WO2011030591A1 - 亜鉛クラスター - Google Patents
亜鉛クラスター Download PDFInfo
- Publication number
- WO2011030591A1 WO2011030591A1 PCT/JP2010/059204 JP2010059204W WO2011030591A1 WO 2011030591 A1 WO2011030591 A1 WO 2011030591A1 JP 2010059204 W JP2010059204 W JP 2010059204W WO 2011030591 A1 WO2011030591 A1 WO 2011030591A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zinc
- cluster
- mmol
- zinc cluster
- general formula
- Prior art date
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- 239000011701 zinc Substances 0.000 title claims abstract description 133
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 95
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- -1 zinc carboxylate Chemical class 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 5
- 238000005917 acylation reaction Methods 0.000 claims description 5
- 150000001414 amino alcohols Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- 238000005809 transesterification reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RPUSRLKKXPQSGP-UHFFFAOYSA-N methyl 3-phenylpropanoate Chemical compound COC(=O)CCC1=CC=CC=C1 RPUSRLKKXPQSGP-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000004776 molecular orbital Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- VUNLDTPRUICHRY-UHFFFAOYSA-L zinc;2,2,2-trifluoroacetate;hydrate Chemical compound O.[Zn+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F VUNLDTPRUICHRY-UHFFFAOYSA-L 0.000 description 6
- 238000007112 amidation reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 3
- QPADYYUBHQRRIR-LLVKDONJSA-N (4s)-2-phenyl-4-propan-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(C)[C@H]1COC(C=2C=CC=CC=2)=N1 QPADYYUBHQRRIR-LLVKDONJSA-N 0.000 description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- SODNLOGCPXYAEK-UHFFFAOYSA-N [4-(oxan-2-yloxymethyl)phenyl]methanol Chemical compound C1=CC(CO)=CC=C1COC1OCCCC1 SODNLOGCPXYAEK-UHFFFAOYSA-N 0.000 description 2
- ZJPJZNKPVIWBSU-UHFFFAOYSA-N [4-(oxan-2-yloxymethyl)phenyl]methyl acetate Chemical compound C1=CC(COC(=O)C)=CC=C1COC1OCCCC1 ZJPJZNKPVIWBSU-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- LDYUGYKDRCVGMQ-UHFFFAOYSA-N butyl 3-phenylpropanoate Chemical compound CCCCOC(=O)CCC1=CC=CC=C1 LDYUGYKDRCVGMQ-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- NWYYWIJOWOLJNR-RXMQYKEDSA-N l-valinol Chemical compound CC(C)[C@H](N)CO NWYYWIJOWOLJNR-RXMQYKEDSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DZYBBBYFLOPVOL-UHFFFAOYSA-N methyl 2-(phenylmethoxycarbonylamino)acetate Chemical compound COC(=O)CNC(=O)OCC1=CC=CC=C1 DZYBBBYFLOPVOL-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000302 molecular modelling Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- YXUKOFVPQCAYKW-UHFFFAOYSA-N tert-butyl 2-(phenylmethoxycarbonylamino)acetate Chemical compound CC(C)(C)OC(=O)CNC(=O)OCC1=CC=CC=C1 YXUKOFVPQCAYKW-UHFFFAOYSA-N 0.000 description 2
- ZOJRGDRNISZTQS-UHFFFAOYSA-N tert-butyl 3-phenylpropanoate Chemical compound CC(C)(C)OC(=O)CCC1=CC=CC=C1 ZOJRGDRNISZTQS-UHFFFAOYSA-N 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
- 150000003512 tertiary amines Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyloxyacetoaldehyde Natural products CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- VVJUKSKDOHGWJE-UHFFFAOYSA-N cyclohexyl 3-phenylpropanoate Chemical compound C1CCCCC1OC(=O)CCC1=CC=CC=C1 VVJUKSKDOHGWJE-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- GCDDWHAOKKZJLL-UHFFFAOYSA-N methyl 4-(oxan-2-yloxy)butanoate Chemical compound COC(=O)CCCOC1CCCCO1 GCDDWHAOKKZJLL-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XBXHCBLBYQEYTI-UHFFFAOYSA-N piperidin-4-ylmethanol Chemical compound OCC1CCNCC1 XBXHCBLBYQEYTI-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- PNRUNMFKTONSIV-UHFFFAOYSA-N tert-butyl 4-(oxan-2-yloxy)butanoate Chemical compound CC(C)(C)OC(=O)CCCOC1CCCCO1 PNRUNMFKTONSIV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/12—Formation or introduction of functional groups containing oxygen of carboxylic acid ester groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/16—Halogenated acetic acids
- C07C53/18—Halogenated acetic acids containing fluorine
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/12—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals containing only hydrogen and carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/349—1,2- or 1,4-additions in combination with further or prior reactions by the same catalyst, i.e. tandem or domino reactions, e.g. hydrogenation or further addition reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a zinc cluster useful as an organometallic catalyst and a catalytic reaction such as a transesterification reaction, an esterification reaction, a direct oxazoline formation reaction from a carbonyl compound, and an amidation reaction.
- Zinc tetranuclear cluster Zn 4 O (OCOR) 6 with zinc atom as the core metal may be generated under high temperature (250 ° C or higher) heating conditions of zinc carboxylates such as zinc acetate (II) hydrate under vacuum. It is known (Non-Patent Document 1). Further, zinc tetranuclear cluster Zn 4 O (OCOCF 3 ) 6 is obtained under the above reaction conditions using zinc trifluoroacetate hydrate. Furthermore, this zinc tetranuclear cluster Zn 4 O (OCOCF 3 ) 6 is known to be useful as a catalyst for ester reaction, transesterification reaction, acylation reaction and amidation reaction (Patent Document 1).
- Non-patent Document 2 a zinc tetranuclear cluster catalyst having a zinc atom having relatively low toxicity as a core metal is also useful in terms of environmental friendliness.
- the problem to be solved by the present invention is to supply a large amount and inexpensively of zinc clusters having a catalytic ability equivalent to that of the conventionally known zinc tetranuclear cluster Zn 4 O (OCOR) 6 under milder conditions. It is to be.
- a zinc carboxylate compound such as zinc acetate hydrate or zinc trifluoroacetate hydrate can be used as a raw material, and it can be produced under milder temperature conditions than before.
- the zinc cluster of the present invention exhibits catalytic activity equivalent to that of the conventional zinc cluster Zn 4 O (OCOR) 6 in transesterification, esterification, direct oxazoline formation from carbonyl compounds, and amidation. I found out.
- the present invention relates to the following [1] to [4].
- R represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and n represents 0.1 to 1
- General formula (2) Zn (OCOR) 2 xH 2 O (2) In general formula (2), R represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and x represents an arbitrary number of 0 or more.
- [3] Acylation of a hydroxyl group with a carboxylic acid or an ester thereof, wherein the zinc cluster according to [1] is used as a catalyst.
- [4] A method for producing an oxazoline comprising reacting a carboxylic acid or an ester thereof with an amino alcohol, wherein the zinc cluster according to [1] is used as a catalyst.
- the zinc cluster represented by the general formula (1) of the present invention exhibits an excellent catalytic activity, and can perform the reaction with good environmental friendliness, operability and economical efficiency under mild reaction conditions.
- the zinc cluster of the present invention is useful as a catalyst for synthesizing intermediates for medicines and agricultural chemicals and also as a zinc oxide precursor compound.
- FIG. 2 shows an ESI-MS spectrum of the zinc cluster obtained in Example 1.
- FIG. Zn 4 O (OCOCF 3 ) 6 (CF 3 COOH) ESI-MS spectrum simulation pattern is shown.
- the infrared spectrophotometric (IR) measurement result of the zinc cluster obtained in Example 1 is shown.
- the structure of [Zn 4 O (OCOCF 3 ) 6 (CF 3 COOH)] estimated from ESI-MS measurement by molecular orbital calculation is shown.
- the structure of the zinc tetranuclear cluster Zn 4 O (OCOCF 3 ) 6 by molecular orbital calculation is shown.
- the zinc cluster of the present invention is represented by the following general formula (1).
- Zn 4 O (OCOR) 6 (RCOOH) n (1)
- R represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom
- n represents a value in the range of 0.1 to 1.
- the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, and t-butyl groups as unsubstituted alkyl groups.
- the halogen atom include fluorine, chlorine, bromine and iodine.
- alkyl group substituted with a halogen atom examples include a perfluoroalkyl group such as a trichloromethyl group, a tribromomethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a heptafluoroisopropyl group.
- a perfluoroalkyl group such as a trichloromethyl group, a tribromomethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a heptafluoroisopropyl group.
- a preferred group is a trifluoromethyl (CF 3 ) group.
- the preferable numerical value of n is preferably in the range of 0.1 to 0.9, more preferably in the range of 0.5 to 0.9.
- the zinc cluster of the present invention is mainly composed of a zinc cluster represented by Zn 4 O (OCOR) 6 (RCOOH), but is a mixture with Zn 4 O (OCOR) 6 which is a conventionally known zinc cluster. It may be.
- the zinc cluster of the present invention can be represented as Zn 4 O (OCOR) 6 (RCOOH) n .
- R is a trifluoromethyl (CF 3 ) group
- the zinc content shows a value in the range of 24.7 wt% to 27.1 wt%. More preferably, the zinc content is in the range of 24.7 wt% to 25.8 wt%.
- the zinc cluster represented by the general formula (1) can be obtained by heating the zinc carboxylate hydrate represented by the following general formula (2).
- Zn (OCOR) 2 xH 2 O (2) (In formula (2), R represents the same meaning as described above, x represents an arbitrary numerical value of 0 or more, and is usually in the range of 1 to 3.) That is, the zinc cluster of the present invention is produced by heating zinc carboxylate hydrate without solvent or in a solvent and efficiently discharging water and carboxylic acid ROCOH removed during the formation of the zinc cluster out of the system. I can do it. Heating may be performed at atmospheric pressure, preferably under reduced pressure.
- the heating temperature is preferably equal to or higher than the temperature at which water and carboxylic acid ROCOH can be removed from the raw material zinc carboxylate hydrate. That is, it is desirably 100 ° C. or higher at atmospheric pressure. Under reduced pressure, the temperature at which water and carboxylic acid ROCOH can be removed can be 100 ° C or less. The temperature may be higher than the removable temperature corresponding to the degree of vacuum. For example, in the case of 290 ⁇ 10 mmHg, the zinc cluster of the present invention can be formed at 75 ° C. or higher. The production of the zinc cluster of the present invention is possible even under a temperature condition where the raw material without solvent is not liquefied and sublimates under solid conditions.
- a solvent when manufacturing in a solvent, if it is a solvent which does not affect the zinc cluster formation of this invention, it can be used.
- it is a low polarity organic solvent.
- benzene, toluene, xylene, hexane, heptane, octane, etc. can be used.
- aromatic solvents such as benzene, toluene and xylene are preferred. That is, a solvent in which zinc carboxylate hydrate (Zn (OCOR) 2 .xH 2 O) can be dissolved at the production temperature and the zinc cluster of the present invention has low solubility is preferable.
- the zinc cluster of this invention can be manufactured on temperature conditions lower than the conventional zinc cluster manufacturing temperature conditions (250 degreeC, 360 degreeC). Preferably it manufactures at 200 degrees C or less, More preferably, it is 100 degrees or less. Since the zinc cluster represented by the general formula (1) of the present invention obtained under the above conditions may be highly hygroscopic or unstable in the air, it can be handled in the presence of an inert gas with little moisture. preferable.
- the inert gas is preferably nitrogen or argon.
- the zinc cluster of the present invention comprises, for example, (i) an acylation reaction of a hydroxyl group (preferably an alcoholic hydroxyl group) with a carboxylic acid or an ester thereof as described in WO2007 / 066661A1 or WO2009 / 047905A1, (ii) It can be used as a catalyst for an amidation reaction in which a carboxylic acid or its ester is reacted with an amine, and (iii) a method for producing an oxazoline in which a carboxylic acid or its ester is reacted with an amino alcohol.
- the amount of the zinc cluster of the present invention used as a catalyst is not particularly limited, but usually 0.001 to 0.9 moles, more preferably 0.001 to 0.3 moles of zinc atoms per mole of raw material.
- the ratio is more preferably 0.001 to 0.1 mol.
- the reaction is usually performed in a solvent.
- Specific examples of the solvent are not particularly limited. For example, aromatic solvents such as toluene, xylene or benzene chloride; aliphatic hydrocarbon solvents such as hexane, heptane or octane; diethyl ether, diisopropyl ether, tert-butyl.
- Ether solvents such as methyl ether, tetrahydrofuran or 1,4-dioxane; amide solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO) . Further, the reaction can be carried out even without solvent.
- amide solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO) . Further, the reaction can be carried out even without solvent.
- a reaction accelerator can be added.
- the reaction accelerator include amines.
- the amines include primary amines such as ethylamine, n-propylamine, n-butylamine, and cyclohexylamine, and secondary amines such as diethylamine, dipropylamine, diisopropylamine, and dicyclohexylamine.
- a tertiary amine or a tertiary amine such as triethylamine, diisopropylethylamine, tributylamine, or pyridine can be used.
- Various reactions using the zinc cluster of the present invention can be performed in the air or in an inert gas atmosphere such as nitrogen gas or argon gas.
- the reaction time is not particularly limited, but is usually about 1 to 45 hours, preferably about 6 to 18 hours, and the reaction temperature is not particularly limited, but is room temperature to about 150 ° C., preferably 50 to 150 ° C., more preferably. Is performed at about 80 to 130 ° C. These conditions can be appropriately changed depending on the type and amount of the raw material used.
- the zinc cluster represented by the general formula (1) is useful in various catalytic reactions as described above, but is also useful as a raw material for forming a zinc oxide film for other uses.
- a zinc cluster film is formed on the substrate surface after forming a zinc cluster from the raw material zinc acetate hydrate by vacuum heating. Further, it has been reported that a zinc oxide (ZnO) film that is more uniform than that in the conventional manufacturing method is produced by performing a heat treatment of 500 ° C. or more.
- Japanese Patent Application Laid-Open No. 2005-305233 shows that a uniform zinc oxide film can be formed while forming zinc clusters in the system by mist CVD using zinc acetate hydrate. It can also be used as such a raw material.
- the zinc cluster of the present invention is also useful as a precursor for forming a zinc oxide film or the like.
- Example 1 Production of Zinc Cluster 30.3 g of zinc trifluoroacetate hydrate (manufactured by Alfa Aesar) (containing 6.6 wt% of water) was introduced into a glass tube sealed at one end. A nitrogen cooling trap was connected to one of the glass tubes, and the pressure was reduced to a vacuum degree of 4 ⁇ 10 ⁇ 1 torr with an oil rotary pump. Subsequently, the glass tube was heated with a heater at 120 ° C. for 1.5 hours, then gradually heated to 160 ° C. and heated at the same temperature for 30 minutes. In about 6 hours, the zinc trifluoroacetate hydrate in the glass tube disappeared and some residue remained. Then, heating was stopped and natural cooling was performed to room temperature.
- zinc trifluoroacetate hydrate manufactured by Alfa Aesar
- the ESI-MS spectrum of the zinc cluster produced in Example 1 is shown in FIG. 1, and an anion [Zn 4 O (OCOCF 3 ) 6 (CF) estimated from Zn 4 O (OCOCF 3 ) 6 (CF 3 COOH) 3 COO)] (-) ESI-MS spectrum simulation pattern is shown in FIG.
- the ESI-MS spectrum (FIG. 1) and the simulation pattern (FIG. 2) show similar patterns.
- the obtained experimental value 1062.6607 and the anion [Zn 4 O (OCOCF 3 ) 6 (CF 3 COO)] ( ⁇ ) : C 14 F 21 O 15 Zn 4 estimated value 1062.66073 are 0.09 ppm. And a very approximate value.
- the zinc content measurement was performed by the following method. That is, the zinc cluster (0.0794 g) obtained in Example 1 was weighed into a 200 ml Erlenmeyer flask and dissolved by adding 50 ml of distilled water. To this was added 5 ml of an acetic acid-sodium acetate (pH 5) buffer solution (manufactured by Nacalai Tesque), and hexamine was added in small portions to adjust the pH to about 5.5.
- pH 5 acetic acid-sodium acetate
- Example 1 the infrared spectrophotometric (IR) measurement result of the zinc cluster obtained in Example 1 is shown in FIG.
- the peaks of the IR spectrum are 426.67 cm-1, 520 cm-1, 729.22 cm-1, 798.99 cm-1, 851.34 cm-1, 1203.43 cm-1, 14438.87 cm-1, 1629.02 cm- 1 and 1708.08 cm-1.
- Example 2 Esterification reaction Under a nitrogen atmosphere, 3-phenylpropionic acid (3.0 mmol), n-butanol (3.6 mmol), the zinc cluster obtained in Example 1 (0.0375 mmol) and diisopropyl ether (5.0 ml) As a result of refluxing the mixture for 18 hours, butyl 3-phenylpropionate was quantitatively obtained.
- Example 3 Transesterification reaction Under a nitrogen atmosphere, methyl 3-phenylpropionate (3.0 mmol), n-butanol (3.6 mmol), the zinc cluster (0.0375 mmol) obtained in Example 1 above and diisopropyl ether (5.0 ml) ) was refluxed for 18 hours, and butyl 3-phenylpropionate was quantitatively obtained.
- Example 4 Transesterification reaction in the presence of alcohol and amine Under nitrogen atmosphere, methyl 3-phenylpropionate (3.0 mmol), cyclohexanol (3.6 mmol), cyclohexylamine (3.6 mmol), obtained in Example 1 above As a result of refluxing a mixture of zinc cluster (0.0375 mmol) and diisopropyl ether (5.0 ml) for 18 hours, cyclohexyl 3-phenylpropionate as an ester was quantitatively obtained. Formation of an amide was not confirmed.
- Example 5 Production of Zinc Cluster 9.70 g of zinc trifluoroacetate hydrate (zinc content 18 wt%, moisture 19 wt%) and toluene were added to a four-necked flask. After replacing the inside of the flask with nitrogen, the inside of the flask was decompressed to 290 ⁇ 10 mmHg with a vacuum pump. Subsequently, when the temperature was gradually increased, the mixture in the flask became transparent and completely dissolved at 60 ° C. After reaching 75 ° C., the solvent was recovered at the same temperature.
- the solvent distillate contained toluene and water, and the heating was stopped when the amount of water in the recovered solvent reached about 20 wt% of the charged amount of zinc trifluoroacetate hydrate.
- the mixture was gradually cooled to ⁇ 5 ° C., stirred at the same temperature for 4 hours, and filtered under nitrogen.
- the obtained white solid was dried at 75 ° C./5 mmHg. After drying, 6.37 g of a white solid was obtained.
- the zinc content of the white solid was measured by the following titration method. That is, about 30 mg of the white solid obtained above was weighed into a 200 ml Erlenmeyer flask. 100 ml of purified water was added and dissolved.
- Example 6 Transesterification in the presence of an amino group Under a nitrogen atmosphere, 0.6907 g (6 mmol) of 4-piperidinemethanol, 64.2 mg (0.06 mmol) of the zinc cluster obtained in Example 5 and ethyl acetate (10.0 ml) As a result of refluxing the mixture for 4 hours, 85.4% of an ester was obtained. The formation of amide was confirmed by 0.7%. In addition, 4.7% of a product in which both esterification and amidation occurred was obtained. The conversion rate was 90.9%.
- Example 7 Transesterification reaction Under a nitrogen atmosphere, methyl 3-phenylpropionate (3.0 mmol), t-butanol (3.6 mmol), the zinc cluster obtained in Example 5 (0.0375 mmol) and diisopropyl ether (5.0 ml) ) was refluxed for 18 hours. As a result, t-butyl 3-phenylpropionate was quantitatively obtained.
- Example 8 Transesterification Reaction Under a nitrogen atmosphere, carbobenzyloxyglycine methyl ester (3.0 mmol), t-butanol (3.6 mmol), the zinc cluster (0.0375 mmol) obtained in Example 5 above and diisopropyl ether (5.0 ml) As a result, the carbobenzyloxyglycine t-butyl ester was obtained in a yield of 91.8%.
- Example 9 Transesterification reaction Under a nitrogen atmosphere, (4-((tetrahydro-2H-pyran-2-yloxy) methyl) phenyl) methanol (3.0 mmol), t-butanol (3.6 mmol), obtained in Example 5 above A mixture of zinc cluster (0.0375 mmol) and diisopropyl ether (5.0 ml) was refluxed for 18 hours. As a result, 4-((tetrahydro-2H-pyran-2-yloxy) methyl) benzyl acetate was obtained in a yield of 92.9%. Obtained.
- the zinc cluster of the present invention showed catalytic activity equal to or higher than that of the conventional zinc cluster Zn 4 O (OCOCF 3 ) 6 .
- Example 10 Acetylation reaction Under a nitrogen atmosphere, a mixture of ((4-triethylsilyloxy) methyl) phenyl) methanol (6 mmol), the zinc cluster (0.075 mmol) obtained in Example 5 above and ethyl acetate (1.7 ml) was prepared. As a result of refluxing for 18 hours, 4-((triethylsilyloxy) methyl) benzyl acetate was obtained in a yield of 86%.
- the zinc cluster of the present invention showed catalytic activity equal to or higher than that of the conventional zinc cluster Zn 4 O (OCOCF 3 ) 6 .
- Example 11 Production of Oxazolines Under a nitrogen atmosphere, methyl benzoate (1.5 mmol), (S) -valinol (1.8 mmol), the zinc cluster obtained in Example 5 above (0.0375 mmol) and chlorobenzene (2.5 ml) As a result of refluxing the mixture for 12 hours, (S) -4-isopropyl-2-phenyloxazoline was obtained in a yield of 86%.
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Abstract
Description
また、トリフルオロ酢酸亜鉛水和物を用いて上記反応条件で亜鉛四核クラスターZn4O(OCOCF3)6が得られる。さらにこの亜鉛四核クラスターZn4O(OCOCF3)6は、エステル反応、エステル交換反応、アシル化反応及びアミド化反応の触媒として有用であることが知られている(特許文献1)。
すなわち、亜鉛四核クラスターZn4O(OCOR)6を触媒として用いることにより、温和な条件で効率的に反応を進行させることが可能である。かつ、比較的毒性も少ない亜鉛原子を核金属に有する亜鉛四核クラスター触媒は、環境に優しい点も有用であることが知られている(非特許文献2)。
[1]下記一般式(1)
Zn4O(OCOR)6(RCOOH)n (1)
(一般式(1)中、Rはハロゲン原子で置換されていてもよい炭素数1~4のアルキル基を表し、nは0.1~1を表す。)
で表される亜鉛クラスター。
[2]一般式(2)
Zn(OCOR)2・xH2O (2)
(一般式(2)中、Rはハロゲン原子で置換されていてもよい炭素数1~4のアルキル基を表し、xは0以上の任意の数を表す。)
で表されるカルボン酸亜鉛水和物を、50℃~200℃の温度で加熱反応させることを特徴とする前記[1]に記載の亜鉛クラスターの製造方法。
[3]前記[1]に記載の亜鉛クラスターを触媒として用いることを特徴とする、カルボン酸またはそのエステルによる水酸基のアシル化反応。
[4]前記[1]に記載の亜鉛クラスターを触媒として用いることを特徴とする、カルボン酸またはそのエステルとアミノアルコールとを反応させるオキサゾリン類の製造方法。
本発明の亜鉛クラスターは、下記一般式(1)で示される。
Zn4O(OCOR)6(RCOOH)n (1)
式(1)中、Rはハロゲン原子で置換されていてもよい炭素数1~4のアルキル基を表し、nは、0.1~1の範囲の値を示す。該アルキル基としては、非置換アルキル基としてメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、s-ブチル基、t-ブチル基が挙げられる。また、ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素が挙げられる。ハロゲン原子で置換されたアルキル基としては、例えば、トリクロロメチル基、トリブロモメチル基、トリフルオロメチル基、ペンタフルオルエチル基、ヘプタフルオロプロピル基、ヘプタフルオロイソプロピル基等のパーフルオロアルキル基などが挙げられる。この中でも好ましい基としては、トリフルオロメチル(CF3)基が挙げられる。
また、好ましいnの数値としては0.1~0.9の範囲、さらに好ましくは0.5~から0.9の範囲が望ましい。本発明の亜鉛クラスターは、Zn4O(OCOR)6(RCOOH)で表される亜鉛クラスターを主成分としているが、従来から知られている亜鉛クラスターであるZn4O(OCOR)6との混合物であっても良い。その場合、本発明の亜鉛クラスターは、Zn4O(OCOR)6(RCOOH)nと示すことが出来る。
Rがトリフルオロメチル(CF3)基の場合では、亜鉛含量が24.7wt%~27.1wt%の範囲の値を示す。さらに好ましくは亜鉛含量が24.7wt%~25.8wt%の範囲が望ましい。
Zn(OCOR)2・xH2O (2)
(式(2)中、Rは前記と同じ意味を表し、xは0以上の任意の数値を表し、通常は1~3の範囲である。)
すなわち、カルボン酸亜鉛水和物を無溶媒、もしくは溶媒下加熱し、亜鉛クラスター形成の際に除かれる水及びカルボン酸ROCOHを系外に効率よく排出することで本発明の亜鉛クラスターを製造することが出来る。加熱は、大気圧で行っても良く、好ましくは減圧下で行う。さらに加熱温度は、原料であるカルボン酸亜鉛水和物から水及びカルボン酸ROCOHが除去できる温度以上であることが望ましい。すなわち、大気圧では100℃以上であることが望ましい。減圧下では、水及びカルボン酸ROCOHが除去できる温度が100℃以下でも可能である。その真空度に対応する除去可能な温度以上であれば良い。例えば、290±10mmHgの場合、75℃以上であれば本発明の亜鉛クラスターを形成することが出来る。
本発明の亜鉛クラスター製造には、無溶媒下原料が液化せず固体条件で昇華する温度条件以下でも可能である。また、溶媒下製造する場合には、本発明の亜鉛クラスター形成に影響しない溶媒であれば、使用可能である。好ましくは、極性の低い有機溶媒である。例えば、ベンゼン、トルエン、キシレン、ヘキサン、ヘプタン、オクタンなどが使用することが出来る。さらに好ましくは、ベンゼン、トルエン、キシレンなどの芳香族系溶媒が好ましい。即ち、カルボン酸亜鉛水和物(Zn(OCOR)2・xH2O)を製造温度で溶解することができ、かつ、本発明の亜鉛クラスターの溶解性が低い溶媒が好ましい。このように、本発明の亜鉛クラスターは、従来の亜鉛クラスター製造温度条件(250℃、360℃)よりも低い温度条件で製造することができる。好ましくは200℃以下、さらに好ましくは100度以下で製造する。
上記条件で得られた本発明の一般式(1)で示される亜鉛クラスターは、高い吸湿性や空気中で不安定な場合があるため、水分の存在が少ない不活性ガス存在下で取り扱うことが好ましい。不活性ガスとしては、好ましくは窒素又はアルゴン等が挙げられる。
本発明の亜鉛クラスターの触媒としての使用量は、特に限定されないが、通常、原料1モルに対して、亜鉛原子が0.001~0.9モル、より好ましくは0.001~0.3モル、さらに好ましくは0.001~0.1モルの割合である。
反応は溶媒中で通常行われる。溶媒の具体例としては、特に限定されないが、例えば、トルエン、キシレン又は塩化ベンゼン等の芳香族系溶媒;ヘキサン、ヘプタン又はオクタン等の脂肪族炭化水素系溶媒;ジエチルエーテル、ジイソプロピルエーテル、tert-ブチルメチルエーテル、テトラヒドロフラン又は1,4-ジオキサン等のエーテル系溶媒;ジメチルホルムアミド(DMF)、ジメチルアセトアミド(DMAc)又はN-メチルピロリドン(NMP)等のアミド系溶媒;ジメチルスルホキシド(DMSO)等が挙げられる。また、無溶媒中でも反応を行うことが出来る。
本発明の亜鉛クラスターを用いた種々の反応は、大気下、又は窒素ガス若しくはアルゴンガス等の不活性ガス雰囲気下で行うことができる。反応時間は、特に限定されないが、通常約1~45時間、好ましくは6~18時間程度であり、反応温度は、特に限定されないが、室温~約150℃、好ましくは50~150℃、より好ましくは約80~130℃程度で行われる。これらの条件は使用される原料等の種類及び量により適宜変更されうる。
一般式(1)で示される亜鉛クラスターは、上記のような各種触媒反応において有用であるが、その他の用途として、酸化亜鉛膜形成の原料としても有用である。例えば、Applied Surface Science (2007), 253(9), 4356-4360には、原料である酢酸亜鉛水和物から真空加熱により系内で亜鉛クラスターを形成後、基板表面に亜鉛クラスター膜を形成して、さらに500度以上の加熱処理をすることで従来の製造法よりも均一な酸化亜鉛(ZnO)膜が生じることが報告されている。
また、特開2005-305233号には、酢酸亜鉛水和物を用いてミストCVD法により系中で亜鉛クラスターを形成させながら、均一な酸化亜鉛膜を形成できる事が示されている。このような原料としても使用可能である。
上記のように、本発明の亜鉛クラスターは、酸化亜鉛膜形成等などの前駆体としても有用である。
以下、実施例により本発明をより具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。
マスクペクトル(MS)測定条件:
装置 LCMS-IT-TOF(SHIMADZU)
測定法 ESI-NEGATIVE MODE
インターフェース電圧 -3.5kV
ネブライズガス流量 1.5L/min
溶媒 DMF
内部質量校正 TFA-Na(m/z 928.8339, 1064.8087, 1200.7835)
フーリエ変換赤外分光測定条件:
装置 Avatar360(Nicolet製)
分子軌道計算:
プログラム Gaussian03(Gaussian社)
亜鉛クラスターの製造
トリフルオロ酢酸亜鉛水和物(Alfa Aesar社製)30.3g(水6.6wt%含有)を、片端を封じたガラス管に導入した。ガラス管の一方に窒素冷却トラップを繋げ、油回転ポンプにて真空度4 x 10-1torrまで減圧した。続いて、ガラス管を120℃で1.5時間ヒーターで加熱した後、徐々に160℃まで昇温し、30分間同温度で加熱した。約6時間でガラス管中のトリフルオロ酢酸亜鉛水和物が無くなり、若干の残渣が残った。
その後、加熱を止め室温まで自然冷却を行った。冷却後、ガラス管と真空ポンプ内に設けたバルブを閉めて、空気及び水分の混入がないようにして、窒素雰囲気に保ったグローブバック内でガラス管に付着した白色固体をかき取った。得られた白色固体は、窒素雰囲気内でシュレンク菅に入れて、水分が入らない状態に密閉した後にバック内から取り出し、重量を測定したところ24.7gの亜鉛クラスターが得られた。
High-resolution ES-MS(negative)スペクトル測定結果
Negative ion HR-ESI-MS m/z: 1062.6074
[M-H]-(calcd. For C14F21O15Zn4 1062.6073)Δ0.09ppm
IRスペクトルのピークは、426.67cm-1、520cm-1、729.22cm-1、798.99cm-1、851.34cm-1、1203.43cm-1、1438.87cm-1、1629.02cm-1、1708.08cm-1であった。
エステル化反応
窒素雰囲気下、3-フェニルプロピオン酸(3.0mmol)、n-ブタノール(3.6mmol)、上記実施例1で得られた亜鉛クラスター(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、3-フェニルプロピオン酸ブチルが定量的に得られた。
エステル交換反応
窒素雰囲気下、3-フェニルプロピオン酸メチル(3.0mmol)、n-ブタノール(3.6mmol)、上記実施例1で得られた亜鉛クラスター(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、3-フェニルプロピオン酸ブチルが定量的に得られた。
アルコールとアミン存在下でのエステル交換反応
窒素雰囲気下、3-フェニルプロピオン酸メチル(3.0mmol)、シクロヘキサノール(3.6mmol)、シクロヘキシルアミン(3.6mmol)、上記実施例1で得られた亜鉛クラスター(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、エステル体である3-フェニルプロピオン酸シクロヘキシルが定量的に得られた。アミド体の生成は確認できなかった。
亜鉛クラスターの製造
トリフルオロ酢酸亜鉛水和物(亜鉛含量18wt%、水分19wt%)9.70gとトルエンを四つ口フラスコに加えた。フラスコ内を窒素で置換した後、真空ポンプにてフラスコ内を290±10mmHgまで減圧した。続いて徐々に加温していくと60℃でフラスコ内の混合物が透明化して完全に溶解した。75℃に到達後、同温にて溶媒回収を行った。溶媒留去物は、トルエンと水が含まれており、回収溶媒中の水の量がトリフルオロ酢酸亜鉛水和物仕込み量の約20wt%になったら加熱を停止した。徐々に-5℃まで冷却し、同温で4時間撹拌後に窒素下ろ過を行った。得られた白色固体を75℃/5mmHgで乾燥を行った。乾燥後、6.37gの白色固体を得た。
上記白色固体の亜鉛含量を以下の滴定法で測定した。すなわち、200mlの三角フラスコに上記で得られた白色固体約30mgを秤量した。精製水100mlを加えて溶解した。さらに緩衝液(酢酸-酢酸ナトリウム、pH5)5mlを加えた。さらにヘキサミン(ヘキサメチルテトラミン)を徐々に加えて、pHを約5に調製した。XO指示薬溶液を数滴加え、0.01mol/LのEDTA標準液で滴定して、亜鉛含量を測定した。終点において、赤紫→黄に変化した。その結果、亜鉛含量は25.58wt%であった。この結果はZn4O(OCOCF3)6(CF3COOH)n(n=0.59)であることを示している。
トリフルオロ酢酸付加体亜鉛クラスターとして収率計算を行うと89.2%の収率であった。また、亜鉛含量結果から亜鉛換算で収率を求めると93.32%であった。
アミノ基存在下でのエステル交換反応
窒素雰囲気下、4-ピペリジンメタノール0.6907g(6mmol)、上記実施例5で得られた亜鉛クラスター64.2mg(0.06mmol)及び酢酸エチル(10.0ml)の混合物を4時間還流した結果、エステル体が85.4%得られた。アミド体の生成は0.7%確認された。また、エステル化とアミド化が共に起こった生成物が4.7%得られた。転換率は、90.9%であった。
エステル交換反応
窒素雰囲気下、3-フェニルプロピオン酸メチル(3.0mmol)、t-ブタノール(3.6mmol)、上記実施例5で得られた亜鉛クラスター(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、3-フェニルプロピオン酸t-ブチルが定量的に得られた。
エステル交換反応
窒素雰囲気下、カルボベンジルオキシグリシンメチルエステル(3.0mmol)、t-ブタノール(3.6mmol)、上記実施例5で得られた亜鉛クラスター(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、カルボベンジルオキシグリシンt-ブチルエステルが収率91.8%で得られた。
エステル交換反応
窒素雰囲気下、 (4-((テトラヒドロ-2H-ピラン-2-イルオキシ)メチル)フェニル)メタノール(3.0mmol)、t-ブタノール(3.6mmol)、上記実施例5で得られた亜鉛クラスター(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、4-((テトラヒドロ-2H-ピラン-2-イルオキシ)メチル)ベンジルアセテートが収率92.9%で得られた。
エステル交換反応
窒素雰囲気下、3-フェニルプロピオン酸メチル(3.0mmol)、t-ブタノール(3.6mmol)、亜鉛クラスターZn4O(OCOCF3)6(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、3-フェニルプロピオン酸t-ブチルが定量的に得られた。
エステル交換反応
窒素雰囲気下、カルボベンジルオキシグリシンメチルエステル(3.0mmol)、t-ブタノール(3.6mmol)、亜鉛クラスターZn4O(OCOCF3)6(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、カルボベンジルオキシグリシンt-ブチルエステルが収率83.8%で得られた。
エステル交換反応
窒素雰囲気下、4-(テトラヒドロ-2H-ピラン-2-イルオキシ)酪酸メチル(3.0mmol)、t-ブタノール(3.6mmol)、亜鉛クラスターZn4O(OCOCF3)6(0.0375mmol)及びジイソプロピルエーテル(5.0ml)の混合物を18時間還流した結果、4-(テトラヒドロ-2H-ピラン-2-イルオキシ)酪酸t-ブチルが収率92.9%で得られた。
アセチル化反応
窒素雰囲気下、((4-トリエチルシリルオキシ)メチル)フェニル)メタノール(6mmol)、上記実施例5で得られた亜鉛クラスター(0.075mmol)及び酢酸エチル(1.7ml)の混合物を18時間還流した結果、4-((トリエチルシリルオキシ)メチル)ベンジルアセテートが86%の収率で得られた。
アセチル化反応
窒素雰囲気下、(4-((テトラヒドロ-2H-ピラン-2-イルオキシ)メチル)フェニル)メタノール(6mmol)、亜鉛クラスターZn4O(OCOCF3)6(0.075mmol)及び酢酸エチル(1.7ml)の混合物を18時間還流した結果、4-((テトラヒドロ-2H-ピラン-2-イルオキシ)メチル)ベンジルアセテートが84%の収率で得られた。
オキサゾリン類の製造
窒素雰囲気下、安息香酸メチル(1.5mmol)、(S)-バリノール(1.8mmol)、上記実施例5で得られた亜鉛クラスター(0.0375mmol)及びクロロベンゼン(2.5ml)の混合物を12時間還流した結果、(S)-4-イソプロピル-2-フェニルオキサゾリンが収率86%で得られた。
オキサゾリン類の製造
窒素雰囲気下、安息香酸メチル(1.5mmol)、(S)-バリノール(1.8mmol)、亜鉛クラスターZn4O(OCOCF3)6(0.0375mmol)及びクロロベンゼン(2.5ml)の混合物を12時間還流した結果、(S)-4-イソプロピル-2-フェニルオキサゾリンが収率84%で得られた。
これらの結果から、本発明の亜鉛クラスターは、従来の亜鉛クラスターZn4O(OCOCF3)6と同等以上の触媒活性を示した。
ESI-MS測定から推定した構造[Zn4O(OCOCF3)6(CF3COOH)]について、分子軌道計算による分子モデリングを行って構造決定を試みた。その結果を図4に示す。なお、分子軌道計算による分子モデリングは、Gaussian03(Gaussian社)を用いて計算を行った((B3LYP/6-31G(d、p)))。
分子軌道計算によりエネルギー的に安定化した構造(図4)を求めた。従来から知られている亜鉛四核クラスターZn4O(OCOCF3)6(図5)よりもZn4O(OCOCF3)6(CF3COOH)(図4)が、5.18Kcal/molエネルギー的に安定化していることが明らかとなった。
Claims (4)
- 下記一般式(1)
Zn4O(OCOR)6(RCOOH)n (1)
(一般式(1)中、Rはハロゲン原子で置換されていてもよい炭素数1~4のアルキル基を表し、nは0.1~1を表す。)
で表される亜鉛クラスター。 - 一般式(2)
Zn(OCOR)2・xH2O (2)
(一般式(2)中、Rはハロゲン原子で置換されていてもよい炭素数1~4のアルキル基を表し、xは0以上の任意の数を表す。)
で表されるカルボン酸亜鉛水和物を、50℃~200℃の温度で加熱反応させることを特徴とする請求項1に記載の亜鉛クラスターの製造方法。 - 請求項1に記載の亜鉛クラスターを触媒として用いることを特徴とする、カルボン酸またはそのエステルによる水酸基のアシル化反応。
- 請求項1に記載の亜鉛クラスターを触媒として用いることを特徴とする、カルボン酸またはそのエステルとアミノアルコールとを反応させるオキサゾリン類の製造方法。
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Also Published As
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CN102482190A (zh) | 2012-05-30 |
CA2772588C (en) | 2016-08-16 |
JP5634130B2 (ja) | 2014-12-03 |
EP2476664B1 (en) | 2015-03-04 |
KR20120089251A (ko) | 2012-08-09 |
JP2011079810A (ja) | 2011-04-21 |
IN2012DN01815A (ja) | 2015-06-05 |
US20120172601A1 (en) | 2012-07-05 |
US8552204B2 (en) | 2013-10-08 |
KR101631351B1 (ko) | 2016-06-16 |
CN102482190B (zh) | 2014-05-07 |
EP2476664A4 (en) | 2013-08-21 |
CA2772588A1 (en) | 2011-03-17 |
EP2476664A1 (en) | 2012-07-18 |
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