JP6806990B2 - α−フルオロアルデヒド類の製造方法 - Google Patents
α−フルオロアルデヒド類の製造方法 Download PDFInfo
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- JP6806990B2 JP6806990B2 JP2016154626A JP2016154626A JP6806990B2 JP 6806990 B2 JP6806990 B2 JP 6806990B2 JP 2016154626 A JP2016154626 A JP 2016154626A JP 2016154626 A JP2016154626 A JP 2016154626A JP 6806990 B2 JP6806990 B2 JP 6806990B2
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- Prior art keywords
- catalyst
- reaction
- chloride
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- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 123
- 239000003054 catalyst Substances 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 55
- 239000002585 base Substances 0.000 claims description 49
- -1 oxyfluoride Chemical compound 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical group [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 150000003058 platinum compounds Chemical class 0.000 claims description 14
- 150000003284 rhodium compounds Chemical class 0.000 claims description 14
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 11
- GPGMRSSBVJNWRA-UHFFFAOYSA-N hydrochloride hydrofluoride Chemical compound F.Cl GPGMRSSBVJNWRA-UHFFFAOYSA-N 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 150000002466 imines Chemical class 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- 150000004678 hydrides Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 3
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- TXUZMGFRPPRPQA-UHFFFAOYSA-K trifluororhodium Chemical compound F[Rh](F)F TXUZMGFRPPRPQA-UHFFFAOYSA-K 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 145
- 235000019441 ethanol Nutrition 0.000 description 66
- 239000000243 solution Substances 0.000 description 40
- 238000005481 NMR spectroscopy Methods 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 28
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 11
- 125000001153 fluoro group Chemical group F* 0.000 description 11
- 239000000539 dimer Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000007810 chemical reaction solvent Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000011903 deuterated solvents Substances 0.000 description 6
- 150000002373 hemiacetals Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000013558 reference substance Substances 0.000 description 6
- 0 *C(C(O)O*)(F)F Chemical compound *C(C(O)O*)(F)F 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 150000007529 inorganic bases Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical class CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004508 fractional distillation Methods 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- JVTSHOJDBRTPHD-UHFFFAOYSA-N 2,2,2-trifluoroacetaldehyde Chemical compound FC(F)(F)C=O JVTSHOJDBRTPHD-UHFFFAOYSA-N 0.000 description 3
- DKNMRIXYSHIIGC-UHFFFAOYSA-N 2,2-difluoroacetaldehyde Chemical compound FC(F)C=O DKNMRIXYSHIIGC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001012 protector Effects 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GZKHDVAKKLTJPO-UHFFFAOYSA-N CCOC(C(F)F)=O Chemical compound CCOC(C(F)F)=O GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 2
- WEEOMNFWRCDRJI-UHFFFAOYSA-N CCOC(C(F)F)O Chemical compound CCOC(C(F)F)O WEEOMNFWRCDRJI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
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- 230000003213 activating effect Effects 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
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- 229910021513 gallium hydroxide Inorganic materials 0.000 description 2
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 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
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- YRQNNUGOBNRKKW-UHFFFAOYSA-K trifluororuthenium Chemical compound F[Ru](F)F YRQNNUGOBNRKKW-UHFFFAOYSA-K 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
<1>
一般式[1]:
で示されるα−フルオロエステル類に、
ルテニウム化合物、ロジウム化合物、または白金化合物を活性炭に担持した触媒、
および、塩基の存在下、水素(H 2 )を反応させることにより、一般式[2]:
で表されるα−フルオロアルデヒド類を製造する方法であって、
前記ルテニウム化合物が、ルテニウムのフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種であり、
前記ロジウム化合物が、ロジウムのフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種であり、
前記白金化合物が、白金のフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種であり、
前記塩基が、イミン系塩基、アルカリ金属もしくはアルカリ土類金属の水素化物、アルカリ金属もしくはアルカリ土類金属の水酸化物、アルカリ金属もしくはアルカリ土類金属炭酸塩、アルカリ金属の炭酸水素塩、アルカリ金属もしくはアルカリ土類金属の酸化物、またはアルカリ金属のアルコキシドである、α−フルオロアルデヒド類を製造する方法。
<2>
前記アルカリ金属のアルコキシドが、ナトリウムエトキシド、カリウムエトキシド、リチウムエトキシド、またはカリウムtert−ブトキシドである、<1>に記載の方法。
<3>
前記触媒が、水素で還元処理した触媒である、<1>または<2>に記載の方法。
<4>
反応を、塩基または触媒を逐次添加することにより行う、<1>乃至<3>の何れかに記載の方法。
<5>
塩基の使用量が、一般式[1]で示されるα−フルオロエステル類1モルに対して0.01モル以上、3モル以下である、<1>乃至<4>の何れかに記載の方法。
<6>
逐次添加が、塩基を少なくとも2回以上に分割して行う、<4>に記載の方法。
<7>
逐次添加が、触媒を少なくとも2回以上に分割して行う、<4>に記載の方法。
<8>
水素圧が0.001〜4MPaの範囲で、かつ、反応温度として0〜40℃の範囲で行う、<1>乃至<7>の何れかに記載の方法。
<9>
アルコール類の存在下で反応を行う、<1>乃至<8>の何れかに記載の方法。
<10>
反応終了後、使用した触媒を回収し、再利用することにより行う、<1>乃至<9>の何れかに記載の方法。
<11>
触媒の回収が、触媒をろ別し、水次いでアルコール類で洗浄することにより行う、<10>に記載の方法。
<12>
反応系中の水分が0.5〜0.001質量%の範囲で行うことを特徴とする、<1>乃至<11>の何れかに記載の方法。
<13>
一般式[2]で示されるα−フルオロアルデヒド類が、下記式
で表されるα−フルオロアルデヒド類等価体として得ることを含む、<1>乃至<12>の何れかに記載の方法。
本発明は、上記<1>〜<13>に係る発明であるが、以下、それ以外の事項(例えば、下記[発明1]−[発明17])についても記載している。
[発明1]
一般式[1]:
で示されるα−フルオロエステル類に、
ルテニウム化合物、ロジウム化合物、または白金化合物を金属酸化物もしくは活性炭に担持した触媒、
および、塩基の存在下、水素(H2)を反応させることにより、一般式[2]:
で表されるα−フルオロアルデヒド類を製造する方法。
[発明2]
塩基がイミン系塩基または無機塩基である、発明1に記載の方法。
[発明3]
塩基がアルカリ金属のアルコキシドである、発明1または2に記載の方法。
[発明4]
反応を、塩基または触媒を逐次添加することにより行う、発明1乃至3の何れかに記載の方法。
[発明5]
塩基の使用量が、一般式[1]で示されるα−フルオロエステル類1モルに対して0.01モル以上、3モル以下である、発明1乃至4の何れかに記載の方法。
[発明6]
逐次添加が、塩基を少なくとも2回以上に分割して行う、発明4に記載の方法。
[発明7]
逐次添加が、触媒を少なくとも2回以上に分割して行う、発明4に記載の方法。
[発明8]
ルテニウム化合物が、ルテニウムのフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種である、発明1乃至7の何れかに記載の方法。
[発明9]
ロジウム化合物が、ロジウムのフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種である、発明1乃至7の何れかに記載の方法。
[発明10]
白金化合物が、白金のフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種である、発明1乃至7の何れかに記載の方法。
[発明11]
金属酸化物が、アルミナ、ジルコニア、チタニア、シリカ、またはマグネシアである、発明1乃至7の何れかに記載の方法。
[発明12]
水素圧が0.001〜4MPaの範囲で、かつ、反応温度として0〜40℃の範囲で行うことを特徴とする、発明1乃至11の何れかに記載の方法。
[発明13]
アルコール類の存在下で反応を行う、発明1乃至12の何れかに記載の方法。
[発明14]
反応終了後、使用した触媒を回収し、再利用することにより行う、発明1乃至13の何れかに記載の方法。
[発明15]
触媒の回収が、触媒をろ別し、水次いでアルコール類で洗浄することにより行う、発明14に記載の方法。
[発明16]
反応系中の水分が0.001〜0.5質量%の範囲で行うことを特徴とする、発明1乃至15の何れかに記載の方法。
[発明17]
一般式[2]で示されるα−フルオロアルデヒド類が、下記式
で表されるα−フルオロアルデヒド類等価体として得ることを含む、発明1乃至16の何れかに記載の方法。
以上のことから、フッ素原子を持つエステル類に対する還元反応は、触媒の種類によって反応性に違いは出るものの、本願発明における目的化合物であるアルデヒド体を工業的に採用し得る条件で、且つ効率よく得ることは非常に困難であると予想された。
更に、塩基や触媒の種類や量、反応試剤の導入方法といった、特定の反応条件に付すことで、極めて高い選択性でもってアルデヒド類を得る知見を得、さらに、反応後に触媒を回収し、本発明に再利用できる知見も得た。
なお、本発明のように、α−フルオロエステル類を、本発明で用いる触媒および塩基の存在下、水素と反応させることにより、α−フルオロアルデヒド類を製造する方法は知られていなかった。
で表されるα,α−ジフルオロ酢酸エステル類が好ましく、大量規模での入手が容易である。
前記金属酸化物または活性炭は、ルテニウム化合物、ロジウム化合物、または白金化合物を担持する「担体」として機能する。
一方、前記活性炭は、各種のものが市販されているのでそれらのうちから選んで使用すればよい。例えば、瀝青炭から製造された活性炭(例えば、カルゴン粒状活性炭CAL(東洋カルゴン(株)製)、椰子殻炭(例えば、日本エンバイロケミカルズ(株)製)などを挙げることができるが、当然これらの種類に限られることはない。
触媒の使用量は、一般式[1]で示されるα−フルオロエステル類に対し、0.01質量%以上であれば良く、1〜100質量%が好ましく、5〜30質量%がより好ましい。
(a)3級アミン、(b)含窒素芳香族複素環式化合物、
(c)次のイミン骨格
−C=N−C−
を有する化合物(なお、本明細書で、この化合物を「イミン系塩基」と言うことがある)、
から選ばれる有機塩基、
(d)無機塩基、
または
(e)水酸化テトラアルキルアンモニウム、
である。それぞれの化合物の具体的な例を、以下、明示する。
一方、無機塩基としてはアルカリ金属のアルコキシドがより好ましく、中でも、ナトリウムエトキシド、カリウムエトキシド、リチウムエトキシドまたはカリウムtert−ブトキシドが極めて好ましい。
で表される化合物が、α−フルオロアルデヒド類等価体として得られる。
本発明において、α−フルオロアルデヒド類を製造する際の「好ましい反応条件」を以下、述べる。
式[1]で表されるα−フルオロエステル類がα,α−ジフルオロ酢酸エステル類であり、
触媒がルテニウム化合物、ロジウム化合物または白金化合物を活性炭に担持した触媒であって、かつ、該触媒の量が、α,α−ジフルオロ酢酸エステル類に対し5〜30質量%であり、
用いる塩基がアルカリ金属のアルコキシドであって、かつ該アルコキシドの量がα,α−ジフルオロ酢酸エステル類1モルに対し、0.01〜3モルであり、
反応溶媒としてアルコール類であって、該アルコール類の量がα,α−ジフルオロ酢酸エステル類1モルに対し、0.05〜7L、
とし、前述した水素圧及び反応温度を採用することにより、後述の実施例で示すように、該目的物を高選択率で得ることができる。
なお、本発明で用いた触媒は、反応後に目的物である式[2]で示されるα−フルオロアルデヒド類を含む反応液をろ別し、該反応液と触媒とを分離させた後、触媒を含む反応残渣に対し、エタノール等のアルコール類で洗浄し、その後回収することで、本発明の反応に再利用することができる。
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
[比較例4]
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
用いたRu/Cをろ過し、エタノール200gで掛け洗浄した。その後Ru/Cを回収して水200gで30分間攪拌した後にろ過し、再度Ru/Cを回収してエタノール200gで30分間攪拌した後にろ過し、回収した触媒を次の反応(実施例16)へ用いた。
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
上記に記載の反応後に、実施例15に記載と同様の操作でRu/Cを回収した。
1H−NMR(基準物質;Me4Si、重溶媒;CDCl3)、δ ppm;1.26(t、3H)、3.63(m、1H)、3.92(m、1H)、4.70(m、1H)、5.60(dt、1H)、ヒドロキシル基のプロトンは帰属できず。
19F−NMR(基準物質;C6F6、重溶媒;CDCl3)、δ ppm;27.9(ddd、2F)。
1H−NMR(基準物質;Me4Si、重溶媒;CDCl3)、δ ppm;3.92(m、2H)、4.79(m、1H)、5.68(dt、1H)、5.91(ddt、1H)、ヒドロキシル基のプロトンは帰属できず。
19F−NMR(基準物質;C6F6、重溶媒;CDCl3)、δ ppm;27.0(ddd、2F)、36.1(dt、2F)。
1H−NMR(基準物質;Me4Si、重溶媒;CDCl3)、δ ppm;1.28(t、3H)、3.67(m、1H)、3.88(m、1H)、4.78(m、0.5H)、4.90(m、0.5H)、5.04(m、1H)、5.64(m、2H)、ヒドロキシル基のプロトンは帰属できず。
19F−NMR(基準物質;C6F6、重溶媒;CDCl3)、δ ppm;27.9(m、4F)。
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
Claims (13)
- 一般式[1]:
で示されるα−フルオロエステル類に、
ルテニウム化合物、ロジウム化合物、または白金化合物を活性炭に担持した触媒、
および、塩基の存在下、水素(H2)を反応させることにより、一般式[2]:
で表されるα−フルオロアルデヒド類を製造する方法であって、
前記ルテニウム化合物が、ルテニウムのフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種であり、
前記ロジウム化合物が、ロジウムのフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種であり、
前記白金化合物が、白金のフッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、及びオキシフッ化塩化物からなる群より選ばれる少なくとも1種であり、
前記塩基が、イミン系塩基、アルカリ金属もしくはアルカリ土類金属の水素化物、アルカリ金属もしくはアルカリ土類金属の水酸化物、アルカリ金属もしくはアルカリ土類金属炭酸塩、アルカリ金属の炭酸水素塩、アルカリ金属もしくはアルカリ土類金属の酸化物、またはアルカリ金属のアルコキシドである、α−フルオロアルデヒド類を製造する方法。 - 前記アルカリ金属のアルコキシドが、ナトリウムエトキシド、カリウムエトキシド、リチウムエトキシド、またはカリウムtert−ブトキシドである、請求項1に記載の方法。
- 前記触媒が、水素で還元処理した触媒である、請求項1または2に記載の方法。
- 反応を、塩基または触媒を逐次添加することにより行う、請求項1乃至3の何れかに記載の方法。
- 塩基の使用量が、一般式[1]で示されるα−フルオロエステル類1モルに対して0.01モル以上、3モル以下である、請求項1乃至4の何れかに記載の方法。
- 逐次添加が、塩基を少なくとも2回以上に分割して行う、請求項4に記載の方法。
- 逐次添加が、触媒を少なくとも2回以上に分割して行う、請求項4に記載の方法。
- 水素圧が0.001〜4MPaの範囲で、かつ、反応温度として0〜40℃の範囲で行う、請求項1乃至7の何れかに記載の方法。
- アルコール類の存在下で反応を行う、請求項1乃至8の何れかに記載の方法。
- 反応終了後、使用した触媒を回収し、再利用することにより行う、請求項1乃至9の何れかに記載の方法。
- 触媒の回収が、触媒をろ別し、水次いでアルコール類で洗浄することにより行う、請求項10に記載の方法。
- 反応系中の水分が0.5〜0.001質量%の範囲で行うことを特徴とする、請求項1乃至11の何れかに記載の方法。
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