WO2010004883A1 - エステル類およびラクトン類の実用的な還元方法 - Google Patents
エステル類およびラクトン類の実用的な還元方法 Download PDFInfo
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- WO2010004883A1 WO2010004883A1 PCT/JP2009/061682 JP2009061682W WO2010004883A1 WO 2010004883 A1 WO2010004883 A1 WO 2010004883A1 JP 2009061682 W JP2009061682 W JP 2009061682W WO 2010004883 A1 WO2010004883 A1 WO 2010004883A1
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- transition metal
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- 150000002148 esters Chemical class 0.000 title claims abstract description 42
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
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- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
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- BVDKYMGISZDCIY-UHFFFAOYSA-N 2-phenylbutane-1,4-diol Chemical compound OCCC(CO)C1=CC=CC=C1 BVDKYMGISZDCIY-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
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- 238000011914 asymmetric synthesis Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
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- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
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- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
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- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- BBKPDHOKNRMWQN-UHFFFAOYSA-N nonane-1,4-diol Chemical compound CCCCCC(O)CCCO BBKPDHOKNRMWQN-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 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
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-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
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 125000005297 thienyloxy group Chemical group S1C(=CC=C1)O* 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B31/00—Reduction in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Definitions
- the base is not particularly limited, but alkali metal hydroxides or alkoxides are preferable, and alkali metal alkoxides are more preferable.
- a desired reaction can be efficiently performed by performing the reaction at a higher temperature than the reduction of ketones, epoxides and imides.
- a suitable reaction temperature is 80 to 150 ° C.
- A represents a cyclopentadienyl (Cp) group or a 1,2,3,4,5-pentamethylcyclopentadienyl (Cp * ) group
- M represents Fe, Ru, or Os.
- B represents halogen, carbon monoxide, acetonitrile, phenyl isocyanide or triphenylphosphine
- C represents a nitrogen-nitrogen (NN) or phosphorus-nitrogen (PN) bidentate ligand.
- C in the group 8 (VIII) transition metal complex represented by the general formula [1] represents an NN or PN bidentate ligand.
- P—C 2 —N is preferable, and Ph 2 P (CH 2 ) 2 NH 2 is particularly preferable.
- NN bidentate ligands can be produced by known methods, and many are commercially available. The PN bidentate ligand is described in Aldrichichima ACTA (USA), 2008, Vol. 41, No. 1, p. 15-26 or the like.
- the reaction solvent may be used in an amount of 0.01 L (liter) or more per 1 mol of the ester represented by the general formula [2] or the lactone represented by the general formula [3]. 0.05 to 2L is preferable, and 0.1 to 1.5L is more preferable. When the reaction is carried out at a low substrate concentration, the reaction rate may decrease. In such a case, the reaction rate is improved by using a suitable amount of the reaction solvent.
- the reaction time is not particularly limited, but is usually within 72 hours. However, since it varies depending on the catalyst system, substrate and reaction conditions, analytical means such as gas chromatography, thin layer chromatography, liquid chromatography, nuclear magnetic resonance, etc. It is preferable that the progress of the reaction is followed by the reaction, and the point of time when the raw material has almost disappeared is the end point of the reaction.
- the inside of the reaction vessel was replaced with hydrogen gas five times, the hydrogen pressure was set to 5 MPa, and the mixture was stirred at 100 ° C. for 21 hours. From the gas chromatographic analysis of the reaction completed liquid, the conversion rate and the area percentage of 1,4-nonanediol (GC area%), which was the target product, were 98.8% and 98.1%, respectively.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
一般式[1]
一般式[1]で示される8(VIII)族遷移金属錯体が一般式[6]
一般式[6]で示される8(VIII)族遷移金属錯体が式[7]
塩基の使用量が8(VIII)族遷移金属錯体1モルに対して15から90モルであることを特徴とする、発明1及至発明3の何れか1つに記載のエステル類またはラクトン類の還元方法。
水素ガス(H2)の圧力が3から7MPaであることを特徴とする、発明1及至発明4の何れか1つに記載のエステル類またはラクトン類の還元方法。
反応温度が80から150℃であることを特徴とする、発明1及至発明5の何れか1つに記載のエステル類またはラクトン類の還元方法。
実施例3の実験操作を代表例として下に示す。
実施例8の実験操作を代表例として下に示す。
アルゴン雰囲気下、シュレンク管に、下記式
アルゴン雰囲気下、シュレンク管に、下記式
アルゴン雰囲気下、シュレンク管に、Cp*RuCl(N-C2 *-N)(0.03mmol,0.05eq)、カリウムtert-ブトキシド16.8mg[0.15mmol,5eq(ルテニウム錯体に対する当量)]、イソプロピルアルコール1.5mLとα―フェニル-γ-ブチロラクトン97.3mg[0.6mmol(ラセミ体)]を加え、凍結脱気を3回繰り返した。得られた溶液をカニュラーにより、ガラス製内筒を有するステンレス鋼(SUS)製耐圧反応容器に移した。反応容器内を水素ガスで5回置換し、水素圧を5MPaに設定し、所定の反応温度で所定の反応時間攪拌した。反応終了液の(キラル)ガスクロマトグラフィー分析より、変換率と目的物である2-フェニル-1,4-ブタンジオール(光学活性体)の光学純度を測定した。
アルゴン雰囲気下、シュレンク管に、Cp*RuCl(N-C2-N)(0.01mmol,0.001eq)、ナトリウムメトキシド135mg[2.5mmol,250eq(ルテニウム錯体に対する当量)]、テトラヒドロフラン4.5mLとジフルオロ酢酸エチル1.24g(10mmol)を加え、凍結脱気を3回繰り返した。得られた溶液をカニュラーにより、ガラス製内筒を有するステンレス鋼(SUS)製耐圧反応容器に移した。反応容器内を水素ガスで5回置換し、水素圧を5MPaに設定し、100℃で24時間攪拌した。反応終了液のガスクロマトグラフィー分析より、変換率と目的物である2,2-ジフルオロエタノールの面積百分率(GCエリア%)は、それぞれ66%、100%であった。
Claims (6)
- 一般式[1]
- 塩基の使用量が8(VIII)族遷移金属錯体1モルに対して15から90モルであることを特徴とする、請求項1及至請求項3の何れか1つに記載のエステル類またはラクトン類の還元方法。
- 水素ガス(H2)の圧力が3から7MPaであることを特徴とする、請求項1及至請求項4の何れか1つに記載のエステル類またはラクトン類の還元方法。
- 反応温度が80から150℃であることを特徴とする、請求項1及至請求項5の何れか1つに記載のエステル類またはラクトン類の還元方法。
Priority Applications (3)
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CN200980126654.6A CN102089266B (zh) | 2008-07-08 | 2009-06-26 | 酯类和内酯类的实用的还原方法 |
EP09794329.4A EP2298723A4 (en) | 2008-07-08 | 2009-06-26 | PRACTICAL PROCEDURE FOR REDUCING ESTERS OR LACTONS |
US12/991,073 US8344187B2 (en) | 2008-07-08 | 2009-06-26 | Practical method for reducing esters or lactones |
Applications Claiming Priority (4)
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JP2008177857 | 2008-07-08 | ||
JP2008-177857 | 2008-07-08 | ||
JP2009150401A JP5451209B2 (ja) | 2008-07-08 | 2009-06-25 | エステル類およびラクトン類の実用的な還元方法 |
JP2009-150401 | 2009-06-25 |
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US (1) | US8344187B2 (ja) |
EP (1) | EP2298723A4 (ja) |
JP (1) | JP5451209B2 (ja) |
CN (1) | CN102089266B (ja) |
WO (1) | WO2010004883A1 (ja) |
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CN102365255B (zh) * | 2009-03-31 | 2015-01-07 | 住友化学株式会社 | 醇化合物的制造方法及其催化剂 |
JP5849710B2 (ja) * | 2011-02-03 | 2016-02-03 | セントラル硝子株式会社 | β−フルオロアルコール類の製造方法 |
CN102766024B (zh) * | 2012-08-09 | 2015-08-12 | 西安近代化学研究所 | 二氟乙醇的制备方法 |
JP2014114257A (ja) * | 2012-12-12 | 2014-06-26 | Takasago Internatl Corp | ルテニウムカルボニル錯体を用いたハロゲン置換安息香酸エステルの還元方法 |
CN104829432B (zh) * | 2015-03-18 | 2017-02-01 | 武汉工程大学 | 一种制备氟代醇的方法 |
RU2646222C2 (ru) * | 2016-07-06 | 2018-03-02 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Способ получения 2-[(оксифенил)метил]бутан-1,4-диолов |
CN108610237B (zh) * | 2018-05-29 | 2021-07-23 | 复旦大学 | 一种合成邻苯二甲醇衍生物的方法 |
ES2953133T3 (es) * | 2019-12-17 | 2023-11-08 | Evonik Oxeno Gmbh & Co Kg | Ester trimetílico del ácido 3,3',3''-(ciclohexano-1,2,4-triil)tripropiónico |
CN114250481B (zh) * | 2021-12-03 | 2023-04-07 | 大连理工大学 | 一种苯酞制邻苯二甲醇的电化学合成方法 |
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WO2006106483A1 (en) * | 2005-04-05 | 2006-10-12 | Firmenich Sa | Hydrogenation of esters with ru/bidentate ligands complexes |
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JP2004300131A (ja) * | 2003-03-20 | 2004-10-28 | Mitsubishi Gas Chem Co Inc | エステル類の水素化によりアルコール類を製造する方法 |
JP5388570B2 (ja) | 2005-04-05 | 2014-01-15 | フイルメニツヒ ソシエテ アノニム | Ru/四座配位子錯体を用いたエステルの水素化 |
ATE458712T1 (de) * | 2006-11-27 | 2010-03-15 | Firmenich & Cie | Hydrierung von estern mit ru/bidentat-ligand- komplexen |
US7772445B2 (en) * | 2007-07-06 | 2010-08-10 | Kanata Chemical Technologies Inc. | Ruthenium catalysts for catalytic hydrogenation |
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2009
- 2009-06-25 JP JP2009150401A patent/JP5451209B2/ja not_active Expired - Fee Related
- 2009-06-26 US US12/991,073 patent/US8344187B2/en not_active Expired - Fee Related
- 2009-06-26 WO PCT/JP2009/061682 patent/WO2010004883A1/ja active Application Filing
- 2009-06-26 EP EP09794329.4A patent/EP2298723A4/en not_active Withdrawn
- 2009-06-26 CN CN200980126654.6A patent/CN102089266B/zh not_active Expired - Fee Related
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JP2004509087A (ja) * | 2000-09-13 | 2004-03-25 | フイルメニツヒ ソシエテ アノニム | 接触水素化法 |
WO2005092825A1 (ja) * | 2004-03-29 | 2005-10-06 | Nagoya Industrial Science Research Institute | 光学活性アルコールの製法 |
WO2006106483A1 (en) * | 2005-04-05 | 2006-10-12 | Firmenich Sa | Hydrogenation of esters with ru/bidentate ligands complexes |
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Also Published As
Publication number | Publication date |
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EP2298723A4 (en) | 2015-07-01 |
CN102089266A (zh) | 2011-06-08 |
US20110092747A1 (en) | 2011-04-21 |
CN102089266B (zh) | 2014-05-07 |
JP2010037329A (ja) | 2010-02-18 |
EP2298723A1 (en) | 2011-03-23 |
US8344187B2 (en) | 2013-01-01 |
JP5451209B2 (ja) | 2014-03-26 |
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