CN109836331A - A kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate - Google Patents
A kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate Download PDFInfo
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- CN109836331A CN109836331A CN201711210609.1A CN201711210609A CN109836331A CN 109836331 A CN109836331 A CN 109836331A CN 201711210609 A CN201711210609 A CN 201711210609A CN 109836331 A CN109836331 A CN 109836331A
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- complex
- acetic acid
- iridium
- ethyl acetate
- catalytic hydrogenation
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Abstract
The present invention provides a kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate, belongs to technical field of organic chemistry.The present invention is using acetic acid as raw material, metal iridium complex is the hydrogenation reaction of catalyst, specifically follows the steps below: weighing complex of iridium, acetic acid, using hydrogen as reducing agent, hydrogenation reduction is carried out, wherein the mass ratio of complex of iridium and acetic acid is 0.00001-0.1；Hydrogen Vapor Pressure is 1.0-10.0Mpa；Reaction temperature is 90-150 DEG C, the reaction time are as follows: 0.5-72h.The invention has the benefit that operation is simple, selectivity of product is high and is easily isolated.
Description
Technical field
The invention belongs to technical field of organic chemistry, and in particular to a kind of complex of iridium catalytic hydrogenation acetic acid ethyl acetate
Method.
Background technique
Acetic acid and ethyl acetate are important chemical products, there is important application in Chemical Manufacture.Acetic acid is due to certainly
The hydrogenation reaction activity of body is low, it usually needs more harsh reaction condition.Heterogeneous catalysis such as Ru, Rh, Pt, Pd, Ir, Ni
Or Cu etc. can be catalyzed acetic acid hydrogenation (Green Chem., 2014,16,911；Org.Process Res.Dev.,2014,18,
289), but more harsh reaction condition is needed.The usual reaction condition of homogeneous catalyst is mild, as Goldberg reports one kind
The complex-catalyzed acetic acid hydrogenation ethyl acetate of Ir, reaction temperature are 120 DEG C, and the reaction time is 65 hours, and Hydrogen Vapor Pressure is
2.7MPa, TON have reached 777.
Summary of the invention
For existing acetic acid hydrogenation ethyl acetate, there are problems: heterogeneous catalysis condition is harsh, and reactivity is low；Homogeneously
Catalytic condition is mild, and reactivity needs to be further increased.The present invention provides one kind using high activity complex of iridium as catalyst,
Using hydrogen as reducing agent, the method for acetic acid hydrogenation ethyl acetate.
A kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate, follows the steps below: weighing iridium cooperation
Object and acetic acid, using hydrogen as reducing agent, complex of iridium is catalyst, carries out reduction reaction；Complex of iridium is with quality of acetic acid ratio
0.0001-0.1, Hydrogen Vapor Pressure is 5-100bar；Reaction temperature is 80-150 DEG C；Reaction time are as follows: 0.5-72h.
The structural formula of the complex of iridium cation are as follows:
L is bidentate ligand.
The structural formula of the bidentate ligand L are as follows:R1It is pyridine ring ortho position, the H of meta or para position,
F、Cl、Br、Me、OMe、OH、NH2Or NMe2Substituent group；OrR2It is pyrazole ring ortho position, meta or para position
H、F、Cl、Br、Me、OMe、OH、NH2Or NMe2Substituent group.
The complex of iridium anion are as follows: trifluoromethanesulfonic acid root (OTf), sulfate radical (SO4), tetrafluoroborate (BF4), nitre
Acid group (NO3), hexafluoro-phosphate radical (PF6), two (fluoroform sulphonyl) imines (NTf2), p-methyl benzenesulfonic acid root (OTs), perchloric acid
Root (ClO4), trifluoroacetic acid root (TFA) or acetate (OAc).
The mass ratio of water and acetic acid in acetic acid is 0-0.8.
The invention has the benefit that complex of iridium dosage is low, catalytic activity is high, reduces production cost.Acetic acid product
Ethyl ester and raw acetic acid are easy to be separated by distillation.By-product is water, does not need additional other solvents, environmentally friendly, is reduced
Production cost.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not by embodiment
Limitation, if the person skilled in the art in the field makes some nonessential improvement to the present invention according to aforementioned present invention content
And adjustment, still fall within protection scope of the present invention.
Embodiment 1
Weighing takes anhydrous acetic acid 1.8g, weighs Cp*Ir catalyst 2.0mg, ligand structure are as follows:Yin from
Son is OTf.System Hydrogen Vapor Pressure is 4MPa, and temperature is 120 DEG C, and the reaction time is 48 hours.Using GC-MS analysis
Final product, generation ethyl acetate amount are 185mg.
Embodiment 2
Weighing takes anhydrous acetic acid 1.8g, weighs Cp*Ir catalyst 2.0mg, ligand structure are as follows:Yin from
Son is OTf.System Hydrogen Vapor Pressure is 0.5MPa, and temperature is 120 DEG C, and the reaction time is 72 hours.Using gas phase-mass spectrometry point
Final product is analysed, generation ethyl acetate amount is 10.5mg.
Embodiment 3
Weighing takes anhydrous acetic acid 1.8g, weighs Cp*Ir catalyst 2.0mg, ligand structure are as follows:Yin from
Son is sulfate radical.System Hydrogen Vapor Pressure is 6MPa, and temperature is 120 DEG C, and the reaction time is 72 hours.Using gas phase-mass spectrometry
Final product is analyzed, generation ethyl acetate amount is 220mg.
Embodiment 4
Weighing takes anhydrous acetic acid 1.8g, weighs Cp*Ir catalyst 2.0mg, ligand structure are as follows:Yin from
Son is OTf.System Hydrogen Vapor Pressure is 4MPa, and temperature is 130 DEG C, and the reaction time is 72 hours.Using GC-MS analysis
Final product, generation ethyl acetate amount are 300mg.
Embodiment 5
Weighing takes anhydrous acetic acid 1.8g, weighs Cp*Ir catalyst 2.0mg, ligand structure are as follows:Yin from
Son is sulfate radical.System Hydrogen Vapor Pressure is 4MPa, and temperature is 80 DEG C, and the reaction time is 72 hours.Using gas phase-mass spectrometry point
Final product is analysed, generation ethyl acetate amount is 9mg.
Claims (5)
1. a kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate, it is characterised in that follow the steps below: claiming
Complex of iridium and acetic acid are taken, using hydrogen as reducing agent, complex of iridium is catalyst, carries out reduction reaction；Complex of iridium and acetic acid
Mass ratio is 0.0001-0.1, and Hydrogen Vapor Pressure is 5-100bar；Reaction temperature is 80-150 DEG C；Reaction time are as follows: 0.5-72h.
2. a kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate described in accordance with the claim 1, it is characterised in that:
The structural formula of the complex of iridium cation are as follows:L is bidentate ligand.
3. a kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate according to claim 2, it is characterised in that
The structural formula of the bidentate ligand L are as follows:
R1It is pyridine ring ortho position, H, F, Cl, Br, Me, OMe, OH, NH of meta or para position2Or NMe2Substituent group；R2It is pyrazole ring neighbour
Position, H, F, Cl, Br, Me, OMe, OH, NH of meta or para position2Or NMe2Substituent group.
4. a kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate described in accordance with the claim 1, it is characterised in that:
The complex of iridium anion are as follows: trifluoromethanesulfonic acid root, sulfate radical, tetrafluoroborate, nitrate anion, hexafluoro-phosphate radical, two (trifluoros
Sulfonyl methane) imines, p-methyl benzenesulfonic acid root, perchlorate, trifluoroacetic acid root or acetate.
5. a kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate described in accordance with the claim 1, it is characterised in that:
The mass ratio of water and acetic acid in acetic acid is 0~0.8:1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711210609.1A CN109836331A (en) | 2017-11-28 | 2017-11-28 | A kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate |
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| CN201711210609.1A CN109836331A (en) | 2017-11-28 | 2017-11-28 | A kind of method of complex of iridium catalytic hydrogenation acetic acid ethyl acetate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120010439A1 (en) * | 2010-05-07 | 2012-01-12 | Celanese International Corporation | Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water |
| US20130035516A1 (en) * | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Process for Purifying a Crude Ethanol Product |
| CN105646143A (en) * | 2016-02-23 | 2016-06-08 | 上海华谊（集团）公司 | Method for co-producing ethanol and ethyl acetate from acetic acid |
| CN106810431A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | The method of complex of iridium catalytic hydrogenation 5 hydroxymethyl furfural 1- hydroxyl -2,5- acetyl butyryls |
-
2017
- 2017-11-28 CN CN201711210609.1A patent/CN109836331A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120010439A1 (en) * | 2010-05-07 | 2012-01-12 | Celanese International Corporation | Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water |
| US20130035516A1 (en) * | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Process for Purifying a Crude Ethanol Product |
| CN106810431A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | The method of complex of iridium catalytic hydrogenation 5 hydroxymethyl furfural 1- hydroxyl -2,5- acetyl butyryls |
| CN105646143A (en) * | 2016-02-23 | 2016-06-08 | 上海华谊（集团）公司 | Method for co-producing ethanol and ethyl acetate from acetic acid |
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Application publication date: 20190604 |