JP5704320B2 - Magnetic nanoparticles fixed osmium (VI) acid salt - Google Patents
Magnetic nanoparticles fixed osmium (VI) acid salt Download PDFInfo
- Publication number
- JP5704320B2 JP5704320B2 JP2011040484A JP2011040484A JP5704320B2 JP 5704320 B2 JP5704320 B2 JP 5704320B2 JP 2011040484 A JP2011040484 A JP 2011040484A JP 2011040484 A JP2011040484 A JP 2011040484A JP 5704320 B2 JP5704320 B2 JP 5704320B2
- Authority
- JP
- Japan
- Prior art keywords
- osmium
- magnetic nanoparticle
- general formula
- formula
- fixed
- 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.)
- Active
Links
- 239000002122 magnetic nanoparticle Substances 0.000 title claims description 56
- DNXIKUNCHIMLQB-UHFFFAOYSA-N osmium(6+) Chemical compound [Os+6] DNXIKUNCHIMLQB-UHFFFAOYSA-N 0.000 title claims description 39
- 239000002253 acid Substances 0.000 title claims description 28
- 150000003839 salts Chemical class 0.000 title claims description 25
- 239000003054 catalyst Substances 0.000 claims description 35
- 230000005291 magnetic effect Effects 0.000 claims description 30
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 23
- 229910000859 α-Fe Inorganic materials 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 238000005906 dihydroxylation reaction Methods 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- AFGAERUSIXWDRP-UHFFFAOYSA-N potassium osmium(6+) Chemical compound [K+].[Os+6] AFGAERUSIXWDRP-UHFFFAOYSA-N 0.000 claims description 9
- -1 comprising ferrite Chemical class 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 12
- 238000006243 chemical reaction Methods 0.000 description 58
- 239000000047 product Substances 0.000 description 37
- 150000002430 hydrocarbons Chemical group 0.000 description 32
- 238000000921 elemental analysis Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052762 osmium Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMHFABZDPUOZTN-UHFFFAOYSA-N O.O.[Os+6].[K+] Chemical compound O.O.[Os+6].[K+] ZMHFABZDPUOZTN-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 229910000487 osmium oxide Inorganic materials 0.000 description 6
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 0 C[N+](C)(CCC[Si]1(OC2CCCCCC*3)OC2C3O1)Cc1cc(OCc2ccccc2)cc(OCc2ccccc2)c1 Chemical compound C[N+](C)(CCC[Si]1(OC2CCCCCC*3)OC2C3O1)Cc1cc(OCc2ccccc2)cc(OCc2ccccc2)c1 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 229930195733 hydrocarbon Natural products 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-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
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 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 2
- 150000002009 diols Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 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 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003622 immobilized catalyst Substances 0.000 description 2
- 238000005342 ion exchange Methods 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
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 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 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 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
- 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 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FXNRGRCXYVLCQN-UHFFFAOYSA-N CCCc1cc(C)cc(C)c1C Chemical compound CCCc1cc(C)cc(C)c1C FXNRGRCXYVLCQN-UHFFFAOYSA-N 0.000 description 1
- BFIMMTCNYPIMRN-UHFFFAOYSA-N Cc1cc(C)c(C)c(C)c1 Chemical compound Cc1cc(C)c(C)c(C)c1 BFIMMTCNYPIMRN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LMTHUWYIXZMVRG-UHFFFAOYSA-N O.O.[K+].[Os+6].[K+] Chemical compound O.O.[K+].[Os+6].[K+] LMTHUWYIXZMVRG-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 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
- 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
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000002386 leaching Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 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
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明は、新規な磁性ナノ粒子固定型オスミウム（VＩ）酸塩、このものを製造する方法、及びこのものから成るオレフィンのジヒドロキシル化反応用触媒に関するものである。 The present invention relates to a novel magnetic nanoparticle-fixed osmium (VI) acid salt, a process for producing the same, and a catalyst for dihydroxylation of olefins 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。 The conventional organic synthesis reaction is mainly a liquid phase reaction. However, in the liquid phase reaction, the catalyst is dissolved in the reaction solution, so that it is not easy to recover and reuse (recycle) the catalyst. For this, post-treatment such as extraction after the reaction, and further operations such as purification are required. In addition, most of the catalysts contain metals, which are mixed into the reaction processing solution, so that they cannot be discharged as they are, and there is a problem in terms of environmental conservation. Therefore, there is a need for a new immobilized catalyst that is easy to recover and reuse the catalyst and is environmentally friendly, and a new synthesis method using the same.
最近触媒の回収、再利用を行うべく、ポリマー樹脂固定型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 types such as a polymer resin fixed catalyst and a catalyst incorporating a fluorous tag have been developed. However, even when these are used, a recovery operation by filtration or an extraction operation using a fluorous solvent is 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型触媒の合成プロセスにおける有用性が報告されている。支持体の粒径が小さいので、固定化に伴う触媒活性の低下は、ポリマー樹脂への固定化の場合よりも小さい。また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, the usefulness in a synthesis process of a magnetic nanoparticle-fixed catalyst in which a catalytic functional site is immobilized on magnetic nanoparticles (Non-patent Document 3) such as triiron tetroxide (magnetite) has been reported. Since the particle size of the support is small, the decrease in catalytic activity accompanying immobilization is smaller than in the case of immobilization on a polymer resin. Moreover, 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. The catalyst can be reused and the catalyst recycling operation 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型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型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 fixed palladium catalysts and copper catalysts have been reported so far. These have higher catalytic activity than the corresponding polystyrene resin-fixed catalysts, and there is almost no decrease in yield even after recycling 4 or 5 times (see Non-Patent Documents 7 and 8).
一方、近年オレフィンのジヒドロキシル化反応に有効なＯｓＯ４ ２−の四級アンモニウム塩とのイオン交換に基づく固定化により、リサイクルが可能な新規固定化酸化オスミウム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無機層状化合物、シリカゲル、ポリスチレン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、１１、１２、１３参照）。 On the other hand, in recent years, a new immobilized osmium oxide catalyst that can be recycled has been developed by immobilization based on ion exchange with a quaternary ammonium salt of OsO 4 2− effective for dihydroxylation of olefins. However, the supports reported so far are inorganic layered compounds, silica gel, polystyrene, dendrimers, and the like, and no immobilization on magnetic nanoparticles has been reported (see Non-Patent Documents 9, 10, 11, 12, and 13). ).
本発明は、このような事情のもとでなされたものであり、磁性ナノ粒子固定型触媒として、オレフィンのジヒドロキシル化反応に用いられる新規な固定型酸化オスミウムを提供することを目的とする。 The present invention has been made under such circumstances, and an object of the present invention is to provide a novel fixed osmium oxide used for dihydroxylation of olefins as a magnetic nanoparticle fixed catalyst.
本発明者らは、前記した磁性ナノ粒子固定型オスミウム（VＩ）酸塩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固定型四級アンモニウム塩とオスミウム（VＩ）酸カリウムとを反応させると、新規な磁性ナノ粒子固定型オスミウム（VＩ）酸塩が容易に得られること、そしてこの磁性ナノ粒子固定型オスミウム（VＩ）酸塩は、オレフィンのジヒドロキシル化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酸化オスミウム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 intensive studies on the above-described magnetic nanoparticle-immobilized osmium (VI) acid salt, the present inventors reacted magnetic nanoparticle-immobilized quaternary ammonium salt with osmium (VI) potassium salt in a solvent. And a novel magnetic nanoparticle-immobilized osmium (VI) acid salt can be easily obtained, and this magnetic nanoparticle-immobilized osmium (VI) acid salt effectively promotes the olefin dihydroxylation reaction, Further, after the completion of the reaction, the magnets are attracted by being brought close to each other and found to be useful as an immobilized osmium oxide catalyst that can be recovered and reused, 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）
［式中、Ｒ1及びＲ4は炭化水素基である。ｓ及びｕは０以上の整数、ｔは０または１であり、但し、ｓ、ｕ、ｔの少なくとも１つは０ではない。Ｒ2は炭化水素基または一般式（II）
で表される基である。］
で表されるオスミウム(VI)酸塩が、当該一般式中のＳｉに結合する３つのＲ4−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、磁性ナノ粒子固定型オスミウム(VI)酸塩。
（２） 磁性ナノ粒子が、Ｍ(II)Ｆｅ 2 Ｏ 4 ［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型オスミウム(VI)酸塩。
（３） 下記の一般式（III）
、
で表される基である。］
で表される四級アンモニウム塩構造を含有する、（２）に記載のフェライトを主成分とする磁性ナノ粒子固定型オスミウム(VI)酸塩。
（４） 一般式（VI）
で表される基である。］
で表される構造を有する四級アンモニウム塩が、当該一般式中のＳｉに結合する３つのＲ4−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、磁性ナノ粒子固定型四級アンモニウム塩と、オスミウム(VI)酸カリウム Ｋ 2 ＯｓＯ 4 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型オスミウム(VI)酸塩の製造方法。
（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、磁性ナノ粒子固定型オスミウム(VI)酸塩の製造方法。
（６） 下記の一般式（VII）、
で表される基である。］
で表される四級アンモニウム塩構造を含有する、フェライトを主成分とする磁性ナノ粒子固定型四級アンモニウム塩と、オスミウム(VI)酸カリウム Ｋ 2 ＯｓＯ 4 とを、溶媒中で反応させることを特徴とする、（５）に記載の、フェライトを主成分とする磁性ナノ粒子固定型オスミウム(VI)酸塩の製造方法。
（７） （１）〜（３）のいずれかに記載の磁性ナノ粒子固定型オスミウム(VI)酸塩から成るオレフィンのジヒドロキシル化反応用触媒。
That is, this application provides the following inventions.
(1) General formula (I)
[Wherein, R 1 and R 4 are hydrocarbon groups. s and u are integers greater than or equal to 0, and t is 0 or 1, provided that at least one of s, u, and t is not 0. R 2 represents a hydrocarbon group or a general formula (II)
It is group represented by these. ]
In osmium (VI) salt represented is, by at least one of the three R 4 -O- groups bonded to Si in the formula is replaced with an oxygen atom in the magnetic nanoparticles, to the magnetic nanoparticles Magnetic nanoparticle-fixed osmium (VI) salt containing an immobilized structure.
(2) 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+ , which may be contained alone or in combination. The magnetic nanoparticle-fixed osmium (VI) acid salt according to (1), wherein the main component is a ferrite having a composition represented by the formula:
(3) The following general formula ( III )
,
It is group represented by these. ]
The magnetic nanoparticle fixed osmium (VI) acid salt containing the ferrite according to (2) as a main component, which contains a quaternary ammonium salt structure represented by:
(4) General formula (VI)
It is group represented by these. ]
In which at least one of three R 4 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticle. (1) characterized by reacting a magnetic nanoparticle-fixed quaternary ammonium salt containing a structure fixed to osmium (VI) potassium K 2 OsO 4 in a solvent. Method for producing magnetic nanoparticle fixed osmium (VI) acid salt.
(5) 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+ , which may be contained alone or in combination. The method for producing a magnetic nanoparticle-fixed osmium (VI) salt according to (4), wherein the main component is ferrite having a composition represented by the formula:
(6) The following general formula ( VII ),
It is group represented by these. ]
A magnetic nanoparticle-fixed quaternary ammonium salt having a quaternary ammonium salt structure represented by the following formula and potassium osmium (VI) acid K 2 OsO 4 in a solvent: The manufacturing method of the magnetic nanoparticle fixed type | mold osmium (VI) salt which has a ferrite as a main component as described in (5) characterized by the above-mentioned.
(7) A catalyst for dihydroxylation reaction of an olefin comprising the magnetic nanoparticle fixed osmium (VI) salt according to any one of (1) to (3).
本発明に係る磁性ナノ粒子固定型オスミウム（VＩ）酸塩は、オレフィンのジヒドロキシル化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-fixed osmium (VI) acid salt according to the present invention is effective as a catalyst in the olefin dihydroxylation reaction, and can be easily recovered by drawing it to the magnet after the reaction is completed, and can also be reused. .
本発明の新規な磁性ナノ粒子固定型オスミウム（VＩ）酸塩は、下記の一般式（Ｉ）
で表される基である。］
で表されるオスミウム（VＩ）酸塩が、当該一般式中のＳｉに結合する３つのＲ４−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、磁性ナノ粒子固定型オスミウム（VＩ）酸塩である。
The novel magnetic nanoparticle fixed osmium (VI) salt of the present invention has the following general formula (I)
It is group represented by these. ]
In the magnetic nanoparticle, at least one of three R 4 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticle. Magnetic nanoparticles fixed osmium (VI) acid salt containing an immobilized structure.
この磁性ナノ粒子固定型オスミウム（VＩ）酸塩について、前記式中の置換基における各符号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。 About this magnetic nanoparticle fixed type | mold osmium (VI) acid salt, those structures shown by each code | symbol in the substituent in the said formula are demonstrated concretely, and those structures are further clarified.
（１）Ｒ１は炭化水素基を表し、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、その炭素数が１〜２２であり、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。
（２）ｓ及びｕは０以上の整数で好ましくは０〜１０である。また、ｔは０または１である。但し、ｓ、ｕ、ｔの少なくとも１つは０ではない。
（３）Ｒ２が炭化水素基の場合、Ｒ１と同様である。Ｒ２が一般式（ＩＩ）で表される場合、Ｒ３はＲ１と同様である。この場合、繰り返し構造の世代数ｎは１以上の整数を示すが、好ましくは１〜６である。繰り返し構造は下記一般式（Ｘ）で表される。
−ＣＨ２−Ｃ６Ｈ３−［Ｏ−ＣＨ２−Ｃ６Ｈ３−［Ｏ−ＣＨ２−Ｃ６Ｈ３−（Ｏ−Ｒ３）２］２］２
(1) R 1 represents a hydrocarbon group, 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 has 1 to 22 carbon atoms, and 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, and cycloheptyl groups.
The aryl group is an aromatic hydrocarbon group that may have a substituent.
Examples of the aromatic hydrocarbon include benzene, biphenyl, terphenyl, naphthalene, anthracene and the like. Examples of the substituent include an alkyl group, 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, such as a benzyl group, a phenethyl group, or an anthracenylmethyl group.
(2) s and u are integers of 0 or more, preferably 0 to 10. T is 0 or 1. However, at least one of s, u, and t is not 0.
(3) When R 2 is a hydrocarbon group, the same as R 1 . When R 2 is represented by the general formula (II), R 3 is the same as R 1 . In this case, the generation number n of the repeating structure is an integer of 1 or more, preferably 1-6. The repeating structure is represented by the following general formula (X).
-CH 2 -C 6 H 3 - [ O-CH 2 -C 6 H 3 - [O-CH 2 -C 6 H 3 - (O-R 3) 2] 2] 2
支持体の磁性ナノ粒子としては、Ｍ（ＩＩ）Ｆｅ２Ｏ４を組成とするフェライト、及びこれを含有する、フェライトを主成分とする磁性を有する鉄化合物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。完全にこの構造でなくてもこの組成を含有する磁性ナノ粒子は何れも支持体と成り得る。例えば、シリカ（ＳｉＯ２）で被覆したフェライトがこれに該当する。また、マグへマイト（γ−Fe2O3）を組成とする磁性ナノ粒子も支持体として用い得る。 As magnetic nanoparticles for the support, ferrite having a composition of M (II) Fe 2 O 4 and an iron compound having magnetism containing ferrite as a main component 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 included alone or in combination. Any magnetic nanoparticle containing this composition, even if not completely in this structure, can be a support. For example, a ferrite coated with silica (SiO 2 ) corresponds to this. Magnetic nanoparticles having a composition of maghemite (γ-Fe 2 O 3 ) can also be used as a support.
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（ＩＩＩ）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（ＩＶ）及び一般式（Ｖ）に示す。
In the above structure, three oxygen atoms on the surface of the iron oxide and silicon are bonded and immobilized. However, in this case, it is not always necessary to fix at three locations of three oxygen atoms, and there may be fixing at two locations with two oxygen atoms or one location with one oxygen atom. Further, there may be a structure in which an oligomer of a silicon compound formed by Si—O—Si bond is fixed to iron oxide. Regardless of the mode of immobilization, it may be immobilized on the surface of magnetic nanoparticles mainly composed of ferrite. An example of a structure immobilized with two oxygen atoms and a structure in which a dimer of a silicon compound is immobilized are shown in general formula (IV) and general formula (V), respectively.
本発明の磁性ナノ粒子固定型オスミウム（VＩ）酸塩に導入されるオスミウムの含有量は、０．００１〜５．０ｍｍｏｌ／ｇ、好ましくは、０．０１〜２．０ｍｍｏｌ／ｇである。
また本磁性ナノ粒子固定型オスミウム（VＩ）酸塩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。
また本磁性ナノ粒子固定型オスミウム（VＩ）酸塩は、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 osmium introduced into the magnetic nanoparticle-fixed osmium (VI) salt of the present invention is 0.001 to 5.0 mmol / g, preferably 0.01 to 2.0 mmol / g.
The primary particle diameter of the present magnetic nanoparticle-fixed osmium (VI) acid salt is 0.5 to 1000 nm, preferably 5 to 100 nm, but is generally often aggregated.
In addition, the present magnetic nanoparticle-fixed osmium (VI) salt has a surface of a magnetic nanoparticle made of a surfactant such as a long-chain alcohol such as octanol or a long-chain carboxylic acid such as oleic acid in order to solve this aggregation. It may be covered.
本発明の磁性ナノ粒子固定型オスミウム（VＩ）酸塩は、下記の一般式（ＶＩ）
で表される基である。］
で表される構造を有する四級アンモニウム塩が、当該一般式中のＳｉに結合する３つのＲ４−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、磁性ナノ粒子固定型四級アンモニウム塩と、オスミウム（VＩ）酸カリウム K2OsO4と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 magnetic nanoparticle fixed osmium (VI) acid salt of the present invention has the following general formula (VI)
It is group represented by these. ]
In the general formula, at least one of the three R 4 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticle, whereby the magnetic nanoparticle It can be produced by reacting a magnetic nanoparticle-fixed quaternary ammonium salt containing a structure fixed to osmium (VI) potassium K 2 OsO 4 in a solvent.
この製法では、ハロゲン化物イオンとオスミウム（VＩ）酸イオン（OsO4 ２−）とのイオン交換により、磁性ナノ粒子固定型オスミウム（VＩ）酸塩が製造される。 In this production method, magnetic nanoparticle fixed osmium (VI) acid salt is produced by ion exchange between halide ions and osmium (VI) acid ions (OsO 4 2− ).
反応溶媒としては水が用いられるが、有機溶媒との混合系でもよい。水と有機溶媒との混合系の場合、有機溶媒としては、アセトニトリル、プロピオニトリル、アセトン、ｔ−ブタノールが好ましいが、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロフラン、ジエチルエーテル、ジクロロメタン等のハロゲン化炭化水素、トルエン、キシレン等の炭化水素、メタノール、エタノール等の脂肪族アルコールなどでもよい。
この溶媒を用いて磁性ナノ粒子固定型四級アンモニウム塩とオスミウム（VＩ）酸カリウム K2OsO4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、オスミウム（VＩ）酸カリウムを溶媒に溶解させたところに磁性ナノ粒子固定型四級アンモニウム塩を添加し、十分に攪拌しながら反応させる。
Water is used as the reaction solvent, but a mixed system with an organic solvent may be used. In the case of a mixed system of water and an organic solvent, the organic solvent is preferably acetonitrile, propionitrile, acetone, or t-butanol, but a halogenated hydrocarbon such as N, N-dimethylformamide, tetrahydrofuran, diethyl ether, or dichloromethane. , Hydrocarbons such as toluene and xylene, and aliphatic alcohols such as methanol and ethanol.
When the reaction between the magnetic nanoparticle-fixed quaternary ammonium salt and potassium osmium (VI) acid K 2 OsO 4 is carried out using this solvent, it is preferable that osmium (VI) acid be used in an inert gas atmosphere such as argon. A magnetic nanoparticle fixed quaternary ammonium salt is added to a place where potassium is dissolved in a solvent, and the mixture is allowed to react with sufficient stirring.
反応条件については、反応温度は室温が好ましい。１００℃まで加熱してもよいが、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０．５〜５０時間程度である。
また、オスミウム（VＩ）酸カリウム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、原料のハロゲン１モルあたり０．０１〜５モル、好ましくは０．４〜０．５モルの範囲のオスミウム（VＩ）酸カリウムが用いられる。
As for the reaction conditions, the reaction temperature is preferably room temperature. Although it may heat to 100 degreeC, an upper limit changes with boiling points of each solvent. The reaction time varies depending on the reaction temperature and other conditions such as the solvent to be used and cannot be determined unconditionally, but is preferably about 0.5 to 50 hours.
The amount of potassium osmium (VI) used is not necessarily limited, but is generally 0.01 to 5 mol, preferably 0.4 to 0.5 mol, per mol of raw material halogen. A range of potassium osmium (VI) is used.
反応終了後、磁石を反応容器に近づけることにより、反応生成物は引き寄せられるので反応溶液をデカンテーションする。さらに溶媒で反応生成物を洗浄し、減圧下乾燥することにより、反応生成物が得られ、赤外線吸収スペクトル（ＩＲ）及び元素分析より目的物の生成が確認される。
本反応により、一段階で目的とする磁性ナノ粒子固定型オスミウム（VＩ）酸塩を製造することができる。
After completion of the reaction, the reaction product is attracted by bringing the magnet closer to the reaction vessel, and the reaction solution is decanted. Further, the reaction product is washed with a solvent and dried under reduced pressure to obtain a reaction product. The production of the target product is confirmed by infrared absorption spectrum (IR) and elemental analysis.
By this reaction, the target magnetic nanoparticle fixed osmium (VI) acid salt can be produced in one step.
前記の製造方法において、原料物質に対応する
一般式（ＶＩ）
で表される基である。］
で表される構造を有する四級アンモニウム塩が、当該一般式中のＳｉに結合する３つのＲ４−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、磁性ナノ粒子固定型四級アンモニウム塩は、一般式（ＶＩ）
で表される四級アンモニウム塩と、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。
Ｒ４の炭化水素基は、アルキル基及びアルケニル基の中から選ばれる基である。
アルキル基は、その炭素数が１〜２０であり、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。
アルケニル基としては、ビニル、プロペニル、ブテニル基等を挙げることができる。
この反応に用いられる溶媒としては、四級アンモニウム塩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。
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、反応液は撹拌するのがよい。
In the above production method, the general formula (VI) corresponding to the raw material
It is group represented by these. ]
In the general formula, at least one of the three R 4 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticle, whereby the magnetic nanoparticle The magnetic nanoparticle-immobilized quaternary ammonium salt containing a structure immobilized on the compound has the general formula (VI)
It can manufacture by heating the quaternary ammonium salt represented by these, and a magnetic nanoparticle in a solvent.
The hydrocarbon group for R 4 is a group selected from an alkyl group and an alkenyl group.
The alkyl group has 1 to 20 carbon atoms and 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 alkenyl groups include vinyl, propenyl, and butenyl groups.
The solvent used in this reaction is not particularly limited as long as it can dissolve the quaternary ammonium salt. For example, hydrocarbons such as toluene, benzene and xylene, alcohols such as ethanol, 1-propanol, 2-propanol and butanol are preferable.
The heating temperature is usually selected in the range of room temperature to 200 ° C, preferably 50 ° C to 120 ° C. Depending on the boiling point of the solvent, refluxing is desirable. Further, the reaction solution is preferably stirred during the reaction.
前項の磁性ナノ粒子固定型四級アンモニウム塩の製造方法において原料物質に対応する下記一般式（ＶＩ）
で表される四級アンモニウム塩は、一般式（ＸＩ）
で表される三級アミンと、一般式（ＸＩＩ）
Ｒ２Ｘ （ＸＩＩ）
（式中Ｒ２及びＸは前記と同じ意味を示す。）
で表される含ハロゲン化合物を溶媒中で加熱することにより製造することができる。
あるいは一般式（ＸＩＩＩ）
で表される含ハロゲン化合物と、一般式（ＸＩＶ）
Ｒ１ ２Ｒ２Ｎ （ＸＩＶ）
（式中Ｒ１及びＲ２は前記と同じ意味を示す。）
で表される三級アミンを溶媒中で加熱することにより製造することができる。
これらの反応に用いられる溶媒としては、三級アミンと含ハロゲン化合物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、アセトン、Ｎ，Ｎ−ジメチルホルムアミド、アセトニトリル、ジメチルスルホキシド、テトラヒドロフランやトルエン、ベンゼン、キシレン等の炭化水素等が好ましく挙げられる。
加熱温度は、通常室温から１５０℃の範囲で選ばれるが、５０℃から１００℃が好ましい。また、反応中、反応液は撹拌するのがよい。
The following general formula (VI) corresponding to the raw material in the method for producing a magnetic nanoparticle-fixed quaternary ammonium salt as described above
The quaternary ammonium salt represented by the general formula (XI)
A tertiary amine represented by general formula (XII)
R 2 X (XII)
(Wherein R 2 and X have the same meaning as described above.)
It can manufacture by heating the halogen-containing compound represented by these in a solvent.
Or general formula (XIII)
A halogen-containing compound represented by the general formula (XIV)
R 1 2 R 2 N (XIV)
(Wherein R 1 and R 2 have the same meaning as described above.)
It can manufacture by heating the tertiary amine represented by these in a solvent.
The solvent used in these reactions is not particularly limited as long as it can dissolve a tertiary amine and a halogen-containing compound. For example, preferred are hydrocarbons such as acetone, N, N-dimethylformamide, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, toluene, benzene, and xylene.
The heating temperature is usually selected in the range of room temperature to 150 ° C, preferably 50 ° C to 100 ° C. Further, the reaction solution is preferably stirred during the reaction.
磁性ナノ粒子固定型オスミウム（VＩ）酸塩を用いることにより、オレフィンのジヒドロキシル化反応が進行するから、本磁性ナノ粒子固定型オスミウム（VＩ）酸塩は、新規ジヒドロキシル化反応用触媒として有用である。 Since the dihydroxylation reaction of olefin proceeds by using magnetic nanoparticle fixed osmium (VI) acid salt, this magnetic nanoparticle fixed osmium (VI) acid salt is useful as a novel catalyst for dihydroxylation reaction. It is.
本発明の磁性ナノ粒子固定型オスミウム（VＩ）酸塩をこのような酸化触媒として用いた反応の１例について、以下に説明する。
前記触媒としての磁性ナノ粒子固定型オスミウム（VＩ）酸塩と共酸化剤存在下に、一般式（ＸＶ）
で表されるオレフィンを溶媒中で反応させ、一般式（ＸＶＩ）
で表されるジオール体を製造することができる。
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。
One example of the reaction using the magnetic nanoparticle fixed osmium (VI) acid salt of the present invention as such an oxidation catalyst will be described below.
In the presence of a magnetic nanoparticle-fixed osmium (VI) salt and a co-oxidant as the catalyst, a compound represented by the general formula (XV)
The olefin represented by general formula (XVI) is reacted in a solvent.
The diol body represented by these can be manufactured.
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.
またこの反応は、通常、溶媒に触媒、原料物質及び共酸化剤を溶解させて行われる。共酸化剤には通常N−メチルモルホリンN−オキシド、フェリシアン化カリウム、過酸化水素、ｔ−ブチルヒドロペルオキシド等が用いられる。溶媒には通常有機溶媒と水との混合溶媒が用いられる。有機溶媒として好ましくはアセトン、アセトニトリル、ジオキサン、ｔ−ブチルアルコール等が単独もしくは組み合わせて用いられる。
また反応は、格別加熱することなく、室温程度で進行させることができるが、加熱により促進させるようにしてもよい。反応中、反応液は攪拌するのがよい。
反応終了後、磁石を反応容器に近づけ磁性ナノ粒子固定型オスミウム（VＩ）酸塩を引き寄せ、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、磁性ナノ粒子固定型酸化オスミウム触媒を回収できる。そして再度反応容器に反応溶媒や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による分離精製により目的物質を得ることができる。
特に窒素上に導入される官能基（Ｒ１、Ｒ２）が嵩高い程、オスミウムの反応溶液中への溶出（リーチング）は抑えられ、より効率的な触媒の回収、再利用（リサイクル）が達成される。例えばＲ２が一般式（ＩＩ）の場合がこれに該当し、円滑な触媒のリサイクルが実現される。
This reaction is usually performed by dissolving a catalyst, a raw material and a co-oxidant in a solvent. As the co-oxidant, N-methylmorpholine N-oxide, potassium ferricyanide, hydrogen peroxide, t-butyl hydroperoxide and the like are usually used. As the solvent, a mixed solvent of an organic solvent and water is usually used. As the organic solvent, acetone, acetonitrile, dioxane, t-butyl alcohol or the like is preferably used alone or in combination.
The reaction can be allowed to proceed at about room temperature without special heating, but may be accelerated by heating. During the reaction, the reaction solution is preferably stirred.
After completion of the reaction, the magnetic nanoparticle-fixed osmium oxide catalyst can be recovered by bringing the magnet close to the reaction vessel and attracting the magnetic nanoparticle-fixed osmium (VI) acid salt and taking out the reaction solution by decantation. The catalyst can be reused by adding a reaction solvent, a reaction substrate, and the like to the reaction vessel again. Moreover, the taken-out reaction solution can be concentrated and the target substance can be obtained by separation and purification by column chromatography.
In particular, the more bulky the functional groups (R 1 , R 2 ) introduced onto nitrogen, the more osmium is dissolved out (leaching) into the reaction solution, and more efficient catalyst recovery and reuse (recycling). Achieved. For example, the case where R 2 is the general formula (II) corresponds to this, and smooth catalyst recycling is realized.
従来、酸化オスミウム触媒のリサイクルには、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型酸化オスミウム触媒は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。 Conventionally, recycling and separation operations have been required to recycle the osmium oxide catalyst, but this magnetic nanoparticle-fixed osmium oxide catalyst can be recovered simply by attracting the catalyst to a magnet and decanting the reaction solution. The advantage of this catalyst is that it can be reused by adding a reaction substrate or the like to the reaction vessel again, and can be easily recycled.
このように、本発明の磁性ナノ粒子固定型オスミウム（VＩ）酸塩は、新規ジヒドロキシル化反応用触媒として有用であり、これを用いることにより溶媒中において効率的にオレフィンのジヒドロキシル化反応を促進させることができる。 Thus, the magnetic nanoparticle-immobilized osmium (VI) salt of the present invention is useful as a novel catalyst for dihydroxylation reaction, and by using this, an olefin dihydroxylation reaction can be efficiently carried out in a solvent. 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）またはシリカ（ＳｉＯ２）で被覆したマグネタイトを用いた。これらの磁性ナノ粒子は、上述の非特許文献３に記載の方法に従い合成した。
また、磁性ナノ粒子に対する四級アンモニウム塩の固定化は、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。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In the following examples, magnetite coated with magnetite (Fe 3 O 4 ) or silica (SiO 2 ) was used as magnetic nanoparticles. These magnetic nanoparticles were synthesized according to the method described in Non-Patent Document 3 above.
Further, the quaternary ammonium salt was immobilized on the magnetic nanoparticles in accordance with the organic group immobilization method described in Non-Patent Document 6 described above.
マグネタイト固定型四級アンモニウム塩の合成の一例を、原料の四級アンモニウム塩の調製も含め参考例として以下に記載する。
参考例
アルゴン雰囲気下、（Ｎ，Ｎ−ジメチルアミノプロピル）トリメトキシシラン（４３５．３ｍｇ）と以下の構造式
次にアルゴン雰囲気下、マグネタイト（５８１．１ｍｇ）と調製した四級アンモニウム塩を脱気したエタノール（１２ｍＬ）に加え、さらに超純水（７８μＬ）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撹拌しながら２０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５回洗浄した。その後
７０℃で真空乾燥し、目的物を得た（黒色粉末、６６６．１ｍｇ）。
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：３４４７、２９８４、２９４５、１１５９、５８４ｃｍ−１
元素分析：Ｃ ５．２７％、Ｈ ０．５９％、Ｎ ０．２４％、Ｂｒ １．１１％
これらの分析結果より、この生成物は以下の構造式で代表される、磁性ナノ粒子に有機基が固定化された化合物と同定された。なお、以下の構造式は、磁性ナノ粒子に対する有機基の固定化の主な形態である、磁性ナノ粒子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、［００１６］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。以下の実施例における構造式についても同様である。
Reference Example Under an argon atmosphere, (N, N-dimethylaminopropyl) trimethoxysilane (435.3 mg) and the following structural formula
Next, in an argon atmosphere, magnetite (581.1 mg) and the prepared quaternary ammonium salt were added to degassed ethanol (12 mL), ultrapure water (78 μL) was further added, and ultrasonic waves were applied for 1 minute. The mixture was heated to reflux for 20 hours with stirring using a stirrer. After completion of the reaction, the product was attracted to the wall surface by bringing the magnet closer, the reaction solution was decanted, and further washed with degassed ethanol 5 times. Then, it vacuum-dried at 70 degreeC, and obtained the target object (black powder, 666.1 mg).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 3447, 2984, 2945, 1159, 584 cm −1
Elemental analysis: C 5.27%, H 0.59%, N 0.24%, Br 1.11%
From these analysis results, this product was identified as a compound having an organic group immobilized on magnetic nanoparticles, represented by the following structural formula. The following structural formula is the main form of immobilization of the organic group to the magnetic nanoparticle, which is a form in which three oxygen atoms on the surface of the iron oxide in the magnetic nanoparticle and silicon of the organic group are bonded. Although described, as described in [0016], the bonding form of the organic group to the magnetic nanoparticles is not limited thereto. The same applies to the structural formulas in the following examples.
実施例１
アルゴン雰囲気下、オスミウム（VＩ）酸カリウム二水和物Ｋ２ＯｓＯ４・２Ｈ２Ｏ４．８ｍｇの水溶液（１ｍｌ）に、以下の構造式
反応後、磁石を反応容器に近づけ生成物を引き寄せデカンテーションし、水で５回洗浄後、生成物を減圧乾燥させることにより、目的物を得た（黒色粉末、収量２０３．８ｍｇ）。
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：３４４５、２９００、１６６１、１１５９、１０４５、９７０、５８１ｃｍ−１
元素分析：Ｃ ４．６０％、Ｈ ０．５５％、Ｎ ０．２０％、Ｏｓ １．１６％
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。
Under an argon atmosphere, osmium (VI) potassium dihydrate K 2 OsO 4 .2H 2 O (4.8 ml) in an aqueous solution (1 ml) has the following structural formula:
After the reaction, the magnet was brought close to the reaction vessel, the product was drawn and decanted, washed with water 5 times, and the product was dried under reduced pressure to obtain the desired product (black powder, yield 203.8 mg).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 3445, 2900, 1661, 1159, 1045, 970, 581 cm −1
Elemental analysis: C 4.60%, H 0.55%, N 0.20%, Os 1.16%
From these analysis results, this product was identified as a compound represented by the following structural formula.
実施例２
アルゴン雰囲気下、オスミウム（VＩ）酸カリウム二水和物Ｋ２ＯｓＯ４・２Ｈ２Ｏ２０．８ｍｇの水溶液（５ｍｌ）に、以下の構造式
反応後、磁石を反応容器に近づけ生成物を引き寄せデカンテーションし、水で５回洗浄後、生成物を減圧乾燥させることにより、目的物を得た（黒色粉末、収量１．００７８ｇ）。
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：３４４７、１６３６、１１５０、１０４９、５７１ｃｍ−１
元素分析：Ｃ ７．９４％、Ｈ ０．８０％、Ｎ ０．１８％、Ｏｓ １．０６％
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。
Under an argon atmosphere, an osmium (VI) potassium dihydrate K 2 OsO 4 · 2H 2 O 20.8 mg aqueous solution (5 ml) was subjected to the following structural formula:
After the reaction, the magnet was brought close to the reaction vessel, the product was drawn and decanted, washed with water 5 times, and the product was dried under reduced pressure to obtain the desired product (black powder, yield 1.0078 g).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 3447, 1636, 1150, 1049, 571 cm −1
Elemental analysis: C 7.94%, H 0.80%, N 0.18%, Os 1.06%
From these analysis results, this product was identified as a compound represented by the following structural formula.
実施例３
アルゴン雰囲気下、オスミウム（VＩ）酸カリウム二水和物Ｋ２ＯｓＯ４・２Ｈ２Ｏ８．０ｍｇの水溶液（１ｍｌ）に、以下の構造式
反応後、磁石を反応容器に近づけ生成物を引き寄せデカンテーションし、水で５回洗浄後、生成物を減圧乾燥させることにより、目的物を得た（黒色粉末、収量２６３．０ｍｇ）。
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：３４４５、２８５０、１６５０、１１００，１０００，５９０ｃｍ−１
元素分析：Ｃ ２．４７％、Ｈ ０．４３％、Ｎ ０．１４％、Ｏｓ １．５７％
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。
Under an argon atmosphere, an osmium (VI) potassium dihydrate K 2 OsO 4 · 2H 2 O 8.0 mg aqueous solution (1 ml) was subjected to the following structural formula:
After the reaction, the magnet was brought close to the reaction vessel, the product was drawn and decanted, washed with water 5 times, and the product was dried under reduced pressure to obtain the desired product (black powder, yield 263.0 mg).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 3445, 2850, 1650, 1100, 1000, 590 cm −1
Elemental analysis: C 2.47%, H 0.43%, N 0.14%, Os 1.57%
From these analysis results, this product was identified as a compound represented by the following structural formula.
実施例４
アルゴン雰囲気下、オスミウム（VＩ）酸カリウム二水和物Ｋ２ＯｓＯ４・２Ｈ２Ｏ１４．３ｍｇの水溶液（３ｍｌ）に、以下の構造式
反応後、磁石を反応容器に近づけ生成物を引き寄せデカンテーションし、水で５回洗浄後、生成物を減圧乾燥させることにより、目的物を得た（黒色粉末、収量８０２．７ｍｇ）。
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：２９５７、２９２２、２８５３、１５８９、１４５６，１１１３，１０４７、６２７、５６３ｃｍ−１
元素分析：Ｃ ５．７６％、Ｈ １．０１％、Ｎ ０．１５％、Ｏｓ ０．９１％
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。
Under an argon atmosphere, an osmium (VI) potassium dihydrate K 2 OsO 4 .2H 2 O 14.3 mg aqueous solution (3 ml) was subjected to the following structural formula:
After the reaction, the product was decanted by bringing the magnet close to the reaction vessel, washed with water 5 times, and then dried under reduced pressure to obtain the desired product (black powder, yield 802.7 mg).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 2957, 2922, 2853, 1589, 1456, 1113, 1047, 627, 563 cm −1
Elemental analysis: C 5.76%, H 1.01%, N 0.15%, Os 0.91%
From these analysis results, this product was identified as a compound represented by the following structural formula.
実施例５
アルゴン雰囲気下、オスミウム（VＩ）酸カリウム二水和物Ｋ２ＯｓＯ４・２Ｈ２Ｏ１３．３ｍｇの水溶液（３ｍｌ）に、以下の構造式
反応後、磁石を反応容器に近づけ生成物を引き寄せデカンテーションし、水で５回洗浄後、生成物を減圧乾燥させることにより、目的物を得た（黒色粉末、収量７０２．３ｍｇ）。
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：２９２２、２８５３、１６３４、１４７０，１０４３，６３３、５５７ｃｍ−１
元素分析：Ｃ ４．０３％、Ｈ ０．７３％、Ｎ ０．１５％、Ｏｓ ０．９３％
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。
Under an argon atmosphere, an osmium (VI) potassium dihydrate K 2 OsO 4 .2H 2 O 13.3 mg aqueous solution (3 ml) was subjected to the following structural formula:
After the reaction, the product was decanted by bringing the magnet close to the reaction vessel, washed 5 times with water, and then dried under reduced pressure to obtain the desired product (black powder, yield 702.3 mg).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 2922, 2853, 1634, 1470, 1043, 633, 557 cm −1
Elemental analysis: C 4.03%, H 0.73%, N 0.15%, Os 0.93%
From these analysis results, this product was identified as a compound represented by the following structural formula.
実施例６
アルゴン雰囲気下、オスミウム（VＩ）酸カリウム二水和物Ｋ２ＯｓＯ４・２Ｈ２Ｏ８．７ｍｇの水溶液（３ｍｌ）に、以下の構造式
反応後、磁石を反応容器に近づけ生成物を引き寄せデカンテーションし、水で５回洗浄後、生成物を減圧乾燥させることにより、目的物を得た（黒色粉末、収量２５４．５ｍｇ）。
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：３０３２、２９２２、１５９５、１４５６、１１５２、１０９２、６２７、５７７、５５２ｃｍ−１
元素分析：Ｃ １１．８５％、Ｈ １．２４％、Ｎ ０．２４％、Ｏｓ １．７０％
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。
Under an argon atmosphere, an 8.7 mg aqueous solution (3 ml) of potassium osmium (VI) potassium dihydrate K 2 OsO 4 .2H 2 O has the following structural formula:
After the reaction, the magnet was brought close to the reaction vessel, the product was drawn and decanted, washed with water 5 times, and the product was dried under reduced pressure to obtain the desired product (black powder, yield 254.5 mg).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 3032, 2922, 1595, 1456, 1152, 1092, 627, 577, 552 cm −1
Elemental analysis: C 11.85%, H 1.24%, N 0.24%, Os 1.70%
From these analysis results, this product was identified as a compound represented by the following structural formula.
実施例７
アルゴン雰囲気下、オスミウム（VＩ）酸カリウム二水和物Ｋ２ＯｓＯ４・２Ｈ２Ｏ１７．７ｍｇの水溶液（３ｍｌ）に、以下の構造式
反応後、磁石を反応容器に近づけ生成物を引き寄せデカンテーションし、水で５回洗浄後、生成物を減圧乾燥させることにより、目的物を得た（黒色粉末、収量１．２０４０ｇ）。
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：３０３２、１５９７、１４５２、１１５９、１０４９、５７２ｃｍ−１
元素分析：Ｃ １１．８０％、Ｈ ０．９５％、Ｎ ０．１２％、Ｏｓ ０．６７％
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。
Under an argon atmosphere, an osmium (VI) potassium dihydrate K 2 OsO 4 .2H 2 O 17.7 mg aqueous solution (3 ml) was subjected to the following structural formula:
After the reaction, the magnet was brought close to the reaction vessel, the product was drawn and decanted, washed with water 5 times, and the product was dried under reduced pressure to obtain the desired product (black powder, yield 1.2040 g).
The results of IR analysis and elemental analysis of this product are as follows.
IR: 3032, 1597, 1452, 1159, 1049, 572 cm −1
Elemental analysis: C 11.80%, H 0.95%, N 0.12%, Os 0.67%
From these analysis results, this product was identified as a compound represented by the following structural formula.
実施例８
アルゴン雰囲気下、アセトン０．７５ｍＬ、水０．７５ｍＬの混合溶液に、実施例１で得られた磁性ナノ粒子固定型オスミウム（VＩ）酸塩（０．０６１５ｍmoｌ/ｇ）１９５ｍｇ、スチレン６１．５ｍｇ、N−メチルモルホリンN−オキシド９０．３ｍｇを順次加え、室温にて４時間撹拌し、反応させた。
反応終了後アセトンを減圧留去し、磁石を反応容器に近づけデカンテーションした。さらに触媒を水で５回洗浄し、反応溶液を含むこれらの水溶液を減圧留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：１）で分離、精製して以下の構造式
Under an argon atmosphere, 195 mg of magnetic nanoparticle-immobilized osmium (VI) acid salt (0.0615 mMol / g) obtained in Example 1 and 61.5 mg of styrene were added to a mixed solution of 0.75 mL of acetone and 0.75 mL of water. N-methylmorpholine N-oxide (90.3 mg) was sequentially added, and the mixture was stirred at room temperature for 4 hours to be reacted.
After completion of the reaction, acetone was distilled off under reduced pressure, and the magnet was decanted close to the reaction vessel. Further, the catalyst was washed 5 times with water, these aqueous solutions containing the reaction solution were distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1). The following structural formula
Claims (7)
で表される基である。］
で表されるオスミウム（VＩ）酸塩が、当該一般式中のＳｉに結合する３つのＲ４−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、磁性ナノ粒子固定型オスミウム（ＶＩ）酸塩。 Formula (I)
It is group represented by these. ]
In the magnetic nanoparticle, at least one of three R 4 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticle. Magnetic nanoparticle-immobilized osmium (VI) acid salt containing an immobilized structure.
で表される基である。］
で表される四級アンモニウム塩構造を含有する、請求項２に記載のフェライトを主成分とする磁性ナノ粒子固定型オスミウム（VＩ）酸塩。 The following general formula (III),
It is group represented by these. ]
The magnetic nanoparticle fixed osmium (VI) acid salt containing ferrite as a main component according to claim 2 and containing a quaternary ammonium salt structure represented by:
で表される基である。］
で表される構造を有する四級アンモニウム塩が、当該一般式中のＳｉに結合する３つのＲ４−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、磁性ナノ粒子固定型四級アンモニウム塩と、オスミウム（VＩ）酸カリウム K2OsO4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型オスミウム（VＩ）酸塩の製造方法。 Formula (VI)
It is group represented by these. ]
In the general formula, at least one of the three R 4 —O— groups bonded to Si in the general formula is replaced with an oxygen atom in the magnetic nanoparticle, whereby the magnetic nanoparticle 2. The magnetic nanoparticle-immobilized quaternary ammonium salt containing a structure immobilized on osmium (VI) potassium K 2 OsO 4 is reacted in a solvent. The manufacturing method of magnetic nanoparticle fixed type | mold osmium (VI) acid salt.
で表される基である。］
で表される四級アンモニウム塩構造を含有する、フェライトを主成分とする磁性ナノ粒子固定型四級アンモニウム塩と、オスミウム（VＩ）酸カリウム K2OsO4とを、溶媒中で反応させることを特徴とする、請求項５に記載の、フェライトを主成分とする磁性ナノ粒子固定型オスミウム（VＩ）酸塩の製造方法。 The following general formula (VII),
It is group represented by these. ]
A magnetic nanoparticle fixed quaternary ammonium salt containing a ferrite as a main component, which contains a quaternary ammonium salt structure represented by the formula, and potassium osmium (VI) K 2 OsO 4 in a solvent. The method for producing a magnetic nanoparticle-fixed osmium (VI) salt mainly comprising ferrite, according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011040484A JP5704320B2 (en) | 2010-03-04 | 2011-02-25 | Magnetic nanoparticles fixed osmium (VI) acid salt |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010047583 | 2010-03-04 | ||
| JP2010047583 | 2010-03-04 | ||
| JP2011040484A JP5704320B2 (en) | 2010-03-04 | 2011-02-25 | Magnetic nanoparticles fixed osmium (VI) acid salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011201862A JP2011201862A (en) | 2011-10-13 |
| JP5704320B2 true JP5704320B2 (en) | 2015-04-22 |
Family
ID=44878916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011040484A Active JP5704320B2 (en) | 2010-03-04 | 2011-02-25 | Magnetic nanoparticles fixed osmium (VI) acid salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5704320B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012165510A1 (en) | 2011-05-31 | 2012-12-06 | 国立大学法人浜松医科大学 | Recovery of reusable osmium tetroxide |
| JP5920820B2 (en) * | 2012-03-05 | 2016-05-18 | 国立研究開発法人産業技術総合研究所 | Magnetic nanoparticles fixed osmium oxide |
| JP6218140B2 (en) * | 2014-02-24 | 2017-10-25 | 国立大学法人富山大学 | Magnetic iron particle supported iodine catalyst |
| CN105268485B (en) * | 2014-07-24 | 2018-01-09 | 中国石油化工股份有限公司 | Produce C2‑10The method of alkanediol |
| JP6708341B2 (en) * | 2016-06-24 | 2020-06-10 | 国立研究開発法人産業技術総合研究所 | Nitrogen-containing heterocyclic carbene-gold(I) complex with immobilized magnetic nanoparticles |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3920917A1 (en) * | 1989-06-26 | 1991-01-03 | Hoechst Ag | OXIDIC HETEROGEN CATALYSTS OF OSMIUM, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE OF OLEFINIC COMPOUNDS IN GLYCLE |
| US6387033B1 (en) * | 2000-11-22 | 2002-05-14 | Council Of Scientific And Industrial Research | Preparation of new layered double hydroxides exchanged with osmate for asymmetric dihydroxylation of olefins to vicinal diols |
| WO2002066158A1 (en) * | 2001-02-22 | 2002-08-29 | Wako Pure Chemical Industries, Ltd. | Osmium tetraoxide carried on polymer having ion-exchange group |
| EP1366814A4 (en) * | 2001-03-09 | 2005-03-30 | Wako Pure Chem Ind Ltd | Osmium oxide deposited on hydrophilic polymer support |
| JP4586200B2 (en) * | 2006-05-10 | 2010-11-24 | 独立行政法人産業技術総合研究所 | Quaternary ammonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle-supported phase transfer catalyst comprising the same, and phase transfer reaction using the same |
| JP4986117B2 (en) * | 2006-06-19 | 2012-07-25 | 独立行政法人産業技術総合研究所 | Phosphonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle supported phase transfer catalyst comprising the phosphonium salt, and phase transfer reaction using the same |
| JP4821459B2 (en) * | 2006-06-27 | 2011-11-24 | 和光純薬工業株式会社 | Fibrous protein-supported osmium catalyst |
| JP2011162377A (en) * | 2010-02-08 | 2011-08-25 | Teijin Ltd | N-oxyl compound-carrying magnetic particle |
-
2011
- 2011-02-25 JP JP2011040484A patent/JP5704320B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011201862A (en) | 2011-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5704320B2 (en) | Magnetic nanoparticles fixed osmium (VI) acid salt | |
| JP2008063314A (en) | Environment-conscious hypervalent iodine reagent | |
| Mai et al. | Cu/Ag-catalyzed double decarboxylative cross-coupling reaction between cinnamic acids and aliphatic acids in aqueous solution | |
| Gholinejad et al. | Magnetic nanoparticles supported oxime palladacycle as a highly efficient and separable catalyst for room temperature Suzuki–Miyaura coupling reaction in aqueous media | |
| WO2013125020A1 (en) | Dehydrogenation catalyst, and carbonyl compound and hydrogen production method using said catalyst | |
| Azizi et al. | Biodegradable choline hydroxide promoted environmentally benign thiolysis of epoxides | |
| JP5894144B2 (en) | Production process of divinylarene dioxide | |
| CN106008401A (en) | Preparation method of N-formamide compound | |
| WO2004091784A1 (en) | Metal catalyst and its use | |
| JP6765098B2 (en) | Magnetic nanoparticles immobilized imidazolium hydrogen carbonate | |
| JP5131813B2 (en) | Catalyst for phase transfer reaction | |
| JP6708341B2 (en) | Nitrogen-containing heterocyclic carbene-gold(I) complex with immobilized magnetic nanoparticles | |
| CN109369448A (en) | A kind of method that bimetal composite oxide catalyzes and synthesizes azobenzene compound | |
| JP5920820B2 (en) | Magnetic nanoparticles fixed osmium oxide | |
| JP4986117B2 (en) | Phosphonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle supported phase transfer catalyst comprising the phosphonium salt, and phase transfer reaction using the same | |
| CN107827913B (en) | 1, 10-phenanthroline-containing N-heterocyclic carbene copper (I) complex and application thereof | |
| JP2002363188A (en) | Carrier-complex composite, alkane oxidation catalyst, and method for synthesizing alkanol | |
| CN113264820B (en) | Method for preparing ketone compound from olefin | |
| JP2018008919A (en) | Method for producing azo compounds | |
| JP2002201156A (en) | METHOD FOR PRODUCING beta-HYDROXYHYDROPEROXIDE COMPOUNDS AND CARBOXYLIC ACID COMPOUNDS AND CATALYST THEREFOR | |
| JP2011241200A (en) | Method for producing styrene oxide compound | |
| Wang et al. | A Facile and Efficient Catalytic System for the Oxidation of Alcohols with Gold (III) and Ionic Liquid Immobilized TEMPO under Solvent-Free Conditions | |
| JP5846438B2 (en) | Polymer containing immobilized quaternary ammonium salt and method for producing the same | |
| JP5093680B2 (en) | Bisquaternary ammonium salt core type dendrimer | |
| JP2003267905A (en) | Method for producing aralkyl ketones and catalyst thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120113 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120113 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130904 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140924 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141107 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150210 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150210 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5704320 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |