CN101906027A - Method for preparing aldehydes or ketones by alcohol oxidation reaction - Google Patents
Method for preparing aldehydes or ketones by alcohol oxidation reaction Download PDFInfo
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Abstract
The invention belongs to the technical field of chemistry and chemical engineering, and relates to a method for catalytic oxidation of an alcoholic compound by a multi-phase load-type metal catalyst under a mild condition. The method comprises the following step of preparing aldehydes or ketones through a multi-phase catalytic oxidation reaction under a mild condition with or without a solvent by using aromatic primary alcohol, secondary alcohol, aliphatic primary alcohol and secondary alcohol compounds with different substituents as a substrate and using a load-type metal catalyst, molecular oxygen or air as an oxidant. The catalytic system of the invention can overcome various defects existing in a traditional catalyst, has the advantages of presenting favorable catalytic activity under the mild condition or even at a normal temperature, keeping high activity and selectivity after being recycled five times or even being stored for six months, satisfying the economic and environmental-protection requirement, and the like, and has industrial utilization potential.
Description
Technical field:
The invention belongs to technical field of chemistry and chemical engineering, relate to the method that a kind of alcohol oxidation reaction prepares aldehydes or ketones, relate in particular to the method for multiphase load shaped metal catalyzer compounds with catalytic oxidation of alcohol under mild conditions.
Background technology
It is intermediate in the important organic chemical industry's production process of a class that prior art discloses aldehyde, ketone compound, and it is widely used in the synthetic of fine chemical product, is medicine intermediate, chemistry of pesticide product, spices and basic chemical synthetic basis.The alcohol oxidation is the principal reaction of synthetic aldehyde ketone compound.For this reason, can use the oxidizing reaction of metal catalytic of the oxygenant of economic and the toxicological harmless particularly important that in industry, seems.
Known traditional inorganic oxidizer such as permanganate and dichromate all have toxicity, and can produce a large amount of wastes, separate and handle the step that these wastes can increase chemical process, cause serious environmental to pollute.At present, many countries have forbidden at these heavy metal oxygenants of industrial use.Therefore, from the angle of economy and environmental protection, the catalytic oxidation system of seeking high-efficiency cleaning becomes inevitable.
Prior art discloses following effective oxidation system, wherein a kind of be with hypochlorite as oxygenant: disclose a kind of by in the presence of heterogeneous inorganic supported ruthenium catalyst as CN1900041A (right of priority DE102005030728.0), use basic metal or alkaline-earth metal aqueous hypochlorite solution as oxygenant, make primary alconol be oxidized to the method for aldehyde.This catalyst system efficient is very high, but produces a large amount of inorganic wastes.And such catalyst system is mainly better to reactive alcohols (as benzylalcohol) effect, and is lower to the Fatty Alcohol(C12-C14 and C12-C18) activity.In addition, a part of primary alconol is not easy to be controlled at one step of aldehyde and can further be oxidized to the shortcoming that acid also is this system.Another kind mainly is to be the catalytic oxidation system of oxygen source with oxygen or air: proposed with the alumina load ruthenium oxygen activation agent such as carbon supported ruthenium catalyst and dihydro dihydroxy naphthlene coexistence, the process of carrying out pure oxidation among the USA4996007.But in this method, since the active deficiency of ruthenium catalyst, the alcohol conversion that can not obtain wishing, unsatisfactory from the productivity angle of oxide compound.At present, golden catalyst system has received concern for the high reactivity of alcohol oxidation reaction, and Choudhary etc. are at Green Chem, and 2005,7 (11), 768 have reported with the load type nano gold to be catalyzer, with molecular oxygen liquid-phase oxidation phenylcarbinol under 140 ℃ condition.Phenylcarbinol optionally is oxidized to phenyl aldehyde, the yield height, and have only the cruel generation of minor by-products phenylformic acid joint.Enache etc. are at Science, and 2006,311 (5759): 362 have adopted TiO
2With the zeolite as carrier material, find that load type gold and gold are under the alloy condition being phenylcarbinol and the very effective catalyzer of octanol oxidation.But reaction is carried out under high pressure (being higher than 100 ℃) condition mostly in the above-mentioned research, the operational condition harshness, and increase the danger of reacting.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, provide a kind of reaction conditions gentleness, operating procedure is simple, selectivity is high alcohol oxidation reaction to prepare the method for aldehydes or ketones.Relate in particular to the method for multiphase load shaped metal catalyzer compounds with catalytic oxidation of alcohol under mild conditions.
The inventive method comprises: fragrant primary alconol, secondary alcohol and fats primary alconol, secondary alcohol compound with different substituents are substrate, with load type metal catalyst, and molecular oxygen (O
2) or air be oxygenant, multi-phase catalytic oxidation prepares aldehyde, ketone method under the mild conditions.
Alcohol oxidation reaction provided by the invention prepares the method for aldehyde, ketone, is substrate with compound shown in the general formula (II), utilizes load type metal catalyst, is oxygenant with the molecular oxygen, promptly is prepared into corresponding aldehyde, ketone under the mild conditions.
Particularly, the invention provides the method for the aldehyde ketone of preparation general formula (I).
Wherein R1, R2 are hydrogen atom, or replacement or unsubstituted alkyl, and it can be alkyl group, group of naphthene base, aromatic alkyl group, and they have 1～20 carbon atom under situation separately.
Related substituting group is selected from halogen atom, nitro, alkoxyl group, aryloxy; Or replacement or unsubstituted heterocyclic group, it preferably has at least one heteroatoms that is selected from oxygen, nitrogen and sulphur.
Above-mentioned R1, R2 can be identical can be different.
The inventive method uses the compound of general formula (II) to be reaction substrate:
Wherein R1, R2 such as above-mentioned corresponding aldehyde ketone definition generates corresponding aldehyde, ketone with molecular oxygen generation alcohol oxidation in the presence of catalyzer.
Above-mentioned substrate consumption is 0.25～2mmol, is preferably 0.5～1mmol.
Catalyzer involved in the present invention is the metal catalyst of loading type, comprises Au/HAP, Au/CeO
2, Au/TiO
2, Au/Fe
2O
3.Pt/C, Au-Pt/C.The method that its preparation process adopts this area investigator to be familiar with is as hydrothermal method, solid-phase synthesis, sol-gel method, liquid-phase precipitation method.Among the present invention, preferable methods is a liquid-phase precipitation method.
The invention discloses the method that golden presoma loads on hydroxyapatite (HAP), comprise pickling process, deposition coprecipitation method, chemical Vapor deposition process.Among the present invention, the preferred deposition coprecipitation method, wherein precipitation agent is selected from ammoniacal liquor or urea, and preferred precipitation agent is a urea.Can be prepared into Au/HAP thus, the Au charge capacity is 0.5～3wt%.Preferred 0.5～2wt%
Among the present invention, catalyst consumption is controlled at 0.05～0.35g in the reaction process, and preferred scope is 0.1～0.2g.
Oxygenant involved in the present invention is a molecular oxygen, and oxygen source can be that air also can be an oxygen.Molecular oxygen flow control 10～40ml/min in the process.Preferable range 20～30ml/min.
Both can exist under the situation in the invention process process and carry out, also can carry out at solvent-free state at solvent.Solvent comprises toluene, water or phenylfluoroform.Solvent load is 5～30ml.Be preferably 10～15ml.
Among the present invention, preferable reaction temperature is 25 ℃～50 ℃.
In reprocessing cycle, use the ordinary method separate solid, for example by filtering or centrifugation, and washing, dry catalyst.
Catalyst system of the present invention has following outstanding advantage:
1) this catalyst system can be at mild conditions, or even promptly shows good catalytic activity under the normal temperature.
2) this catalyst system not only can use in the condition that solvent exists, and also can use under solvent-free situation, and have the performance that is better than traditional catalyzer.
3) this catalyst system high-selectivity oxidation of not being only applicable to reactive alcohols becomes aldehyde and ketone, and be applicable to Fatty Alcohol(C12-C14 and C12-C18) and alicyclic ring alcohol under mild conditions highly selective be oxidized to aldehyde and ketone.
4) employed catalyzer uses activity and the selectivity that still keeps high in this catalyst system after 5 reprocessing cycle.
5) employed catalyzer can be deposited the activity and the selectivity that still keep high after 6 months in this catalyst system under no particular surroundings protection.
Described above characteristics can overcome all deficiencies that traditional catalyst exists, and satisfy economic environmental protection requirement, and a kind of method that the industrial utilization prospect is arranged is provided.
For the ease of understanding, below will describe in detail of the present invention by specific embodiment.It needs to be noted, specific examples only is in order to illustrate, obviously those of ordinary skill in the art can illustrate according to this paper, within the scope of the invention the present invention is made various corrections and change, and these corrections and change are also included in the scope of the present invention.
Embodiment:
Embodiment 1
Utilizing the hydroxyapatite (HAP) of liquid phase synthesizing method, is precipitation agent with urea, utilizes the presoma (HAuCl of gold
4), with deposition-precipitation method golden nanometer particle is loaded on the HAP, 1.5wt%Au/HAP through the washing, drying, 300 the degree roastings, obtain the 1.5wt%Au/HAP. catalyzer.Add the 150mg catalyzer in three-necked bottle, the 1mmol phenylcarbinol is a solvent with 10ml toluene, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 15 hours under the room temperature condition, obtains phenyl aldehyde, transformation efficiency 99%, selectivity 95%.
Comparison example 1
In three-necked bottle, add 150mg 1.5wt%Au/TiO
2Catalyzer, the 1mmol phenylcarbinol is a solvent with 10ml toluene, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 15 hours under the room temperature condition, obtains phenyl aldehyde, transformation efficiency 53%, selectivity 90%.
Comparison example 2
In three-necked bottle, add 150mg 1.5wt%Ru/Al
2O
3Catalyzer, the 1mmol phenylcarbinol is a solvent with 10ml toluene, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 25 hours under the room temperature condition, obtains phenyl aldehyde, transformation efficiency 77%, selectivity 96%.
Embodiment 2
Preparation of Catalyst such as embodiment 1 add 150mg catalyzer, 0.5mmol hexalin in three-necked bottle, with 10ml toluene is solvent, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 30 hours under the room temperature condition, obtain pimelinketone, transformation efficiency 76%, selectivity 99%.
Embodiment 3
Preparation of Catalyst such as embodiment 1 add 150mg catalyzer, 0.5mmol sec-n-octyl alcohol in three-necked bottle, with 10ml toluene is solvent, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 36 hours under the room temperature condition, obtain methyln-hexyl ketone, transformation efficiency 81%, selectivity 99%.
Embodiment 4
Preparation of Catalyst such as embodiment 1 add 150mg catalyzer, 0.5mmol p-nitrophenyl methyl alcohol in three-necked bottle, with 10ml toluene is solvent, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 48 hours under the room temperature condition, obtain paranitrobenzaldehyde, transformation efficiency 59%, selectivity 99%.
Embodiment 5
Preparation of Catalyst such as embodiment 1 add 150mg catalyzer, 1mmol1-phenylethyl alcohol in three-necked bottle, with 10ml toluene is solvent, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 11.5 hours under the room temperature condition, obtain methyl phenyl ketone, transformation efficiency 99%, selectivity 99%.
Embodiment 6
Preparation of Catalyst such as embodiment 1 add 150mg catalyzer, 1mmol1-phenylethyl alcohol in three-necked bottle, with 10ml toluene is solvent, and air velocity is 20ml/min, and (25 ℃) magnetic agitation is 32 hours under the room temperature condition, obtain methyl phenyl ketone, transformation efficiency 99%, selectivity 99%.
Embodiment 7
Preparation of Catalyst such as embodiment 1 add 150mg catalyzer, 1mmol1-phenylethyl alcohol in three-necked bottle, with the 10ml phenylfluoroform is solvent, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 10 hours under the room temperature condition, obtain methyl phenyl ketone, transformation efficiency 99%, selectivity 99%.
Embodiment 8
Preparation of Catalyst such as embodiment 1 add 150mg catalyzer, 1mmol1-phenylethyl alcohol in three-necked bottle, with the 10ml deionized water is solvent, and oxygen gas flow rate is 20ml/min, 90 ℃ of magnetic agitation of temperature of reaction 2 hours, obtain methyl phenyl ketone, transformation efficiency 96%, selectivity 98%.
Embodiment 9
Preparation of Catalyst such as embodiment 1 add the catalyzer after the 150mg circulation 5 times, the 1mmol1-phenylethyl alcohol in three-necked bottle, with 10ml toluene is solvent, and oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 13 hours under the room temperature condition, obtain methyl phenyl ketone, transformation efficiency 99%, selectivity 99%.
Embodiment 10
Preparation of Catalyst such as embodiment 1; adding 150mg in three-necked bottle does not have under any particular surroundings protection and deposits 6 months catalyzer; the 1mmol1-phenylethyl alcohol; with 10ml toluene is solvent; oxygen gas flow rate is 20ml/min, and (25 ℃) magnetic agitation is 10 hours under the room temperature condition, obtains methyl phenyl ketone; transformation efficiency 87%, selectivity 99%.
Claims (18)
1. an alcohol oxidation reaction prepares the method for aldehydes or ketones, it is characterized in that, fragrant primary alconol, secondary alcohol and fats primary alconol, secondary alcohol compound with different substituents are substrate, with load type metal catalyst, molecular oxygen or air are oxygenant, at solvent or solvent-free state, multi-phase catalytic oxidation prepares aldehydes or ketones under the mild conditions.
2. by the described method of claim 1, it is characterized in that described aldehydes or ketones has the structure of general formula (I),
Wherein R1, R2 are hydrogen atom, or replacement or unsubstituted alkyl, and it is alkyl group, group of naphthene base or aromatic alkyl group, and it has 1～20 carbon atom respectively;
Described substituting group is selected from halogen atom, nitro, alkoxyl group or aryloxy; Or replacement or unsubstituted heterocyclic group, wherein at least one is selected from the heteroatoms of oxygen, nitrogen and sulphur;
Described R1, R2 are identical or different.
3. by claim 1 or 2 described methods, it is characterized in that it is reaction substrate that described method adopts the compound of general formula (II):
Wherein, R1, R2 are hydrogen atom or replacement or unsubstituted alkyl, and it is alkyl group, group of naphthene base or aromatic alkyl group, and it has 1～20 carbon atom respectively; Described substituting group is selected from halogen atom, nitro, alkoxyl group or aryloxy; Or replacement or unsubstituted heterocyclic group, wherein at least one is selected from the heteroatoms of oxygen, nitrogen and sulphur;
Described R1, R2 are identical or different.
4. method according to claim 1 is characterized in that described metal catalyst is the heterogeneous metal catalyzer, and wherein the metal that is comprised is selected from Pd, Pt, Au, Ru, Os, among Co or the Fe one or more.
5. method according to claim 4 is characterized in that described metal is selected from Pd, Ru, Pt or Au.
6. method according to claim 1 is characterized in that, described its carrier of load metal catalyst is selected from Fe
2O
3, SiO
2, Al
2O
3, hydroxyapatite, CeO
2, C or TiO
2
7. method according to claim 6 is characterized in that the metal catalyst of described loading type is selected from Au/HAP, Au/CeO
2, Au/TiO
2, Au/Fe
2O
3, Pt/C or Au-Pt/C.
8. method according to claim 1 is characterized in that, described method adopts hydrothermal method, solid-phase synthesis, sol-gel method or liquid-phase precipitation method.
9. method according to claim 6 is characterized in that, in the described method preparation process, adopts pickling process, and deposition coprecipitation method or chemical Vapor deposition process carry out golden presoma load.
10. method according to claim 6 is characterized in that, in the described method preparation process, adopts the deposition coprecipitation method to carry out golden presoma load.
11. according to the method for claim 9 or 10, wherein depositing coprecipitation method employing ammoniacal liquor or urea is precipitation agent.
12. according to the method for claim 11, wherein said precipitation agent is a urea.
13. the method according to claim 1 is characterized in that, described temperature of reaction is 20 ℃～100 ℃.
14. according to the method for claim 13, wherein said temperature of reaction is 25 ℃～50 ℃.
15. the method according to claim 1 is characterized in that, the pressure of described reaction is normal pressure.
16. the method according to claim 3 is characterized in that, described substrate consumption is 0.5～3mmol; The carrier of described load type nano gold is a hydroxyapatite, and the charge capacity of nanometer gold is 0.5～3wt%; Catalyst consumption is 0.05～0.50g.
17. method according to claim 1 is characterized in that described molecular oxygen oxidation agent, its oxygen source is an air or oxygen, and in the reaction process, the molecular oxygen flow is 10～40ml/min.
18. method according to claim 1 is characterized in that described solvent is selected from toluene, water or phenylfluoroform, solvent load is 5～30ml.
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| CN2009100526726A CN101906027A (en) | 2009-06-05 | 2009-06-05 | Method for preparing aldehydes or ketones by alcohol oxidation reaction |
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| CN103772169A (en) * | 2014-02-12 | 2014-05-07 | 复旦大学 | Method for synthesizing low-impurity content glyoxal through gas phase oxidation |
| WO2014158096A1 (en) * | 2013-03-28 | 2014-10-02 | Agency For Science, Technology And Research | A metal-doped hydroxyapatite catalyst |
| CN104341280A (en) * | 2013-07-25 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde and ketone through alcohol oxidation |
| CN105001065A (en) * | 2015-07-28 | 2015-10-28 | 辽宁石油化工大学 | Method for preparing benzaldehyde through catalyst for benzyl alcohol oxidation |
| CN105152829A (en) * | 2015-09-14 | 2015-12-16 | 扬州大学 | Method for synthesizing ketones from methyl tertiary alcohol |
| CN105983427A (en) * | 2015-01-30 | 2016-10-05 | 中国科学院大连化学物理研究所 | Apatite loaded platinum catalyst as well as preparation method and application thereof |
| CN108083960A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method of alcohol oxidation reaction aldehydes or ketones |
| CN109422632A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of method of catalysis oxidation prenol isoamyl olefine aldehydr |
| CN109836315A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of catalysis preparation method of veratraldehyde |
| CN110078670A (en) * | 2018-10-30 | 2019-08-02 | 北京怡力生物科技有限公司 | A kind of preparation method of environmental-friendly 2- acetyl group benzimidazole |
| CN110075830A (en) * | 2019-04-03 | 2019-08-02 | 河南师范大学 | The method that the immobilized palladium nanocatalyst catalytic phenylmethanol oxidation reaction of nano carbon microsphere prepares benzaldehyde |
| CN111116358A (en) * | 2020-01-15 | 2020-05-08 | 苏州爱玛特生物科技有限公司 | Novel synthesis method of benzene ring polysubstituted compound based on benzoylformic acid |
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| CN111468110A (en) * | 2020-04-21 | 2020-07-31 | 王永芝 | Gas-solid phase reaction double-noble metal catalyst and preparation method thereof |
| CN114405525A (en) * | 2022-01-27 | 2022-04-29 | 河北大学 | Transition metal substituted noble metal hydroxyapatite catalyst and preparation method and application thereof |
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