21.2。
MS(ESI)[M+H]+197.65。
实施例16
合成N-4-甲氧基苄基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6c,138mg(1mmol)4-甲基苯甲醇代替苯甲醇,其他操作条件同实施例14,反应结束后得到187mg无色油状物,即N-4-甲氧基苄基苯胺,其产率为88%。
1H NMR(400MHz,CDCl3)δ7.30(d,J=8.4Hz,2H),7.18(t,J=7.8Hz,2H),6.89(d,J=8.5Hz,2H),6.72(t,J=7.3Hz,1H),6.64(d,J=7.7Hz,2H),4.26(s,2H),3.95(s,1H),3.81(s,3H)。
13C NMR(100MHz,CDCl3)δ159.0,148.3,131.5,129.4,128.9,117.6,114.1,112.9,55.4,47.9。
MS(ESI)[M+H]+213.60。
实施例17
合成N-2-萘甲基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6d,158mg(1mmol)2-萘甲醇代替苯甲醇,其他操作条件同
实施例14,反应结束后得到200mg无色油状物,即N-2-萘甲基苯胺,其产率为85%。
1H NMR(400MHz,CDCl3)δ7.85-7.81(m,4H),7.51-7.48(m,3H),7.19(t,J=7.6Hz,2H),6.74(t,J=7.4Hz,1H),6.69(d,J=8.1Hz,2H),4.51(s,2H),4.14(s,1H)。
13C NMR(100MHz,CDCl3)δ148.3,137.1,133.6,132.9,129.4,128.5,127.9,127.8,126.3,126.0,125.9,117.8,113.1,48.6。
MS(ESI)[M+H]+233.65。
实施例18
合成N-4-氟-苄基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6ba,126mg(1mmol)4-氟苯甲醇代替苯甲醇,其他操作条件同实施例14,反应结束后得到160mg无色油状物,即N-4-氟-苄基苯胺,其产率为80%。
1H NMR(400MHz,CDCl3)δ7.36-7.33(m,2H),7.18(t,J=7.6Hz,2H),7.03(t,J=8.6Hz,2H),6.74(t,J=7.3Hz,1H),6.63(d,J=7.9Hz,2H),4.31(s,2H),4.02(s,1H)。
13C NMR(100MHz,CDCl3)δ162.2(d,JC-F=246.4Hz),148.1,135.2(d,JC-F=2.9Hz),129.4,129.1(d,JC-F=8.0Hz),117.8,115.5(d,JC-F=21.2Hz),113.0,47.7。
MS(ESI)[M+H]+201.60。
实施例19
合成N-4-氯-苄基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bb,142mg(1mmol)4-氯苯甲醇代替苯甲醇,其他操作条件同实施例14,反应结束后得到184mg无色油状物,即N-4-氯-苄基苯胺,其产率为84%。
1H NMR(400MHz,CDCl3)δ7.31(s,4H),7.18(t,J=7.4Hz,2H),6.74(t,J=7.2Hz,1H),6.62(d,J=7.9Hz,2H),4.32(s,2H),4.06(s,1H)。
13C NMR(100MHz,CDCl3)δ148.0,138.1,133.0,129.4,128.9,128.8,117.9,113.0,47.7。
MS(ESI)[M+H]+217.50。
实施例20
合成N-4-溴-苄基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bc,186mg(1mmol)4-溴苯甲醇代替苯甲醇,其他操作条件同实施例14,反应结束后得到216mg无色油状物,即N-4-溴-苄基苯胺,其产率为82%。
1H NMR(400MHz,CDCl3)δ7.48(d,J=8.1Hz,2H),7.28(s,2H),7.19(t,J=7.6Hz,2H),6.75(t,J=7.1Hz,1H),6.63(d,J=8.2Hz,2H),4.32(s,2H),4.07(s,1H)。
13C NMR(100MHz,CDCl3)δ147.9,138.7,131.8,129.4,129.2,121.0,117.9,113.0,47.8。
MS(ESI)[M+H]+263.30。
实施例21
合成N-3-苯基丙基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6a,136mg(1mmol)苯丙醇代替苯甲醇,其他操作条件同实施例14,反应结束后得到168mg无色油状物,即N-3-苯基丙基苯胺,其产率为80%。
1H NMR(400MHz,CDCl3)δ7.31(t,J=7.5Hz,2H),7.25–7.15(m,5H),6.70(t,J=7.0Hz,1H),6.59(d,J=8.3Hz,2H),3.61(s,1H),3.16(t,J=6.9Hz,2H),2.75(t,J=7.6Hz,2H),2.00-1.93(m,2H)。
13C NMR(100MHz,CDCl3)δ148.5,141.8,129.3,128.6,128.5,126.1,117.3,112.9,43.5,33.5,31.2。
MS(ESI)[M+H]+211.60。
双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂催化苯甲醇与芳香胺偶联合成N-烷基化合物的应用,其反应通式如下:
实施例22
合成N-苄基-4-甲基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6b,107mg(1mmol)4-甲基苯胺代替苯胺,其他操作条件同实施例14,反应结束后得到152mg黄色油状物,即N-苄基-4-甲基苯胺,其产率为78%。
1H NMR(400 MHz,CDCl3)δ7.36(q,J=7.6 Hz,4H),7.29(d,J=7.1 Hz,1H),7.00(d,J=7.8 Hz,2H),6.58(d,J=7.7 Hz,2H),4.32(s,2H),3.91(s,1H),2.25(s,3H)。
13C NMR(100 MHz,CDCl3)δ146.0,139.8,129.9,128.7,127.6,127.3,126.9,113.1,48.8,20.5。
MS(ESI)[M+H]+197.65。
实施例23
合成N-苄基-4-甲氧基苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6c,123mg(1mmol)4-甲氧基苯胺代替苯胺,其他操作条件同实施例14,反应结束后得到168mg棕色固体,即N-苄基-4-甲氧基苯胺,其产率为78%。
1H NMR(400 MHz,CDCl3)δ7.36(q,J=7.5 Hz,4H),7.28(d,J=7.0 Hz,1H),6.78(d,J=8.7 Hz,2H),6.61(d,J=8.7 Hz,2H),4.29(s,2H),3.75(s,3H)。
13C NMR(100 MHz,CDCl3)δ152.2,142.5,139.8,128.7,127.6,127.2,115.0,114.2,55.9,49.3。
MS(ESI)[M+H]+213.60。
实施例24
合成N-苄基-4-氟苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6d,111mg(1mmol)4-氟苯胺代替苯胺,其他操作条件同实施例14,反应结束后得到172mg无色油状物,即N-苄基-4-氟苯胺,其产率为85%。
1H NMR(400MHz,CDCl3)δ7.45–7.32(m,4H),7.32–7.27(m,1H),6.88(t,J=8.4Hz,2H),6.62–6.52(m,2H),4.30(s,2H)。
13C NMR(100MHz,CDCl3)δ156.0(d,JC-F=236.3Hz),144.6,139.4,128.8,127.6,127.4,115.8(d,J C-F=22.2Hz),113.8(d,J C-F=7.4Hz),49.0。
MS(ESI)[M+H]+201.60。
实施例25
合成N-苄基-4-氯苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6ba,127mg(1mmol)4-氯苯胺代替苯胺,其他操作条件同实施例14,反应结束后得到208mg无色油状物,即N-苄基-4-氯苯胺,其产率为96%。
1H NMR(400MHz,CDCl3)δ7.35(d,J=3.9Hz,4H),7.29(dd,J=8.3,4.0Hz,1H),7.11(d,J=8.1Hz,2H),6.55(d,J=8.1Hz,2H),4.30(s,2H),4.07(s,1H)。
13C NMR(100MHz,CDCl3)δ146.8,139.1,129.2,128.8,127.5,127.5,122.2,114.0,48.5。
MS(ESI)[M+H]+217.60。
实施例26
合成N-苄基-4-溴苯胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6bc,171mg(1mmol)4-溴苯胺代替苯胺,其他操作条件同实施例14,反应结束后得到240mg无色油状物,即N-苄基-4-溴苯胺,其产率为91%。
1H NMR(400MHz,CDCl3)δ7.36(d,J=4.1Hz,4H),7.32–7.28(m,1H),7.25(d,J=8.9Hz,2H),6.51(d,J=8.5Hz,2H),4.31(s,2H),4.08(s,1H)。
13C NMR(100MHz,CDCl3)δ147.2,139.0,132.1,128.8,127.5,127.5,114.5,109.2,48.4。
MS(ESI)[M+H]+263.40。
实施例27
合成N-苄基-1-萘胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6be,143mg(1mmol)1-萘胺代替苯胺,其他操作条件同实施例14,反应结束后得到216mg白色固体,即N-苄基-1-萘胺,其产率为93%。
1H NMR(400MHz,CDCl3)δ7.83(t,J=8.5Hz,2H),7.46(t,J=7.7Hz,4H),7.38(dd,J=13.6,6.0Hz,2H),7.35–7.30(m,2H),7.27(d,J=7.0Hz,1H),6.65(d,J=7.4Hz,1H),4.71(s,1H),4.51(s,2H)。
13C NMR(100MHz,CDCl3)δ143.3,139.2,134.4,128.9,128.8,127.9,127.5,126.7,125.9,124.9,123.5,120.0,117.8,104.9,48.8。
MS(ESI)[M+H]+233.60。
实施例28
合成N-苄基-2-萘胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6a,143mg(1mmol)2-萘胺代替苯胺,其他操作条件同实施例14,反应结束后得到212mg白色固体,即N-苄基-2-萘胺,其产率为91%。
1H NMR(400MHz,CDCl3)δ7.70–7.55(m,3H),7.43(d,J=7.4Hz,2H),7.36(dd,J=13.7,6.9Hz,3H),7.30(t,J=7.2Hz,1H),7.20(t,J=7.4Hz,1H),6.93(d,J=8.7Hz,1H),6.85(s,1H),4.45(s,2H),4.24(s,1H)。
13C NMR(100MHz,CDCl3)δ145.9,139.3,135.3,129.1,128.8,127.8,127.7,127.5,126.5,126.1,122.2,118.0,104.8,48.5。
MS(ESI)[M+H]+233.60。
实施例29
合成N-苄基吡啶-2-胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6b,94mg(1mmol)2-氨基吡啶代替苯胺,其他操作条件同实施例14,反应结束后得到160mg白色固体,即N-苄基吡啶-2-胺,其产率为86%。
1H NMR(400MHz,CDCl3)δ8.11(d,J=4.6Hz,1H),7.44–7.30(m,5H),7.29(s,1H),6.63–6.56(m,1H),6.38(d,J=8.4Hz,1H),4.85(s,1H),4.51(d,J=5.8Hz,2H)。
13C NMR(100MHz,CDCl3)δ158.8,148.3,139.3,137.6,128.7,127.5,127.3,113.3,106.9,46.4。
MS(ESI)[M+H]+184.60。
实施例30
合成N-苄基吡啶-3-胺,具体按照以下步骤进行:
按照实施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6c,94mg(1mmol)3-氨基吡啶代替苯胺,其他操作条件同实施例14,反应结束后得到156mg白色固体,即N-苄基吡啶-3-胺,其产率为85%。
1H NMR(400MHz,CDCl3)δ8.13(s,1H),7.96(s,1H),7.35(d,J=4.1Hz,4H),7.29(d,J=4.2Hz,1H),7.07(dd,J=7.8,4.3Hz,1H),6.87(d,J=8.2Hz,1H),4.35(s,2H)。
13C NMR(100MHz,CDCl3)δ144.1,138.9,138.6,136.2,128.8,127.5,127.5,123.8,118.6,47.9。
MS(ESI)[M+H]+184.60。
实施例31
合成N-苄基吡啶-4-胺,具体按照以下步骤进行:
按照施例14中N-苄基苯胺的合成方法,用双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂6d,94mg(1mmol)4-氨基吡啶代替苯胺,其他操作条件同实施例14,反应结束后得到148mg白色固体,即N-苄基吡啶-4-胺,其产率为80%。
1H NMR(400MHz,CDCl3)δ8.20(d,J=3.3Hz,2H),7.39–7.28(m,5H),6.49(d,J=5.1Hz,2H),4.77(s,1H),4.38(d,J=5.1Hz,2H)。
13C NMR(100MHz,CDCl3)δ153.4,150.2,138.0,129.0,127.8,127.5,107.9,47.1。
MS(ESI)[M+H]+184.60。
Claims (8)
1.一种新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其特征在于:具有如式一所示的结构:
其中,R为甲基、异丙基、苯基或均三甲基苯基;X为氯、六氟磷酸基、四氟硼酸基、四苯基硼酸基、三氟甲磺酸基或四(3,5-二(三氟甲基)苯基)硼酸基。
2.一种权利要求1所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的制备方法,其特征在于:是将氧化银和相应的双齿磷-氮杂咪唑氯盐配体加入到二氯甲烷溶液中,避光,室温,氮气保护条件下反应12~24h;然后在氮气保护下加入与配体0.5当量的[Ru(p-cymene)Cl2]2,室温反应12~24h;反应后过滤、重结晶或用二氯甲烷-甲醇过硅胶柱分离,得到双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂,其中阴离子X为Cl。
3.根据权利要求2所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的制备方法,其特征在于:氧化银和双齿磷-氮杂咪唑氯盐配体的摩尔用量比为(1~2):1。
4.根据权利要求2所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的制备方法,其特征在于:将阴离子X为Cl的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂和等摩尔量的相应阴离子的银盐(X=PF6,OTf或BF4)或钠盐(X=BArF或BPh4),在二氯甲烷溶液中搅拌2~5h,旋干、过柱,得到不同X阴离子(X=PF6、OTf、BF4、BArF或BPh4)的双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂。
5.一种权利要求1所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的用途,其特征在于:是作为金属催化剂催化醇与胺的反应,用于合成制备N-烷基类化合物。
6.根据权利要求5所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的用途,其特征在于:所述N-烷基类化合物的通式为:
所述醇的通式为:
所述胺的通式为:
其中,R1为吸电子取代基氟、氯、溴,或给电子取代基甲基、甲氧基;R2为芳香取代基或脂肪取代基。
7.根据权利要求5所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的用途,其特征在于:合成制备N-烷基类化合物是将所述新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂、醇、胺和碱加入到溶剂中,氮气保护下在50~90℃反应2~12h;反应完毕,降至室温,加水淬灭,用乙酸乙酯萃取,浓缩、纯化、干燥,得到N-烷基类化合物。
8.根据权利要求7所述的新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂的用途,其特征在于:所述新型双齿磷-氮杂卡宾对伞花烃型钌配合物催化剂、醇、胺和碱的摩尔比为(0.001~0.05):1:1:1;所述的碱为叔丁醇钾;所述的溶剂为甲苯。
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