JP6669962B2 - α,α−ジフルオロアセトアルデヒドの製造方法 - Google Patents
α,α−ジフルオロアセトアルデヒドの製造方法 Download PDFInfo
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- JP6669962B2 JP6669962B2 JP2016009618A JP2016009618A JP6669962B2 JP 6669962 B2 JP6669962 B2 JP 6669962B2 JP 2016009618 A JP2016009618 A JP 2016009618A JP 2016009618 A JP2016009618 A JP 2016009618A JP 6669962 B2 JP6669962 B2 JP 6669962B2
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- Prior art keywords
- difluoroacetaldehyde
- formula
- mol
- hemiacetal
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- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 51
- -1 alkali metal alkoxide Chemical class 0.000 claims description 19
- 239000002585 base Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012327 Ruthenium complex Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical group [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 7
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 7
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 7
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 claims description 4
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 2
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 230000009467 reduction Effects 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 150000002373 hemiacetals Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- DKNMRIXYSHIIGC-UHFFFAOYSA-N 2,2-difluoroacetaldehyde Chemical compound FC(F)C=O DKNMRIXYSHIIGC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003638 chemical reducing agent 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
- 238000004508 fractional distillation Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 0 *OC(C(F)F)O Chemical compound *OC(C(F)F)O 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- FMDMKDPUFQNVSH-UHFFFAOYSA-N ethyl 3,3,3-trifluoropropanoate Chemical compound CCOC(=O)CC(F)(F)F FMDMKDPUFQNVSH-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
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- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 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
- 125000006015 bromomethoxy group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
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- 125000006165 cyclic alkyl group Chemical group 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
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- 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
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- 239000013076 target substance Substances 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
- 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
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
で表されるルテニウム錯体(以下、本明細書で「Ru−SNS」と書くことがある。)が、一般式[1]:
で表されるα,α−ジフルオロ酢酸エステル類の還元において、高い変換率のみならず、該エステル類の過剰還元によるβ,β−ジフルオロエタノール(詳細は後述する)の副生を抑制した高い選択率をも可能にし、極めて無駄の少ない工業的製造方法を提供できる非常に有効な水素化触媒または前駆体になる事を見出した。
さらに、反応の変換率と選択率が共に高いため、出発原料の回収や副生するβ,β−ジフルオロエタノールの分離といった精製の負荷を軽減することも可能である。
従来技術の課題を解決できるα,α−ジフルオロアセトアルデヒドの工業的な製造方法を提供することができる点で、本発明の優位性は非常に高いものである。
[発明1]
式[1]で表されるα,α−ジフルオロ酢酸エステル類を、式[2]で表されるルテニウム錯体および塩基の存在下、水素(H2)と反応させ、式[3]:
で表されるα,α−ジフルオロアセトアルデヒドアルキルヘミアセタールを製造する方法において、
塩基としてアルカリ金属アルコキシドを用い、該アルカリ金属アルコキシドの使用量をα,α−ジフルオロ酢酸エステル類1モルに対して0.001モル以上、
水素圧を1.0MPa〜10MPa(絶対圧)とし、
該反応におけるα,α−ジフルオロ酢酸エステル類の変換率を80%以上で、
かつ、
α,α−ジフルオロ酢酸エステル類から生成するα,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドアルキルヘミアセタールと、
副生するβ,β−ジフルオロエタノールとの選択率が、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドアルキルヘミアセタール:β,β−ジフルオロエタノール=90%以上:10%以下となるように反応させることを特徴とする、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドアルキルヘミアセタールの製造方法。
[発明2]
アルカリ金属アルコキシドが、リチウムメトキシド、ナトリウムメトキシド、カリウムメトキシド、リチウムエトキシド、ナトリウムエトキシド、カリウムエトキシド、リチウムイソプロポキシド、ナトリウムイソプロポキシド、カリウムイソプロポキシド、リチウムtert−ブトキシド、ナトリウムtert−ブトキシドまたはカリウムtert−ブトキシドである、発明1に記載の製造方法。
[発明3]
アルカリ金属アルコキシドが、リチウムメトキシド、ナトリウムメトキシド、カリウムメトキシド、リチウムエトキシド、ナトリウムエトキシドまたはカリウムエトキシドである、発明1または2に記載の製造方法。
α,α−ジフルオロ酢酸エチルを、式[2]で表されるルテニウム錯体および塩基の存在下、水素(H2)と反応させ、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドエチルヘミアセタールを製造する方法において、
塩基としてナトリウムエトキシドを用い、該エトキシドの使用量をα,α−ジフルオロ酢酸エチル1モルに対して0.01〜5.0モル、
水素圧を2.0MPa〜6.0MPa(絶対圧)とし、
該反応におけるα,α−ジフルオロ酢酸エチルの変換率を90%以上で、
かつ、
α,α−ジフルオロ酢酸エチルから生成するα,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドエチルヘミアセタールと、
副生するβ,β−ジフルオロエタノールとの選択率を、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドエチルヘミアセタール:β,β−ジフルオロエタノール=93%以上:7%以下となるように反応させることを特徴とする、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドエチルヘミアセタールの製造方法。
[発明5]
反応を、アルコール類の溶媒を用い、かつ、反応温度を30℃以下で行うことを特徴とする、発明1乃至4の何れかに記載の製造方法。
脂肪族炭化水素類、芳香族炭化水素類、ハロゲン類またはエーテル類の溶媒を用いる場合、+50℃以下で行えば良く、+45〜−30℃が好ましく、+40〜−20℃が特に好ましく、+35〜−10℃が極めて好ましい。
本発明の有用性を最大限に発揮させるには、アルコール類の溶媒を用いて、反応温度を25℃以下で行うことが特に好ましい。
α,α−ジフルオロ酢酸エステル類の変換率が80%以上で、かつ、
α,α−ジフルオロ酢酸エステル類から生成するα,α−ジフルオロアセトアルデヒド類と、
副生するβ,β−ジフルオロエタノールとの選択率がそれぞれ90%以上、10%以下といった、良好な条件で目的物であるα,α−ジフルオロアセトアルデヒド類を製造できる(但し、α,α−ジフルオロアセトアルデヒド類とβ,β−ジフルオロエタノール、両方の和を100とする)。
α,α−ジフルオロ酢酸エステル類の変換率が90%以上で、かつ、
α,α−ジフルオロ酢酸エステル類から生成するα,α−ジフルオロアセトアルデヒド類と、
副生するβ,β−ジフルオロエタノールの選択率が93%以上、7%以下の条件でα,α−ジフルオロアセトアルデヒド類を製造できる。
α,α−ジフルオロ酢酸エステル類から生成するα,α−ジフルオロアセトアルデヒド類と副生するβ,β−ジフルオロエタノールの選択率がそれぞれ95%以上、5%以下といった、極めて良好な条件で目的物であるα,α−ジフルオロアセトアルデヒド類を製造できる(後述の実施例1〜5、実施例7〜9、実施例11〜14)。
なお、本発明は、前述した条件を採用することにより、変換率が80%以上であって、α,α-ジフルオロアセトアルデヒド類と副生するβ,β−ジフルオロエタノールの選択率がそれぞれ90%以上、10%以下といった条件で目的物を製造することができるが、目的物であるα,α−ジフルオロアセトアルデヒド類を高い純度で得ることができれば、高純度化するための精製工程、例えば高い理論段数の分別蒸留を必要としない。例えば、後述の実施例で開示している選択率を達成することは、同時に後述する精製工程の手間を軽減できる為、工業的な製造としても本発明の優位性は非常に高い。
前記後処理過程にて、一般式[3]で表されるα,α−ジフルオロアセトアルデヒドの、該アルデヒドの安定等価体として、特に一般式[5]:
で表されるα,α−ジフルオロアセトアルデヒドアルキルヘミアセタール体由来の二量体が得られる場合、それをメタノールまたはエタノールと接触させることにより、α,α−ジフルオロアセトアルデヒドのヘミアセタール体に収束させる精製操作も可能である。
[実施例1〜14]および[比較例1〜8]
実施例1〜14および比較例1〜8の一般的製造方法を以下に示す。
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
または下記式:
[比較例9]
ステンレス鋼(SUS)製耐圧反応容器に、下記式:
以上、実施例1〜14及び比較例1〜8について、表として以下にまとめる。
Claims (5)
- 一般式[1]:
で表されるα,α−ジフルオロ酢酸エステル類を、式[2]:
で表されるルテニウム錯体および塩基の存在下、水素(H2)と反応させ、式[3]:
で表されるα,α−ジフルオロアセトアルデヒドアルキルヘミアセタールを製造する方法において、
ルテニウム錯体の使用量が、前記α,α−ジフルオロ酢酸エステル類1モルに対し、0.000001モル以上、0.00013モル以下であり、
塩基としてアルカリ金属アルコキシドを用い、該アルカリ金属アルコキシドの使用量をα,α−ジフルオロ酢酸エステル類1モルに対して0.001モル以上、
水素圧を1.0MPa〜10MPa(絶対圧)とし、
反応をアルコール系溶媒中で行い、
反応温度を−30℃以上、+30℃以下とし、
該反応におけるα,α−ジフルオロ酢酸エステル類の変換率を80%以上で、
かつ、
α,α−ジフルオロ酢酸エステル類から生成するα,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドアルキルヘミアセタールと、副生するβ,β−ジフルオロエタノールとの選択率が、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドアルキルヘミアセタール:β,β−ジフルオロエタノール=90%以上:10%以下となるように反応させることを特徴とする、
α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドアルキルヘミアセタールの製造方法。 - 反応温度を、0℃以上、+25℃以下とする、
請求項1に記載の製造方法。 - アルカリ金属アルコキシドが、リチウムメトキシド、ナトリウムメトキシド、カリウムメトキシド、リチウムエトキシド、ナトリウムエトキシド、カリウムエトキシド、リチウムイソプロポキシド、ナトリウムイソプロポキシド、カリウムイソプロポキシド、リチウムtert−ブトキシド、ナトリウムtert−ブトキシドまたはカリウムtert−ブトキシドである、請求項1又は請求項2に記載の製造方法。
- アルカリ金属アルコキシドが、リチウムメトキシド、ナトリウムメトキシド、カリウムメトキシド、リチウムエトキシド、ナトリウムエトキシドまたはカリウムエトキシドである、請求項1乃至請求項3の何れかに記載の製造方法。
- α,α−ジフルオロ酢酸エチルを、式[2]:
で表されるルテニウム錯体および塩基の存在下、水素(H2)と反応させ、式[3]:
で表されるα,α−ジフルオロアセトアルデヒドエチルヘミアセタールを製造する方法において、
塩基としてナトリウムエトキシドを用い、該エトキシドの使用量をα,α−ジフルオロ酢酸エチル1モルに対して0.01〜5.0モル、
水素圧を2.0MPa〜6.0MPa(絶対圧)とし、
該反応におけるα,α−ジフルオロ酢酸エステル類の変換率を90%以上で、
かつ、
α,α−ジフルオロ酢酸エチルから生成するα,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドエチルヘミアセタールと、
副生するβ,β−ジフルオロエタノールとの選択率を、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドエチルヘミアセタール:β,β−ジフルオロエタノール=93%以上:7%以下となるように反応させることを特徴とする、
請求項1乃至請求項4の何れかに記載の、α,α−ジフルオロアセトアルデヒドまたはα,α−ジフルオロアセトアルデヒドエチルヘミアセタールの製造方法。
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