CN101768033B - Method for reducing carbonyl to methylene by catalytic hydrogenation - Google Patents
Method for reducing carbonyl to methylene by catalytic hydrogenation Download PDFInfo
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- CN101768033B CN101768033B CN2010100113251A CN201010011325A CN101768033B CN 101768033 B CN101768033 B CN 101768033B CN 2010100113251 A CN2010100113251 A CN 2010100113251A CN 201010011325 A CN201010011325 A CN 201010011325A CN 101768033 B CN101768033 B CN 101768033B
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Abstract
The invention relates to a method for reducing carbonyl to methylene by catalytic hydrogenation in which load chitosan schiff base palladium serves as catalyst, oxygen serves as reducing agent and carbonyl can be reduced to methylene by catalytic liquid phase hydrogenation under constant pressure. The invention features mild reaction conditions, high carbonyl conversion rate, solid particle catalyst and has the advantages of no pollution, easy separation of catalyst from product and recoverable capability.
Description
Technical field
The method that to the present invention relates to a kind of catalytic hydrogenating reduction carbonyl be methylene radical particularly take the loading chitosan Schiff-base Palladium as catalyzer, is the method for methylene radical with fragrant carbonyl reduction.
Background technology
The carbonyl direct-reduction is methylene radical, it is a kind of important organic chemical reactions, especially fragrant carbonyl compound, reduction by carbonyl, can produce the chain-like alkyl aromatic compound, and the chain-like alkyl aromatic hydrocarbons industrial important raw material that is a class such as the chain alkyl Phenylsulfonic acid, is the important source material of sanitising agent.The method that contains aromatic ring carbonyl compound hydrogenating reduction methylene radical adopts Clemmensen reduction method and WolffL-Kishner-huang-Minlon reduction usually.Before a kind ofly make catalyzer with zinc amalgam, mercury metal causes severe contamination to environment; Rear a kind of then existing needs high temperature, and corrodibility waits by force not enough.Report is also arranged in recent years to contain Cu-Cr, Fe or Ni catalyzer come catalysis of carbonyl compound hydrogenating reduction methylene radical, but these catalyst activities are lower, and need higher reaction temperatures (200～300 ℃).Palladium-based catalyst is as a kind of important catalytic hydrogenating reduction catalyzer, the catalytic performance of its carbonyl reduction methylene radical is also reported to some extent, utilize Pd-[Rh (cod) Cl such as David report] 2 be catalyzer, catalytic hydrogenating reduction fragrance carbonyl is methylene radical (J.Mol.Catal.A 187 (2002) 277-281), this method catalyzer preparation is complicated, the catalytic reduction selectivity is low, and in hydrogenation process, aromatic ring is also by hydrogenating reduction.
Summary of the invention
The method that to have the purpose of this invention is to provide a kind of catalytic hydrogenating reduction carbonyl be methylene radical, this kind method mild condition, selectivity is good, cost is low, pollution-free.
Purpose of the present invention is achieved through the following technical solutions:
A kind of catalytic hydrogenating reduction carbonyl is the method for methylene radical, comprises the steps:
(1) props up the carbonyl compound that adds solvent, loading chitosan Schiff-base Palladium catalyzer and structure such as general formula I in the test tube at a tool;
(2) prop up the logical hydrogen exhaust of test tube to tool, eliminate the air in the reactor, pass into hydrogen with 10～100ml/min flow velocity again, under 25～100 ℃ of temperature, constant temperature stirring reaction 1～20 hour gets the corresponding alkyl-aromatic compounds of general formula I I;
Described each the raw material consumption of step (1) is 0.3～1ml (loading chitosan Schiff-base Palladium catalyzer of the solvent of the structure of solid 0.2～1g) such as the carbonyl compound of general formula I, 10～100ml and 0.1～1g.
The described solvent of above-mentioned steps (1) is ethanol or methyl alcohol or Virahol.
The carbonyl compound of the described structure of above-mentioned steps (1) such as general formula I wherein R1 is optional aryl without replacing or replacing, and R2 is alkyl or the optional aryl without replacing or replacing of hydrogen, straight chain or branching.
The alkyl of described straight chain or branching comprises saturated with undersaturated, preferable methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, 1-propenyl, 2-propenyl, hexenyl.
Described aryl is phenyl or naphthyl.Substituting group preferable methyl, ethyl, propyl group, hydroxyl, amino, methoxyl group, oxyethyl group, chlorine or the nitro of aryl.
The example of useful fragrant carbonyl compound comprises methyl phenyl ketone, Propiophenone, Tetralone an intermediate of Sertraline, phenyl aldehyde, salicylaldhyde, α-naphthaldehyde, phenylacrolein, 1-acrylophenone, benzophenone.
The preferred silicon dioxide carried Chitosan Schiff-base Palladium catalyzer of used loading chitosan Schiff-base Palladium catalyzer, also can select gac, aluminum oxide, zeolite or integral-filled structure is carrier loaded Chitosan Schiff-base Palladium catalyzer.
Contain palladium 0.1～10% (wt%) in the used supported catalyst, preferred 2～7% (wt%).
The reaction the solvent that uses be lower alcohol such as methyl alcohol, ethanol or Virahol, preferred alcohol.
Temperature of reaction is 25～100 ℃, preferred 30～70 ℃.
The catalytic hydrogenation reaction time is 1～20 hour, preferred 2～10 hours.
With respect to prior art, utilize the loading chitosan Schiff-base Palladium to be catalyzer, catalytic hydrogenating reduction fragrance carbonyl is that the method for methylene radical has the following advantages:
1, reaction conditions is gentle, and selected cleaner production route carries out under the temperature of normal pressure hydrogen atmosphere and 30～70 ℃, and obtaining surprising high carbonyl transformation efficiency and high carbonyl reduction is the selectivity of methylene radical.
2, use hydrogen to be reductive agent, cleaning, pollution-free and cost is low.
3, selected catalyzer is solid particulate, is easy to and product separation.
4, owing to adopt loaded catalyst, greatly reduce the consumption of activeconstituents palladium.
5, operation is simple, easily row.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but protection scope of the present invention is not limited to the scope that embodiment represents.
Used loading chitosan Schiff-base Palladium catalyzer is that silicon-dioxide, gac, aluminum oxide, zeolite or integral-filled structure are carrier loaded Chitosan Schiff-base Palladium catalyzer among the embodiment.Preferentially select silicon dioxide carried Chitosan Schiff-base Palladium catalyzer, the preparation method is as follows: chitosan is added in the acetic acid solution of 1.5% (wt%), the stirring at room dissolving, add carrier, after stirring, regulate pH value to 13 with the Na0H solution of 1mol/L, suction filtration, being washed to pH is 8, use again ethanol, acetone drip washing after, in 60 ℃ of lower vacuum-drying 10h; Add successively again methyl alcohol, glacial acetic acid and aldehyde, preferred salicylic aldehyde, reflux 12 hours is filtered, and it is colourless to be washed till filtrate with methyl alcohol, obtains silicon dioxide carried Chitosan Schiff-base in 60 ℃ of lower vacuum-dryings.According to the silicon dioxide carried Chitosan Schiff-base of mass ratio: palladium salt=10: 1, take by weighing silicon dioxide carried Chitosan Schiff-base and PdCl2, add ethanol, 30 ℃ of back flow reaction 72h, it is colourless to be washed till washing lotion with the ethanol extracting, 50 ℃ in vacuum is dried to constant weight, obtains silicon dioxide carried Chitosan Schiff-base catalyzer.Adjust the mass ratio of silicon dioxide carried Chitosan Schiff-base and palladium salt, can obtain the catalyzer of different palladium content.
Utilizing the method also can prepare gac, aluminum oxide, zeolite or integral-filled structure is carrier loaded Chitosan Schiff-base Palladium catalyzer.Catalyst system therefor all uses with form in small, broken bits, and granularity is lower than 1mm, is preferably 200～400um.
Embodiment 1
The hydrogenation reduction of methyl phenyl ketone props up in vitro at tool and carries out, the silicon dioxide carried Chitosan Schiff-base Palladium catalyzer of 0.5mL methyl phenyl ketone, 15mL alcohol solvent, 0.2g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 10ml/min flow velocity again, be heated to 40 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 5 hours, the transformation efficiency of methyl phenyl ketone and the selectivity of ethylbenzene reach 100%.
Embodiment 2
The hydrogenation reduction of phenyl aldehyde props up in vitro at tool and carries out, the loading chitosan Schiff-base Palladium catalyzer of 0.5mL phenyl aldehyde, 10mL methanol solvate, 0.3g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 60ml/min flow velocity again, be heated to 35 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 5 hours, the transformation efficiency of phenyl aldehyde and the selectivity of toluene reach 100%.
Embodiment 3
The hydrogenation reduction of benzophenone props up in vitro at tool and carries out, the loading chitosan Schiff-base Palladium catalyzer of 0.5g benzophenone, 30mL alcohol solvent, 0.5g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 60ml/min flow velocity again, be heated to 50 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 6 hours, the transformation efficiency of benzophenone and the selectivity of ditane reach 100%.
Embodiment 4
The hydrogenation reduction of aubepine props up in vitro at tool and carries out, the loading chitosan Schiff-base Palladium catalyzer of 0.5mL aubepine, 15mL alcohol solvent, 0.6g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 50ml/min flow velocity again, be heated to 60 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 2 hours, the transformation efficiency of aubepine and the selectivity of p-methyl anisole reach 100%.
Embodiment 5
The hydrogenation reduction of salicylaldhyde props up in vitro at tool and carries out, the loading chitosan Schiff-base Palladium catalyzer of 0.5mL salicylaldhyde, 10mL alcohol solvent, 0.3g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 70ml/min flow velocity again, be heated to 30 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 3 hours, the transformation efficiency of salicylaldhyde and the selectivity of ortho-methyl phenol reach 100%.
Embodiment 6
To N, the hydrogenation reduction of N-dimethylaminobenzaldehyde props up in vitro at tool and carries out, with 0.3gN, the loading chitosan Schiff-base Palladium catalyzer of N-dimethylaminobenzaldehyde, 15mL alcohol solvent, 0.3g adds wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 70ml/min flow velocity again, be heated to 30 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas-chromatography～GC-MS hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 3 hours, to N, the transformation efficiency of N-dimethylaminobenzaldehyde reaches N, N, and the selectivity of 3-Three methyl Benzene reaches 100%.
Embodiment 7
The hydrogenation reduction of α-Tetralone an intermediate of Sertraline props up in vitro at tool and carries out, the loading chitosan Schiff-base Palladium catalyzer of 0.5mL α-Tetralone an intermediate of Sertraline, 10mL isopropanol solvent, 0.8g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 80ml/min flow velocity again, be heated to 60 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 10 hours, the transformation efficiency of α-Tetralone an intermediate of Sertraline reaches 100%, and the selectivity of naphthane reaches 98%.
Embodiment 8
The hydrogenation reduction of adjacent hydroxyl-alpha naphthaldehyde props up in vitro at tool and carries out, the loading chitosan Schiff-base Palladium catalyzer of the adjacent hydroxyl-alpha naphthaldehyde of 0.5mL, 10mL alcohol solvent, 0.5g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 40ml/min flow velocity again, be heated to 100 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 5 hours, the transformation efficiency of adjacent hydroxyl-alpha naphthaldehyde and the selectivity of adjacent methyl-Beta Naphthol 99MIN reach 100%.
Embodiment 9
The hydrogenation reduction of ketone musk of resting in peace props up in vitro at tool and carries out, the rest in peace loading chitosan Schiff-base Palladium catalyzer of ketone musk, 40mL alcohol solvent, 0.6g of 0.6g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 40ml/min flow velocity again, be heated to 50 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.Reacted under these conditions 10 hours, the selectivity of the transformation efficiency of the ketone musk of resting in peace and 1,2-diphenylethane reaches 100%.
Embodiment 10
The hydrogenation reduction of Propiophenone props up in vitro at tool and carries out, the loading chitosan Schiff-base Palladium catalyzer of 0.7mL Propiophenone, 15mL alcohol solvent, 0.2g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 100ml/min flow velocity again, be heated to 45 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 3 hours, the transformation efficiency of Propiophenone and the selectivity of propyl benzene reach 100%.
Embodiment 11
The hydrogenation reduction of methyl phenyl ketone props up in vitro at tool and carries out, the silicon dioxide carried Chitosan Schiff-base Palladium catalyzer of 1mL methyl phenyl ketone, 30mL alcohol solvent, 0.8g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 40ml/min flow velocity again, be heated to 40 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 5 hours, the transformation efficiency of methyl phenyl ketone and the selectivity of ethylbenzene reach 100%.
Embodiment 12
The hydrogenation reduction of methyl phenyl ketone props up in vitro at tool and carries out, the silicon dioxide carried Chitosan Schiff-base Palladium catalyzer of 0.2mL methyl phenyl ketone, 10mL alcohol solvent, 0.2g is added wherein, logical hydrogen, exhaust through replacing continuously, eliminate the air in the test tube after, pass into hydrogen with the 60ml/min flow velocity again, be heated to 40 ℃, follow the tracks of reaction with TLC, question response is cooled to room temperature after finishing, filtering catalyst, dried for standby.With gas chromatograph-mass spectrometer hydrogenation products is carried out qualitative and quantitative analysis.
Reacted under these conditions 5 hours, the transformation efficiency of methyl phenyl ketone and the selectivity of ethylbenzene reach 100%.
Embodiment 13
The method that catalyzer among the embodiment 1 is pressed among the embodiment 1 is used four times continuously, measure respectively transformation efficiency and selectivity at every turn, the results are shown in Table 1, as can be seen from the table, be repeatedly used catalyzer after, its active fall is little, but methyl phenyl ketone is reduced to the selectivity of ethylbenzene to descend comparatively obvious, and the selectivity that is reduced to 2 phenylethyl alcohol improves, and namely carbonyl reduction is the elective reduction of methylene radical, and the selectivity that is reduced to hydroxyl strengthens.
Table 1:
| The catalyzer access times | Transformation efficiency (%) | Selectivity (%) |
| For the first time | 100 | 100 |
| For the second time | 100 | 95 |
| For the third time | 100 | 82 |
| The 4th time | 95 | 67 |
Claims (7)
1. the method that the catalytic hydrogenating reduction carbonyl is methylene radical is characterized in that, comprises the steps:
(1) props up the carbonyl compound that adds solvent, loading chitosan Schiff-base Palladium catalyzer and structure such as formula I in the test tube at a tool;
(2) prop up the logical hydrogen exhaust of test tube to tool, eliminate the air in the reactor, pass into hydrogen with 10～100ml/min flow velocity again, under 25～100 ℃ of temperature, constant temperature stirring reaction 1～20 hour gets the corresponding alkyl-aromatic compounds of general formula II;
R wherein
1Be optional aryl without replacing or replacing, R
2Alkyl or optional aryl without replacing or replacing for hydrogen, straight chain or branching; Described loading chitosan Schiff-base Palladium catalyzer is silicon-dioxide, gac, aluminum oxide or zeolite-loaded Chitosan Schiff-base Palladium catalyzer; Described solvent is ethanol, methyl alcohol or Virahol.
2. method claimed in claim 1, it is characterized in that, described each the raw material consumption of step (1) is: the loading chitosan Schiff-base Palladium catalyzer of the solvent of 10～100ml, 0.1～1g and the carbonyl compound of structure such as formula I, consumption 0.3～1ml when described carbonyl compound is liquid, consumption 0.2～1g during for solid.
3. method claimed in claim 1 is characterized in that, the alkyl of described straight chain or branching is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, 1-propenyl, 2-propenyl or hexenyl.
4. method claimed in claim 1 is characterized in that, described aryl is phenyl or naphthyl, and the substituting group of aryl is methyl, ethyl, propyl group, hydroxyl, amino, methoxyl group, oxyethyl group, chlorine or nitro.
5. method claimed in claim 1 is characterized in that, described loading chitosan Schiff-base Palladium catalyzer is silicon dioxide carried Chitosan Schiff-base Palladium catalyzer.
6. claim 1 or 2 described methods is characterized in that, described loading chitosan Schiff-base Palladium catalyzer contains palladium 0.1～10%.
7. method claimed in claim 1 is characterized in that, the constant temperature stirring reaction time is 2～10 hours.
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| CN102432515B (en) * | 2010-11-17 | 2013-08-14 | 江苏恒祥化工有限责任公司 | Preparation technology for N-ethyl pyrrolidine |
| CN106542972B (en) * | 2016-10-30 | 2019-06-14 | 中南民族大学 | A kind of normal temperature and pressure reducing carbonyl is the method for methylene |
| CN111217670B (en) * | 2018-11-25 | 2021-04-09 | 中国科学院大连化学物理研究所 | Method for catalytically reducing carbonyl in compound into methylene |
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Non-Patent Citations (4)
| Title |
|---|
| "壳聚糖负载贵金属催化剂的研究进展";张鹏 等;《化学进展》;20060531;第18卷(第5期);第556-562页 * |
| 孙强 等."二氧化硅负载聚（丙烯腈-乙烯基三乙氧基硅）钯（II）络合物对羰基氢化还原成甲基或亚甲基的催化研究".《合成化学》.1996,第4卷(第2期),第146-150页. |
| 孙强 等."二氧化硅负载聚(丙烯腈-乙烯基三乙氧基硅)钯(II)络合物对羰基氢化还原成甲基或亚甲基的催化研究".《合成化学》.1996,第4卷(第2期),第146-150页. * |
| 张鹏 等."壳聚糖负载贵金属催化剂的研究进展".《化学进展》.2006,第18卷(第5期),第556-562页. |
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