JP6708341B2 - Nitrogen-containing heterocyclic carbene-gold(I) complex with immobilized magnetic nanoparticles - Google Patents
Nitrogen-containing heterocyclic carbene-gold(I) complex with immobilized magnetic nanoparticles Download PDFInfo
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- JP6708341B2 JP6708341B2 JP2016125898A JP2016125898A JP6708341B2 JP 6708341 B2 JP6708341 B2 JP 6708341B2 JP 2016125898 A JP2016125898 A JP 2016125898A JP 2016125898 A JP2016125898 A JP 2016125898A JP 6708341 B2 JP6708341 B2 JP 6708341B2
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- 229910052737 gold Inorganic materials 0.000 title claims description 68
- 239000010931 gold Substances 0.000 title claims description 68
- 239000002122 magnetic nanoparticle Substances 0.000 title claims description 47
- -1 halide ion Chemical class 0.000 claims description 147
- 239000003054 catalyst Substances 0.000 claims description 44
- 230000005291 magnetic effect Effects 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 150000002430 hydrocarbons Chemical group 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 22
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 15
- 238000005913 hydroamination reaction Methods 0.000 claims description 14
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 13
- 239000007983 Tris buffer Substances 0.000 claims description 13
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 claims description 8
- 229910000859 α-Fe Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 34
- 229910052710 silicon Inorganic materials 0.000 description 34
- 239000010703 silicon Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 150000004693 imidazolium salts Chemical class 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 238000007259 addition reaction Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 7
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 239000003622 immobilized catalyst Substances 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ZSYQVVKVKBVHIL-UHFFFAOYSA-N 1-tert-butyl-4-ethynylbenzene Chemical compound CC(C)(C)C1=CC=C(C#C)C=C1 ZSYQVVKVKBVHIL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 0 CN1C=CN(*)C1** Chemical compound CN1C=CN(*)C1** 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- YQALRAGCVWJXGB-UHFFFAOYSA-M gold(1+);methylsulfanylmethane;chloride Chemical compound CS(C)=[Au]Cl YQALRAGCVWJXGB-UHFFFAOYSA-M 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 239000011541 reaction mixture Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 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 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWNXIDDYGKZWEY-UHFFFAOYSA-J tetrabromoiron Chemical compound Br[Fe](Br)(Br)Br BWNXIDDYGKZWEY-UHFFFAOYSA-J 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、新規な磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体、このものを製造する方法、及びこのものから成る炭素−炭素多重結合への付加反応用触媒に関するものである。 TECHNICAL FIELD The present invention relates to a novel magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex, a method for producing the same, and a catalyst for addition reaction to a carbon-carbon multiple bond comprising the same. ..
従来の有機合成反応は液相反応が中心であるが、液相反応では、触媒は反応溶液に溶解しているため、触媒の回収、再利用(リサイクル)が容易でなく、触媒のリサイクルを図るには、反応後の抽出などの後処理、さらには精製などの操作が必要とされる。また触媒の多くは金属を含有し、これが反応処理液に混入してくるため、そのままでは排出できず、環境保全の面からも問題がある。そこで触媒の回収、再利用が容易で、環境にも優しい新規固定化触媒やそれを用いる新しい合成手法が求められている。 Conventional organic synthesis reactions are mainly liquid-phase reactions, but in liquid-phase reactions, the catalyst is dissolved in the reaction solution, so it is not easy to recover and reuse (recycle) the catalyst, and the catalyst is recycled. Requires post-treatment such as extraction after the reaction, and further operation such as purification. Further, most of the catalysts contain metals, which are mixed in the reaction solution, and therefore cannot be discharged as they are, which is problematic in terms of environmental protection. Therefore, there is a need for a new immobilized catalyst that is easy to recover and reuse, and is environmentally friendly, and a new synthetic method using the same.
最近触媒の回収、再利用を行うべく、固相固定化触媒やフルオラスタグを導入した触媒等が種々開発されている。しかしこれらを用いた場合も濾別による回収操作やフルオラス溶媒を用いた抽出操作が必要とされる(非特許文献１、２参照)。 Recently, in order to recover and reuse the catalyst, various solid-phase-immobilized catalysts, fluorous-tagged catalysts, and the like have been developed. However, even when these are used, a collection operation by filtration and an extraction operation using a fluorous solvent are required (see Non-Patent Documents 1 and 2).
近年四酸化三鉄(マグネタイト)等の磁性ナノ粒子(非特許文献３)に触媒機能性部位を固定化した磁性ナノ粒子固定化触媒の合成プロセスにおける有用性が報告されている。反応後に磁石を反応容器に近づけると触媒は引き寄せられるので、デカンテーションにより反応生成物を含む反応溶液を取り出すことができ、さらに触媒が残った反応容器に反応溶媒と反応基質を加えることにより、触媒を再利用でき、触媒のリサイクルの操作が簡便である(非特許文献４、５、６参照)。 In recent years, usefulness in a synthesis process of a magnetic nanoparticle-immobilized catalyst in which a catalytic functional site is immobilized on magnetic nanoparticles such as triiron tetraoxide (magnetite) has been reported (Non-patent Document 3). Since the catalyst is attracted when the magnet is brought close to the reaction vessel after the reaction, the reaction solution containing the reaction product can be taken out by decantation, and the reaction solvent and the reaction substrate are added to the reaction vessel in which the catalyst remains, thereby the catalyst is added. Can be reused, and the operation of recycling the catalyst is simple (see Non-Patent Documents 4, 5, and 6).
例えば、これまでに磁性ナノ粒子固定化パラジウム触媒や銅触媒などが報告されている。これらは対応するポリスチレン樹脂固定化触媒よりも触媒活性は高く、またリサイクルを４，５回程度行っても収率の低下は殆どない(非特許文献７、８参照)。 For example, magnetic nanoparticle-immobilized palladium catalysts and copper catalysts have been reported so far. These have higher catalytic activity than the corresponding polystyrene resin-immobilized catalysts, and even if the recycling is repeated about 4 or 5 times, there is almost no decrease in yield (see Non-Patent Documents 7 and 8).
一方、近年炭素−炭素多重結合への付加反応に有効な含窒素複素環カルベン−金(Ｉ)錯体構造を有する、リサイクルが可能な新規固定化含窒素複素環カルベン−金(Ｉ)錯体触媒が開発されている。しかしこれまでに報告されている支持体はシリカやデンドリマー等であり、磁性ナノ粒子への固定化は報告されていない(非特許文献９、１０、特許文献１参照)。 On the other hand, in recent years, a new recyclable immobilized nitrogen-containing heterocyclic carbene-gold(I) complex catalyst having a nitrogen-containing heterocyclic carbene-gold(I) complex structure effective for addition reaction to carbon-carbon multiple bond has recently been developed. Being developed. However, the supports that have been reported so far are silica and dendrimers, and immobilization on magnetic nanoparticles has not been reported (see Non-Patent Documents 9, 10 and Patent Document 1).
本発明は、このような事情のもとでなされたものであり、磁性ナノ粒子固定化触媒として、炭素−炭素多重結合への付加反応に用いられる新規な固定化含窒素複素環カルベン−金(Ｉ)錯体を提供することを目的とする。 The present invention has been made under such circumstances, and as a magnetic nanoparticle-immobilized catalyst, a novel immobilized nitrogen-containing heterocyclic carbene-gold (used for an addition reaction to a carbon-carbon multiple bond) ( I) The purpose is to provide a complex.
本発明者らは、前記した磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体について鋭意研究を重ねた結果、溶媒中において磁性ナノ粒子と含窒素複素環カルベン−金(Ｉ)錯体構造を有するケイ素化合物とを反応させると、新規な磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体が容易に得られること、そしてこの磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、炭素−炭素多重結合への付加反応を効率的に促進させ、さらに反応終了後磁石を近づけることにより引き寄せられ、回収、再利用可能な固定化含窒素複素環カルベン−金(Ｉ)錯体触媒として有用であることを見出し、これらの知見に基づいて本発明を完成するに至った。 As a result of earnest studies on the above-mentioned magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex, the present inventors have found that the magnetic nanoparticles and the nitrogen-containing heterocyclic carbene-gold(I) complex are dissolved in a solvent. A novel magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex can be easily obtained by reacting with a silicon compound having a structure, and this magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold complex The (I) complex efficiently promotes the addition reaction to the carbon-carbon multiple bond, and is attracted by bringing the magnet closer after the reaction is completed, and is recovered and reusable. Immobilized nitrogen-containing heterocyclic carbene-gold ( I) It was found to be useful as a complex catalyst, and the present invention has been completed based on these findings.
すなわち、この出願は以下の発明を提供するものである。
（１）一般式（Ｉ）
で表される含窒素複素環カルベン−金（Ｉ）錯体が、当該一般式中のＳｉに結合する３つのＲ１−Ｏ−基の少なくとも１つが磁性ナノ粒子中の酸素原子と置き換わることにより、当該磁性ナノ粒子に固定化された構造を含有する、磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒。（２）磁性ナノ粒子が、Ｍ（ＩＩ）Ｆｅ２Ｏ４（式中、Ｍ（ＩＩ）は、Ｆｅ２＋、Ｃｏ２＋、Ｎｉ２＋、Ｍｎ２＋、Ｚｎ２＋、Ｍｇ２＋またはＣｕ２＋であり、単独でも複数が組み合わされて含まれてもよい。）で表される組成のフェライトを主成分とすることを特徴とする、（１）に記載の磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒。
（３）下記の一般式（ＩＩ）、
で表される磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体構造を含有する、（２）に記載の磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒。
（４）一般式（Ｖ）
で表される構造を有する含窒素複素環カルベン−金（Ｉ）錯体と、磁性ナノ粒子とを、溶媒中で反応させることを特徴とする、（１）に記載の磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒の製造方法。
（５）磁性ナノ粒子が、Ｍ（ＩＩ）Ｆｅ２Ｏ４（式中、Ｍ（ＩＩ）は、Ｆｅ２＋、Ｃｏ２＋、Ｎｉ２＋、Ｍｎ２＋、Ｚｎ２＋、Ｍｇ２＋またはＣｕ２＋であり、単独でも複数が組み合わされて含まれてもよい。）で表される組成のフェライトを主成分とすることを特徴とする、（４）に記載の、磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒の製造方法。
（６）下記の一般式（ＩＩ）、
で表される磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体構造を含有する、（４）に記載の、磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒の製造方法。
（７）（１）ないし（３）のいずれかに記載の炭素−炭素多重結合のヒドロアミノ化反応用触媒と、助触媒としてトリフルオロメタンスルホン酸を用いる、炭素−炭素多重結合をヒドロアミノ化する触媒反応方法。
That is, this application provides the following inventions.
(1) General formula (I)
In the nitrogen-containing heterocyclic carbene-gold (I) complex represented by, at least one of the three R 1 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticles, A catalyst for hydroamination reaction of carbon-carbon multiple bonds, which comprises a magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex containing a structure immobilized on the magnetic nanoparticles. (2) The magnetic nanoparticles are M(II)Fe 2 O 4 (wherein M(II) is Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ , Zn 2+ , Mg 2+ or Cu 2+ , and Alternatively, a plurality of them may be contained in combination.) The magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold (1) according to (1), wherein the main component is ferrite having a composition represented by I) A catalyst for a carbon-carbon multiple bond hydroamination reaction comprising a complex.
(3) The following general formula (II),
The carbon composed of the nitrogen-containing heterocyclic carbene-gold(I) complex having the magnetic nanoparticles immobilized thereon according to (2), which contains the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex structure. A catalyst for the hydroamination reaction of carbon multiple bonds .
(4) General formula (V)
The nitrogen-containing heterocyclic carbene-gold (I) complex having the structure represented by the formula (4) and the magnetic nanoparticles are reacted in a solvent, wherein the magnetic nanoparticles are immobilized on the nitrogen-containing nitrogen. A method for producing a catalyst for hydroamination reaction of carbon-carbon multiple bonds, which comprises a heterocyclic carbene-gold(I) complex.
(5) The magnetic nanoparticles are M(II)Fe 2 O 4 (wherein M(II) is Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ , Zn 2+ , Mg 2+ or Cu 2+ , and However, a plurality of them may be contained in combination.) The magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold according to (4), characterized in that the main component is ferrite having a composition represented by (I) A method for producing a catalyst for a carbon-carbon multiple bond hydroamination reaction comprising a complex.
(6) The following general formula (II),
Containing gold (I) complex structure, (4) according to the magnetic nanoparticles immobilized nitrogen-containing heterocyclic carbene - - in magnetic nanoparticles immobilized nitrogen-containing heterocyclic carbene represented made of gold (I) complexes A method for producing a catalyst for hydroamination reaction of carbon-carbon multiple bonds .
(7) A catalytic reaction for hydroaminating a carbon-carbon multiple bond using the catalyst for hydroamination reaction of a carbon-carbon multiple bond according to any one of ( 1) to (3) and trifluoromethanesulfonic acid as a cocatalyst. Way .
本発明に係る磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、炭素−炭素多重結合への付加反応における触媒として有効であり、反応終了後磁石に引き寄せることにより容易に回収でき、また再利用も可能である。 The magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex according to the present invention is effective as a catalyst in an addition reaction to a carbon-carbon multiple bond, and can be easily recovered by attracting it to a magnet after completion of the reaction. It can also be reused.
本発明の新規な磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、下記の一般式(Ｉ)
で表される含窒素複素環カルベン−金(Ｉ)錯体が、当該一般式中のＳｉに結合する３つのＲ1−Ｏ−基の少なくとも１つが磁性ナノ粒子中の酸素原子と置き換わることにより、当該磁性ナノ粒子に固定化された構造を含有する、磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体である。
The novel magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex of the present invention has the following general formula (I):
In the nitrogen-containing heterocyclic carbene-gold (I) complex represented by, at least one of the three R 1 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticles, The magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex contains a structure immobilized on the magnetic nanoparticles.
この磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体について、前記式中の置換基における各符号等で示される内容を具体的に説明することにより、それらの構造をさらに明らかにする。 The structure of the nitrogen-containing heterocyclic carbene-gold(I) complex with magnetic nanoparticles immobilized thereon will be further clarified by specifically explaining the contents represented by the respective symbols and the like in the substituents in the above formula. ..
（１）Ｒ1は炭素数が１〜４のアルキル基を表し、直鎖状、分岐鎖状の何れであってもよい。具体的には、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｔ−ブチルなどの基を挙げることができる。
（２）Ｒ2は炭素数が１〜２０の炭化水素基を表し、炭化水素基は、アルキル基、シクロアルキル基、アリール基及びアラルキル基の中から選ばれる基である。アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。具体的には、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｔ−ブチル、ｎ−ペンチル、ｉ−ペンチル、ｔ−ペンチル、へキシル、ヘプチル、オクチル、ノニル、デカニルなどの基を挙げることができる。
シクロアルキル基は、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル基等を挙げることができる。
アリール基は、置換基を有してもよい芳香族炭化水素基である。
芳香族炭化水素としては、ベンゼン、ビフェニル、テルフェニル、ナフタレン、アントラセン等を挙げることができる。置換基としてはアルキル基等が挙げられ、また２以上の置換基を有していて差し支えない。アルキル基としては炭素数１から３のアルキル基であり、メチル基、エチル基、プロピル基、ｉ−プロピル基を挙げることができる。
アラルキル基は、側鎖としてアルキル基を持つ芳香族炭化水素の側鎖から１個の水素原子が失われた構造であり、ベンジル基、フェネチル基、アントラセニルメチル基等である。
（３）ｎは１〜３０のいずれかの整数で、好ましくは１〜１２である。
（４）Ｌはハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、ヘキサフルオロアンチモネートイオン、トリス(トリフルオロメタンスルホニル)炭素酸イオン、トリフルオロ酢酸イオン、有機カルボン酸イオン、硝酸イオン、硫酸水素イオン、テトラクロロ鉄(III)酸イオン、テトラブロモ鉄(III)酸イオン、トルエンスルホン酸イオン、チオシアン酸イオン、シアン化物イオン、アジ化物イオン、又はビス(トリフルオロメタンスルホニル)イミデートイオンである。
(1) R 1 represents an alkyl group having 1 to 4 carbon atoms, which may be linear or branched. Specific examples include groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl.
(2) R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is a group selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. The alkyl group may be linear or branched. Specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, hexyl, heptyl, octyl, nonyl, Mention may be made of groups such as decanyl.
Examples of the cycloalkyl group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl group and the like.
The aryl group is an aromatic hydrocarbon group which may have a substituent.
Examples of aromatic hydrocarbons include benzene, biphenyl, terphenyl, naphthalene, and anthracene. Examples of the substituent include an alkyl group and the like, and may have two or more substituents. The alkyl group is an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and an i-propyl group.
The aralkyl group has a structure in which one hydrogen atom is lost from the side chain of an aromatic hydrocarbon having an alkyl group as a side chain, and examples thereof include a benzyl group, a phenethyl group and an anthracenylmethyl group.
(3) n is an integer of 1 to 30, and preferably 1 to 12.
(4) L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris(trifluoromethanesulfonyl)carbonate ion, trifluoroacetate ion , Organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis( Trifluoromethanesulfonyl)imidate ion.
支持体の磁性ナノ粒子としては、当該磁性ナノ粒子中の酸素原子が、上述の一般式(Ｉ)で表される含窒素複素環カルベン−金(Ｉ)錯体中のＳｉに結合する３つのＲ1−Ｏ−基の少なくとも１つと置き換わることにより、該錯体が前記磁性ナノ粒子に固定化されるものであれば、どのような化合物や組成のものでもよい。例えば、マグへマイト(γ−Ｆｅ2Ｏ3)等の磁性鉄化合物ナノ粒子などを挙げることができるが、好適には、Ｍ(II)Ｆｅ2Ｏ4を組成とするフェライトナノ粒子(より好適には、マグネタイトＦｅ3Ｏ4)、又は、該フェライトを主成分(５０ｗｔ％以上)とする磁性ナノ粒子を用いることができる。Ｍ(II)としては、Ｆｅ2+、Ｃｏ2+、Ｎｉ2+、Ｍｎ2+、Ｚｎ2+、Ｍｇ2+及びＣｕ2+が挙げられ、これらが単独でも複数が組み合わされて含まれてもよい。磁性ナノ粒子は、磁力による回収に悪影響のない程度(例えば、５０ｗｔ％未満)の非磁性部分(例えば、シリカ(ＳｉＯ2)の被覆)を有していてもよい。 As the magnetic nanoparticles of the support, three R atoms in which the oxygen atom in the magnetic nanoparticles is bonded to Si in the nitrogen-containing heterocyclic carbene-gold (I) complex represented by the above general formula (I) are used. Any compound or composition may be used as long as the complex is immobilized on the magnetic nanoparticles by replacing at least one 1- O- group. For example, magnetic iron compound nanoparticles such as maghemite (γ-Fe 2 O 3 ) can be mentioned, but preferably ferrite nanoparticles having M(II)Fe 2 O 4 as a composition (more preferable) For this, magnetite Fe 3 O 4 ) or magnetic nanoparticles containing the ferrite as a main component (50 wt% or more) can be used. Examples of M(II) include Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ , Zn 2+ , Mg 2+ and Cu 2+ , and these may be contained alone or in combination. Good. The magnetic nanoparticles may have a non-magnetic portion (for example, a coating of silica (SiO 2 )) to the extent that the recovery by magnetic force is not adversely affected (for example, less than 50 wt %).
以下に、磁性ナノ粒子としてフェライトを用いた場合を例にとって、磁性ナノ粒子支持体への有機基の固定化の形態を説明する。固定化の主な形態として、一般式(II)が挙げられる。
上記の構造は鉄酸化物の表面の３個の酸素原子とケイ素が結合し、固定化されている。しかしこの場合、必ずしも酸素３原子の３箇所で固定化している必要はなく、酸素２原子での２箇所や酸素１原子での１箇所での固定化もあり得る。またＳｉ−Ｏ−Ｓｉ結合により形成されたケイ素化合物のオリゴマーが鉄酸化物に固定化された構造もあり得る。固定化の様式は問わず、フェライトを主成分とする磁性ナノ粒子の表面に固定化されていればよい。酸素原子２個で固定化した構造とケイ素化合物の二量体が固定化した構造の一例をそれぞれ一般式(III)及び一般式(IV)に示す。
In the above structure, three oxygen atoms on the surface of iron oxide and silicon are bonded and fixed. However, in this case, it is not always necessary to fix at three positions of three oxygen atoms, and it is also possible to fix at two positions of two oxygen atoms and one position of one oxygen atom. There may be a structure in which an oligomer of a silicon compound formed by a Si-O-Si bond is fixed to iron oxide. Regardless of the mode of immobilization, it may be immobilized on the surface of the magnetic nanoparticles whose main component is ferrite. An example of a structure in which two oxygen atoms are fixed and a structure in which a dimer of a silicon compound is fixed are shown in general formula (III) and general formula (IV), respectively.
本発明の磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体に導入される金の含有量は、０.００１〜５.０ｍｍｏｌ／ｇ、好ましくは、０.０１〜２.０ｍｍｏｌ／ｇである。
また、磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体の一次粒子の粒径は、０.５〜１０００ｎｍ、好ましくは５〜１００ｎｍであるが、一般に凝集していることが多い。
また、磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、この凝集を解くために、磁性ナノ粒子の表面が、オクタノール等の長鎖アルコールやオレイン酸等の長鎖カルボン酸等の界面活性剤で覆われていてもよい。
The content of gold introduced into the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex of the present invention is 0.001 to 5.0 mmol/g, preferably 0.01 to 2.0 mmol/g. It is g.
The primary particles of the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex have a particle size of 0.5 to 1000 nm, preferably 5 to 100 nm, but generally they are often aggregated.
In order to release this aggregation, the surface of the magnetic nanoparticles has a long-chain alcohol such as octanol or a long-chain carboxylic acid such as oleic acid in order to release this aggregation. It may be covered with a surface active agent.
本発明の磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、下記の一般式(Ｖ)
で表される構造を有する含窒素複素環カルベン−金(Ｉ)錯体が、当該一般式中のＳｉに結合する３つのＲ1−Ｏ−基の少なくとも１つが磁性ナノ粒子中の酸素原子と置き換わることにより、当該磁性ナノ粒子に固定化された構造を含有する、磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、一般式(Ｖ)
で表される、ケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体と、磁性ナノ粒子とを、溶媒中加熱することにより製造することができる。
The nitrogen-containing heterocyclic carbene-gold(I) complex with immobilized magnetic nanoparticles of the present invention has the following general formula (V):
In the nitrogen-containing heterocyclic carbene-gold(I) complex having a structure represented by the formula, at least one of the three R 1 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticles. As a result, the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold (I) complex containing the structure immobilized on the magnetic nanoparticles is represented by the general formula (V):
It can be produced by heating the nitrogen-containing heterocyclic carbene-gold(I) complex containing silicon and the magnetic nanoparticles, which are represented by
この反応に用いられる溶媒としては、ケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体を溶解し得るものであればよく、特に制限されない。例えば、トルエン、ベンゼン、キシレン等の炭化水素、エタノール、１−プロパノール、２−プロパノール、ブタノール等のアルコール等が好ましく挙げられる。また少量の水を添加することにより、Ｓｉ−Ｏ−Ｓｉ結合により形成されたケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体のオリゴマーが生成し固定化することもあるので、導入される金の含有量の向上が見込まれる。
加熱温度は、通常室温から２００℃の範囲で選ばれるが、５０℃から１２０℃が好ましい。溶媒の沸点によっては還流することが望ましい。また、反応中、反応液は攪拌するのがよい。また反応時間は、反応温度及び使用する溶媒等その他の条件により異なり一概に定めることはできないが、好ましくは５〜５０時間程度である。
また、ケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体の使用量については、必ずしも限定する必要はないが、一般的には、原料の磁性ナノ粒子１グラムあたり０.０１〜１グラム、好ましくは０.１〜０.５グラムの範囲の、ケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体が用いられる。また原料の磁性ナノ粒子は調製後、反応溶媒に含浸して保存されたものを用いてもよい。
The solvent used in this reaction is not particularly limited as long as it can dissolve the nitrogen-containing heterocyclic carbene-gold(I) complex containing silicon. Preferred examples include hydrocarbons such as toluene, benzene and xylene, and alcohols such as ethanol, 1-propanol, 2-propanol and butanol. Further, by adding a small amount of water, an oligomer of a nitrogen-containing heterocyclic carbene-gold(I) complex containing silicon formed by a Si-O-Si bond may be formed and immobilized, so that it is introduced. The gold content is expected to improve.
The heating temperature is usually selected in the range of room temperature to 200°C, preferably 50°C to 120°C. Refluxing is desirable depending on the boiling point of the solvent. Moreover, during the reaction, the reaction solution is preferably stirred. The reaction time varies depending on the reaction temperature and other conditions such as the solvent used and cannot be determined unconditionally, but is preferably about 5 to 50 hours.
Further, the amount of the nitrogen-containing heterocyclic carbene-gold(I) complex containing silicon is not necessarily limited, but generally 0.01 to 1 g per 1 g of the raw material magnetic nanoparticles. A nitrogen-containing heterocyclic carbene-gold(I) complex containing silicon, preferably in the range of 0.1 to 0.5 gram, is used. Further, the magnetic nanoparticles as a raw material may be used after being prepared and then impregnated with a reaction solvent and stored.
原料物質として用いられる、一般式(Ｖ)で表される構造を有する含窒素複素環カルベン−金(Ｉ)錯体は、下記の一般式(VI)
で表される、ケイ素を含有するイミダゾリウム塩と酸化銀(Ｉ)とを溶媒中で反応させることにより得られる、ケイ素を含有する含窒素複素環カルベンの溶液と下記の式(ＶII)、
ＡｕＬ[Ｓ(ＣＨ3)2] (ＶII)
(式中、Ｌはハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、ヘキサフルオロアンチモネートイオン、トリス(トリフルオロメタンスルホニル)炭素酸イオン、トリフルオロ酢酸イオン、有機カルボン酸イオン、硝酸イオン、硫酸水素イオン、テトラクロロ鉄(III)酸イオン、テトラブロモ鉄(III)酸イオン、トルエンスルホン酸イオン、チオシアン酸イオン、シアン化物イオン、アジ化物イオン、又はビス(トリフルオロメタンスルホニル)イミデートイオンを示す)
の組成で表される金(Ｉ)化合物を混合し溶媒中で反応させ、反応混合物を所定の手段により濾過することにより反応生成物を得ることができる。
A nitrogen-containing heterocyclic carbene-gold (I) complex having a structure represented by the general formula (V), which is used as a raw material, has the following general formula (VI)
And a solution of a nitrogen-containing heterocyclic carbene containing silicon, obtained by reacting a silicon-containing imidazolium salt with silver (I) oxide in a solvent, and the following formula (VII),
AuL [S (CH 3) 2 ] (VII)
(In the formula, L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris(trifluoromethanesulfonyl)carbonate ion, trifluoroacetic acid Ion, organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis (Indicates trifluoromethanesulfonyl)imidate ion)
The reaction product can be obtained by mixing the gold (I) compound represented by the above composition and reacting in a solvent, and filtering the reaction mixture by a predetermined means.
まず、酸化銀(Ｉ)との反応により、ケイ素を含有する含窒素複素環カルベンが得られる。
反応溶媒としては、ケイ素を含有するイミダゾリウム塩を程よく溶解できるものであり、かつ反応に関与しないものが用いられる。具体的には１，２−ジクロロエタン、Ｎ，Ｎ−ジメチルホルムアミド、アセトニトリル、アセトン、テトラヒドロフラン、ジエチルエーテル等が好ましく、これらの溶媒は単独又は混合溶媒の形で使用される。その中でも好ましい反応溶媒としては、１，２−ジクロロエタンが挙げられる。
First, a nitrogen-containing heterocyclic carbene containing silicon is obtained by a reaction with silver(I) oxide.
As the reaction solvent, those which can dissolve the imidazolium salt containing silicon to a sufficient extent and which do not participate in the reaction are used. Specifically, 1,2-dichloroethane, N,N-dimethylformamide, acetonitrile, acetone, tetrahydrofuran, diethyl ether and the like are preferable, and these solvents are used alone or in the form of a mixed solvent. Among them, a preferable reaction solvent is 1,2-dichloroethane.
また、用いる酸化銀(Ｉ)の使用量については、必ずしも限定する必要はないが、一般的には、ケイ素を含有するイミダゾリウム塩１モルあたり０.５〜４モル、好ましくは０.５〜２モルの範囲の酸化銀(Ｉ)が用いられる。
この溶媒を用いてケイ素を含有するイミダゾリウム塩と酸化銀(Ｉ)との反応を行うに際しては、好ましくは、アルゴン等の不活性ガス雰囲気下、ケイ素を含有するイミダゾリウム塩を溶媒に添加して得られる溶液に必要量の酸化銀(Ｉ)を加えた後、十分に攪拌しながら反応させる。
The amount of silver(I) oxide used is not necessarily limited, but generally 0.5 to 4 mol, preferably 0.5 to 5 mol per mol of the imidazolium salt containing silicon. Silver(I) oxide in the range of 2 moles is used.
When the reaction of the imidazolium salt containing silicon with silver (I) oxide is performed using this solvent, preferably, the imidazolium salt containing silicon is added to the solvent under an atmosphere of an inert gas such as argon. The required amount of silver(I) oxide is added to the resulting solution, and the reaction is carried out with sufficient stirring.
反応条件については、反応温度は好ましくは室温ないし１６０℃の範囲であるが、それぞれの溶媒の沸点により上限が異なる。また反応時間は、反応温度及び使用する溶媒等のその他の条件により異なり一概に定めることはできないが、好ましくは２〜５０時間程度である。
反応溶液を一部取り出し、この1Ｈ ＮＭＲ測定より、イミダゾリウム塩がなくなり含窒素複素環カルベンが生成したことが確認される。
Regarding the reaction conditions, the reaction temperature is preferably in the range of room temperature to 160° C., but the upper limit varies depending on the boiling point of each solvent. The reaction time varies depending on the reaction temperature and other conditions such as the solvent used and cannot be determined unconditionally, but is preferably about 2 to 50 hours.
A part of the reaction solution was taken out and the 1 H NMR measurement confirmed that the imidazolium salt disappeared and a nitrogen-containing heterocyclic carbene was produced.
含窒素複素環カルベンの生成を確認後、この溶液に金(Ｉ)化合物を加えることにより、ジメチルスルフィドが解離するとともに、含窒素複素環カルベン−金(Ｉ)錯体が生成される。 After confirming the formation of the nitrogen-containing heterocyclic carbene, a gold(I) compound is added to this solution to dissociate the dimethyl sulfide and to generate a nitrogen-containing heterocyclic carbene-gold(I) complex.
用いる金(Ｉ)化合物の使用量については、必ずしも限定する必要はないが、一般的には、ケイ素を含有する含窒素複素環カルベン１モルあたり１〜４モル、好ましくは１〜１.５モルの範囲の金(Ｉ)化合物が用いられる。
このケイ素を含有する含窒素複素環カルベンと金(Ｉ)化合物との反応を行うに際しては、好ましくは、アルゴン等の不活性ガス雰囲気下、ケイ素を含有する含窒素複素環カルベン溶液に必要量の金(Ｉ)化合物を加えた後、十分に攪拌しながら反応させる。
The amount of the gold (I) compound used is not necessarily limited, but is generally 1 to 4 mol, preferably 1 to 1.5 mol per mol of the nitrogen-containing heterocyclic carbene containing silicon. Gold(I) compounds in the range of are used.
When the reaction of the nitrogen-containing heterocyclic carbene containing silicon with the gold (I) compound is carried out, it is preferable to add a necessary amount of the nitrogen-containing heterocyclic carbene solution containing silicon under an inert gas atmosphere such as argon. After adding the gold (I) compound, the reaction is carried out with sufficient stirring.
反応条件については、反応温度は好ましくは室温ないし８０℃の範囲であるが、室温程度で十分進行する。また反応時間は、反応温度及び使用する溶媒等のその他の条件により異なり一概に定めることはできないが、好ましくは１〜２０時間程度である。
反応溶液を一部取り出し、この1Ｈ ＮＭＲ測定より、ケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体が生成したことが確認される。
Regarding the reaction conditions, the reaction temperature is preferably in the range of room temperature to 80° C., but the reaction proceeds at about room temperature. The reaction time varies depending on the reaction temperature and other conditions such as the solvent used and cannot be determined unconditionally, but is preferably about 1 to 20 hours.
A part of the reaction solution was taken out, and the 1 H NMR measurement confirmed that a nitrogen-containing heterocyclic carbene-gold(I) complex containing silicon was formed.
反応終了後、アルゴン雰囲気下セライト濾過により、銀化合物や過剰の金(Ｉ)化合物などが分離除去され、減圧留去により目的物が得られ、1Ｈ ＮＭＲ測定よりケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体の生成が確認される。 After completion of the reaction, by celite filtration under an argon atmosphere, silver compounds and an excess of gold (I) compounds such separated off, the desired product is obtained by vacuum distillation, nitrogen-containing heterocyclic ring containing silicon from 1 H NMR measurements Formation of a carbene-gold(I) complex is confirmed.
一般式(VI)で表されるケイ素を含有するイミダゾリウム塩は、
一般式(VIII)
で表されるＮ−置換イミダゾールと、一般式(ＩＸ)
で表される、ケイ素・ハロゲンを含有する化合物を、溶媒中で反応させることにより製造することができる。
The imidazolium salt containing silicon represented by the general formula (VI),
General formula (VIII)
And an N-substituted imidazole represented by the general formula (IX)
It can be produced by reacting a compound containing silicon/halogen represented by
これらの製法では、Ｎ−置換イミダゾールの、アルキル基を有しない窒素原子が、ハロゲン原子に隣接する炭素原子上に求核攻撃するため、Ｎ−アルキル化が進行し、ケイ素を含有するイミダゾリウム塩が製造される。 In these production methods, the nitrogen atom having no alkyl group of the N-substituted imidazole nucleophilically attacks on the carbon atom adjacent to the halogen atom, so that the N-alkylation proceeds and the silicon-containing imidazolium salt proceeds. Is manufactured.
反応溶媒としてはＮ−置換イミダゾールとケイ素・ハロゲンを含有する化合物を程よく溶解できるものであり、かつ反応に関与しないものが用いられる。具体的にはＮ，Ｎ−ジメチルホルムアミド、アセトニトリル、アセトン、テトラヒドロフラン、ジエチルエーテルやジクロロメタン等のハロゲン化炭化水素等が好ましく、これらの溶媒は単独又は混合溶媒の形で使用される。その中でも好ましい反応溶媒としては、Ｎ，Ｎ−ジメチルホルムアミドやアセトニトリルやこれらの混合溶媒が挙げられる。
この溶媒を用いてＮ−置換イミダゾールとケイ素・ハロゲンを含有する化合物との反応を行うに際しては、好ましくは、アルゴン等の不活性ガス雰囲気下、Ｎ−置換イミダゾールとケイ素・ハロゲンを含有する化合物とを溶媒に添加して得られる溶液を十分に攪拌しながら反応させる。
As the reaction solvent, those which can dissolve the N-substituted imidazole and the compound containing silicon/halogen in a proper amount and which do not participate in the reaction are used. Specifically, halogenated hydrocarbons such as N,N-dimethylformamide, acetonitrile, acetone, tetrahydrofuran, diethyl ether and dichloromethane are preferable, and these solvents are used alone or in the form of a mixed solvent. Among them, preferable reaction solvents include N,N-dimethylformamide, acetonitrile and mixed solvents thereof.
In carrying out the reaction of the N-substituted imidazole with the compound containing silicon/halogen using this solvent, preferably, the compound containing N-substituted imidazole and the compound containing silicon/halogen under an inert gas atmosphere such as argon. Is added to the solvent and the resulting solution is reacted with sufficient stirring.
反応条件については、反応温度は好ましくは室温ないし１６０℃の範囲であるが、それぞれの溶媒の沸点により上限が異なる。また反応時間は、反応温度及び使用する溶媒等のその他の条件により異なり一概に定めることはできないが、好ましくは２〜５０時間程度である。
また、ケイ素・ハロゲンを含有する化合物の使用量については、必ずしも限定する必要はないが、一般的には、Ｎ−置換イミダゾール１モルあたり１〜３モル、好ましくは１〜１.３モルの範囲のケイ素・ハロゲンを含有する化合物が用いられる。
Regarding the reaction conditions, the reaction temperature is preferably in the range of room temperature to 160° C., but the upper limit varies depending on the boiling point of each solvent. The reaction time varies depending on other conditions such as the reaction temperature and the solvent used and cannot be determined unconditionally, but it is preferably about 2 to 50 hours.
The amount of the compound containing silicon/halogen used is not necessarily limited, but is generally 1 to 3 mol, preferably 1 to 1.3 mol per mol of the N-substituted imidazole. Compounds containing silicon/halogen are used.
反応溶液を一部取り出し、この1Ｈ ＮＭＲ測定より、Ｎ−置換イミダゾールがなくなりイミダゾリウム塩が生成したことが確認される。反応溶液の減圧留去により、ケイ素を含有するイミダゾリウム塩が得られた。 A part of the reaction solution was taken out and the 1 H-NMR measurement confirmed that the N-substituted imidazole had disappeared and an imidazolium salt had been produced. The reaction solution was distilled off under reduced pressure to obtain an imidazolium salt containing silicon.
磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体を用いることにより、炭素−炭素多重結合への付加反応が進行することから、本磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、付加反応用新規触媒として有用である。 Since the addition reaction to the carbon-carbon multiple bond proceeds by using the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex, the present magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex The I) complex is useful as a new catalyst for addition reaction.
本発明の磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体をこのような付加反応用触媒として用いた反応の１例について、以下に説明する。 One example of the reaction in which the nitrogen-containing heterocyclic carbene-gold(I) complex on which magnetic nanoparticles are immobilized according to the present invention is used as a catalyst for such an addition reaction will be described below.
前記触媒として磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体の存在下に、一般式(Ｘ)
で表されるアルキンと、一般式(XI)
で表されるアミンを反応させ、一般式(XII)
及び一般式(XIII)
で表されるイミンを製造することができる。この場合、アルキンによっては片方のみ生成する場合もある。
上記炭化水素基は特に限定されず、アルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基等が挙げられる。
In the presence of a nitrogen-containing heterocyclic carbene-gold(I) complex having magnetic nanoparticles immobilized thereon as the catalyst, the compound of the general formula (X)
And an alkyne represented by the general formula (XI)
By reacting an amine represented by the general formula (XII)
And the general formula (XIII)
An imine represented by can be produced. In this case, depending on the alkyne, only one may be generated.
The hydrocarbon group is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group and an aralkyl group.
この反応は、通常溶媒を用いないで行われるが、用いてもよい。溶媒を用いる場合、原料物質と反応しないジクロロメタン、１，２−ジクロロエタン、トルエン、テトラヒドロフラン、１，４−ジオキサン、Ｎ，Ｎ−ジメチルホルムアミド等が用いられる。
また反応は加熱するのが好ましく、通常６０−１２０℃で行われる。反応中、反応液は攪拌するのがよい。また助触媒としてトリフルオロメタンスルホン酸等のプロトン酸を添加することにより、反応は加速される。
磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体の使用量については、必ずしも限定する必要はないが、一般的には、アミンまたはアルキンのうち、使用量が少ない方の基質１モルあたり０.００１〜０.２モル、好ましくは０.００５〜０.０５モルの範囲の磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体が用いられる。
This reaction is usually performed without using a solvent, but it may be used. When a solvent is used, dichloromethane, 1,2-dichloroethane, toluene, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide or the like that does not react with the raw material is used.
Further, the reaction is preferably heated, and usually carried out at 60 to 120°C. During the reaction, the reaction solution is preferably stirred. The reaction is accelerated by adding a protic acid such as trifluoromethanesulfonic acid as a cocatalyst.
The amount of the nitrogen-containing heterocyclic carbene-gold(I) complex on which the magnetic nanoparticles are immobilized is not necessarily limited, but in general, 1 mol of the substrate of the amine or alkyne with the smaller amount is used. The amount of the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex is 0.001 to 0.2 mol, preferably 0.005 to 0.05 mol.
反応終了後、磁石を反応容器に近づけ磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体を引き寄せ、デカンテーションにより反応溶液を取り出すことにより、磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体触媒を回収できる。そして再度反応容器に反応基質等を添加することにより、触媒の再利用が可能である。また取り出した反応溶液を濃縮しカラムクロマトグラフィー等による分離精製により目的物質を得ることができる。 After completion of the reaction, the magnet was brought close to the reaction vessel to attract the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold (I) complex, and the reaction solution was taken out by decantation to remove the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene- The gold(I) complex catalyst can be recovered. Then, the catalyst can be reused by adding the reaction substrate and the like to the reaction vessel again. Further, the reaction solution taken out is concentrated and the target substance can be obtained by separation and purification by column chromatography or the like.
従来、含窒素複素環カルベン−金(Ｉ)錯体触媒の回収・再利用(リサイクル)には、濾過操作や分液操作等が必要であったが、本磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体触媒を用いた場合、触媒を磁石に引き寄せ、反応溶液をデカンテーションするだけで回収でき、再度反応容器に反応基質等を添加することにより再利用が可能であり、容易にリサイクルが実現される点が本触媒の利点といえる。 In the past, collection and reuse (recycling) of the nitrogen-containing heterocyclic carbene-gold(I) complex catalyst required filtration and liquid separation operations, but the present magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene was used. -When a gold (I) complex catalyst is used, the catalyst can be collected by simply attracting the catalyst to the magnet and decanting the reaction solution, and can be reused by adding a reaction substrate or the like to the reaction vessel again, and easily. The advantage of this catalyst is that it can be recycled.
このように、本発明の磁性ナノ粒子固定化含窒素複素環カルベン−金(Ｉ)錯体は、炭素−炭素多重結合への付加反応用新規触媒として有用であり、これを用いることにより効率的に炭素−炭素多重結合への付加反応を促進させることができる。 As described above, the magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex of the present invention is useful as a novel catalyst for an addition reaction to a carbon-carbon multiple bond, and by using it, it can be efficiently used. The addition reaction to the carbon-carbon multiple bond can be promoted.
次に、実施例により本発明を更に詳細に説明するが、本発明はこれらの例により何ら限定されるものではない。
なお、以下の実施例では磁性ナノ粒子として、マグネタイト(Ｆｅ3Ｏ4)を用いた。マグネタイトは、上述の非特許文献３に記載の方法に従い合成した。
また、磁性ナノ粒子に固定化するケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体は、上述の非特許文献９に記載された合成方法に準じて行った。
また、磁性ナノ粒子に対するケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体の固定化は、上述の非特許文献６に記載された有機基の固定化方法に準じて行った。
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the following examples, magnetite (Fe 3 O 4 ) was used as the magnetic nanoparticles. Magnetite was synthesized according to the method described in Non-Patent Document 3 described above.
Further, the silicon-containing nitrogen-containing heterocyclic carbene-gold(I) complex immobilized on the magnetic nanoparticles was prepared according to the synthesis method described in Non-Patent Document 9 described above.
Further, the immobilization of the silicon-containing nitrogen-containing heterocyclic carbene-gold(I) complex on the magnetic nanoparticles was carried out according to the organic group immobilization method described in Non-Patent Document 6 described above.
マグネタイト固定化含窒素複素環カルベン−金(Ｉ)錯体の合成例を、原料のケイ素を含有する含窒素複素環カルベン−金(Ｉ)錯体の調製も含め(参考例)以下に記載する。
［参考例１］
アルゴン雰囲気下、以下の構造式(XIV)
次にアルゴン雰囲気下、調製したケイ素を含有するイミダゾリウム塩を１，２−ジクロロエタン(４０ｍＬ)に溶解させ、酸化銀(Ｉ)(４７１.６ｍｇ)を加え、遮光し室温で１８時間攪拌した後、クロロ(ジメチルスルフィド)金(Ｉ)(６１５.９ｍｇ)を加え、遮光し室温で４時間攪拌した。１，２−ジクロロエタンを用い反応液のセライト濾過により、銀塩を除去した。濾液の真空留去により、目的物を得た(淡紫色油状 １.０３３４ｇ)。
このものの1Ｈ ＮＭＲと13Ｃ ＮＭＲの結果は次のとおりである。
1Ｈ ＮＭＲ(４００ＭＨｚ；ＣＤＣｌ3)δ７.２０(ｄ，Ｊ＝１.９Ｈｚ，１Ｈ)，６.９５(ｓ，２Ｈ)，６.８７(ｄ，Ｊ＝１.９Ｈｚ，１Ｈ)，４.２９(ｔ，Ｊ＝７.１Ｈｚ，２Ｈ)，３.８４(ｑ，Ｊ＝７.０Ｈｚ，６Ｈ)，２.３２(ｓ，３Ｈ)，２.０９−２.０３(ｍ，２Ｈ)，２.００(ｓ，６Ｈ)，１.２４(ｔ，Ｊ＝７.０Ｈｚ，９Ｈ)，０.６５(ｔ，Ｊ＝８.２Ｈｚ，２Ｈ).
13Ｃ ＮＭＲ(１００ＭＨｚ；ＣＤＣｌ3)δ１７１.８，１３９.６，１３４.８４，１３４.７７，１２９.４，１２１.９，１２０.７，５８.６，５３.５，２５.０，２１.１，１８.３，１７.８，７.３.
これらの分析結果より、この生成物は以下の構造式(XVII)
[Reference Example 1]
The following structural formula (XIV) under an argon atmosphere
Next, the prepared imidazolium salt containing silicon was dissolved in 1,2-dichloroethane (40 mL) under an argon atmosphere, silver(I) oxide (471.6 mg) was added, and the mixture was shielded from light and stirred at room temperature for 18 hours. , Chloro(dimethylsulfide)gold(I) (615.9 mg) were added, and the mixture was stirred at room temperature for 4 hours while protected from light. The silver salt was removed by Celite filtration of the reaction solution using 1,2-dichloroethane. The target substance was obtained by vacuum evaporation of the filtrate (1.0334 g of a pale purple oil).
The results of 1 H NMR and 13 C NMR of this product are as follows.
1 H NMR (400 MHz; CDCl 3 ) δ 7.20 (d, J=1.9 Hz, 1 H), 6.95 (s, 2 H), 6.87 (d, J=1.9 Hz, 1 H), 4. 29(t, J=7.1Hz, 2H), 3.84(q, J=7.0Hz, 6H), 2.32(s, 3H), 2.09-2.03(m, 2H), 2.00 (s, 6H), 1.24 (t, J = 7.0Hz, 9H), 0.65 (t, J = 8.2Hz, 2H).
13 C NMR (100 MHz; CDCl 3 ) δ 171.8, 139.6, 134.84, 134.77, 129.4, 121.9, 120.7, 58.6, 53.5, 25.0, 21. .1, 18.3, 17.8, 7.3.
From these analysis results, this product has the following structural formula (XVII)
［実施例１］
アルゴン雰囲気下、マグネタイト(３.３３１７ｇ)と参考例１で調製した含窒素複素環カルベン−金(Ｉ)錯体(１.０３３４ｇ)を脱気したエタノール(６０ｍＬ)に加え、さらに超純水(４２４μＬ)を加え、１分間超音波をかけた後、メカニカルスターラーを用いて攪拌しながら１８時間加熱還流した。反応終了後、磁石を近づけることにより、生成物を壁面に引き寄せ、反応溶液をデカンテーションし、さらに脱気したエタノールで８回洗浄した。その後４０℃で真空乾燥し、目的物を得た(黒色粉末、３.０４０８ｇ)。
このもののＩＲ分析と元素分析の結果は次の通りである。
ＩＲ：３０８６，２９１６，１６５１，１５５８，１５１２，１４５８，１０４２，９４９，９０３，８５６ｃｍ-1
元素分析：Ｃ ２.８７％、Ｈ ０.４５％、Ｎ ０.３４％、Ｃｌ ０.９３％、Ａu ５.７６％
これらの分析結果より、この生成物は以下の構造式(XVIII)で代表される、マグネタイトに有機基が固定化されたマグネタイト固定化含窒素複素環カルベン−金(Ｉ)錯体と同定された。なお、以下の構造式は、マグネタイトに対する有機基の固定化の主な形態である、マグネタイト中の鉄酸化物の表面の３個の酸素原子と有機基のケイ素が結合する形態で記載されているが、［００１７］において述べたように、有機基の磁性ナノ粒子に対する結合形態はこれに限られるものではない。
Under an argon atmosphere, magnetite (3.3317 g) and the nitrogen-containing heterocyclic carbene-gold(I) complex (1.0334 g) prepared in Reference Example 1 were added to degassed ethanol (60 mL), and ultrapure water (424 μL) was added. ) Was added and ultrasonic waves were applied for 1 minute, and then the mixture was heated under reflux for 18 hours with stirring using a mechanical stirrer. After completion of the reaction, the product was attracted to the wall surface by approaching the magnet, the reaction solution was decanted, and further washed with degassed ethanol 8 times. Then, it was vacuum dried at 40° C. to obtain the target product (black powder, 3.0408 g).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 3086, 2916, 1651, 1558, 1512, 1458, 1042, 949, 903, 856 cm -1
Elemental analysis: C 2.87%, H 0.45%, N 0.34%, Cl 0.93%, Au 5.76%
From these analysis results, this product was identified as a magnetite-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex represented by the following structural formula (XVIII), in which an organic group was immobilized on magnetite. In addition, the following structural formulas are described in a form in which three oxygen atoms on the surface of iron oxide in magnetite are bonded to silicon of the organic group, which is the main form of immobilization of the organic group to magnetite. However, as described in [0017], the binding form of the organic group to the magnetic nanoparticles is not limited to this.
［実施例２］
アルゴン雰囲気下、実施例１で得られたマグネタイト固定化含窒素複素環カルベン−金(Ｉ)錯体(０.２０ｍｍｏｌ/ｇ)２９９.８ｍｇ(アミンとしてのアニリンに対し２ｍｏｌ％)、アニリン２７８.６ｍｇ、エチニルベンゼン９１９.５ｍｇと助触媒としてトリフルオロメタンスルホン酸９ｍｇ(アミンとしてのアニリンに対し２ｍｏｌ％)を加え、１００℃にて２４時間メカニカルスターラーを用いて攪拌し、反応させた。
反応終了後、磁石を反応容器に近づけデカンテーションした。さらに触媒を少量のエチニルベンゼンで３回洗浄し反応液と合わせ、この溶液に内部標準として４−ｔ−ブチルトルエンを添加し、1Ｈ ＮＭＲより以下の構造式(XIX)
Under an argon atmosphere, the magnetite-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex obtained in Example 1 (0.20 mmol/g) 299.8 mg (2 mol% based on aniline as amine) and aniline 278.6 mg. , 919.5 mg of ethynylbenzene and 9 mg of trifluoromethanesulfonic acid as a cocatalyst (2 mol% with respect to aniline as an amine) were added, and the mixture was stirred at 100° C. for 24 hours using a mechanical stirrer to react.
After the reaction was completed, the magnet was brought close to the reaction vessel and decanted. Furthermore, the catalyst was washed with a small amount of ethynylbenzene three times, combined with the reaction solution, and 4-t-butyltoluene was added to this solution as an internal standard. From 1 H NMR, the following structural formula (XIX)
［実施例３］
アルゴン雰囲気下、実施例１で得られたマグネタイト固定化含窒素複素環カルベン−金(Ｉ)錯体(０.２０ｍｍｏｌ/ｇ)２９９.７ｍｇ(アミンとしての４−ブロモアニリンに対し２ｍｏｌ％)、４−ブロモアニリン５１６.２ｍｇ、４−ｔ−ブチルエチニルベンゼン１.４２２９ｇと助触媒としてトリフルオロメタンスルホン酸９ｍｇ(アミンとしての４−ブロモアニリンに対し２ｍｏｌ％)を加え、１００℃にて２４時間メカニカルスターラーを用いて攪拌し、反応させた。
反応終了後、磁石を反応容器に近づけデカンテーションした。さらに触媒を少量の４−ｔ−ブチルエチニルベンゼンで３回洗浄し反応液と合わせ、この溶液に内部標準として４−ｔ−ブチルトルエンを添加し、1Ｈ ＮＭＲより以下の構造式(ＸＸ)
Under an argon atmosphere, the magnetite-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex obtained in Example 1 (0.20 mmol/g) 299.7 mg (2 mol% based on 4-bromoaniline as an amine), 4 -Bromoaniline 516.2 mg, 4-t-butylethynylbenzene 1.4229 g and trifluoromethanesulfonic acid 9 mg (2 mol% relative to 4-bromoaniline as amine) as a co-catalyst were added, and the mechanical stirrer was operated at 100°C for 24 hours. Was stirred and reacted.
After the reaction was completed, the magnet was brought close to the reaction vessel and decanted. Further, the catalyst was washed with a small amount of 4-t-butylethynylbenzene three times, combined with the reaction solution, and 4-t-butyltoluene was added to this solution as an internal standard. From 1 H NMR, the following structural formula (XX) was used.
［実施例４］
アルゴン雰囲気下、実施例１で得られたマグネタイト固定化含窒素複素環カルベン−金(Ｉ)錯体(０.２０ｍｍｏｌ/ｇ)３００.４ｍｇ(アミンとしての４−ブロモアニリンに対し２ｍｏｌ％)、４−ブロモアニリン５１５.８ｍｇ、オクチン９９２.４ｍｇと助触媒としてトリフルオロメタンスルホン酸９ｍｇ(アミンとしての４−ブロモアニリンに対し２ｍｏｌ％)を加え、１００℃にて２４時間メカニカルスターラーを用いて攪拌し、反応させた。
反応終了後、磁石を反応容器に近づけデカンテーションした。さらに触媒を少量のオクチンで３回洗浄し反応液と合わせ、この溶液に内部標準として４−ｔ−ブチルトルエンを添加し、1Ｈ ＮＭＲより以下の構造式(XXI)
Under an argon atmosphere, the magnetite-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex obtained in Example 1 (0.20 mmol/g) 300.4 mg (2 mol% based on 4-bromoaniline as amine), 4 -Bromoaniline 515.8 mg, octyne 992.4 mg and trifluoromethanesulfonic acid 9 mg (2 mol% relative to 4-bromoaniline as amine) as a co-catalyst were added, and the mixture was stirred at 100°C for 24 hours using a mechanical stirrer, It was made to react.
After the reaction was completed, the magnet was brought close to the reaction vessel and decanted. Furthermore, the catalyst was washed 3 times with a small amount of octyne, combined with the reaction solution, and 4-t-butyltoluene was added to this solution as an internal standard. From 1 H NMR, the following structural formula (XXI)
Claims (7)
で表される含窒素複素環カルベン−金（Ｉ）錯体が、当該一般式中のＳｉに結合する３つのＲ１−Ｏ−基の少なくとも１つが磁性ナノ粒子中の酸素原子と置き換わることにより、当該磁性ナノ粒子に固定化された構造を含有する、磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒。 General formula (I)
In the nitrogen-containing heterocyclic carbene-gold (I) complex represented by, at least one of the three R 1 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticles, A catalyst for hydroamination reaction of carbon-carbon multiple bonds, which comprises a magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex containing a structure immobilized on the magnetic nanoparticles.
で表される磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体構造を含有する、請求項２に記載の磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒。 The following general formula (II),
The carbon composed of the nitrogen-containing heterocyclic carbene-gold(I) complex having magnetic nanoparticles immobilized thereon according to claim 2, which contains a magnetic nanoparticle-immobilized nitrogen-containing heterocyclic carbene-gold(I) complex structure. A catalyst for the hydroamination reaction of carbon multiple bonds .
で表される構造を有する含窒素複素環カルベン−金（Ｉ）錯体と、磁性ナノ粒子とを、溶媒中で反応させることを特徴とする、請求項１に記載の磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒の製造方法。 General formula (V)
The nitrogen-containing heterocyclic carbene-gold(I) complex having a structure represented by the formula (9) and the magnetic nanoparticles are reacted in a solvent, wherein the magnetic nanoparticles are immobilized on the nitrogen-containing complex. A method for producing a catalyst for hydroamination reaction of carbon-carbon multiple bonds, which comprises a heterocyclic carbene-gold(I) complex.
で表される磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体構造を含有する、請求項４に記載の、磁性ナノ粒子固定化含窒素複素環カルベン−金（Ｉ）錯体からなる炭素−炭素多重結合のヒドロアミノ化反応用触媒の製造方法。 The following general formula (II),
Magnetic nanoparticles immobilized nitrogen-containing heterocyclic carbene represented in - containing gold (I) complex structure, according to claim 4, the magnetic nanoparticles immobilized nitrogen-containing heterocyclic carbene - made of gold (I) complexes A method for producing a catalyst for hydroamination reaction of carbon-carbon multiple bonds .
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| ES2555613B2 (en) * | 2014-06-26 | 2016-04-22 | Universidad De Alcalá | NHC heterogeneized palladium complexes and their uses as recoverable catalysts |
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