CN104193600B - A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide - Google Patents

A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide Download PDF

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CN104193600B
CN104193600B CN201410389855.8A CN201410389855A CN104193600B CN 104193600 B CN104193600 B CN 104193600B CN 201410389855 A CN201410389855 A CN 201410389855A CN 104193600 B CN104193600 B CN 104193600B
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alcohol
aluminium oxide
catalyst
promoter
ketones
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CN104193600A (en
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王秋芬
郑庚修
赵晶晶
杨倩
姜守相
许燕
战付旭
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University of Jinan
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University of Jinan
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A kind of catalyst system and catalyzing with aluminium oxide as promoter, efficient high selectivity air oxidation alcohol becomes the new method of aldehydes or ketones, solvent-free, without containing n-donor ligand, alkali-free under conditions of, based on substrate 3 mmol benzyl alcohol, the 2 of 2 ~ 3 mol%, 2,6,6 tetramethyl piperidine nitrogen oxygen free radicals are major catalyst, 1 ~ 2 mol% mantoquita, the aluminium oxide of 0.8 ~ 1 g, the pressure of oxygen or air is 0.1 ~ 0.5 MPa, reaction temperature is 20 ~ 80 DEG C, and the response time is 1 ~ 24 hour, and the conversion ratio of benzyl alcohol is 100%, product benzaldehyde selectivity is 100%, productivity 92%.The present invention is a kind of simple catalyst system and catalyzing, and this system activity is high, low price, and operation is simple, and catalytic reaction condition is gentle, and aluminium oxide can be easily separated and recycles, and there is not pollution, it is easy to industrialized production, is a kind of good method preparing aldehyde.

Description

A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide
Technical field
The present invention relates to a kind of with Al2O3, TEMPO and CuBr2For new catalyst system and catalyzing, efficient high selective catalysis air oxygen Change the method that alcohol prepares aldehyde and ketone, be specifically related to optionally be oxidized to by alcohol efficiently height as oxidant using air or oxygen The method of aldehydes or ketones.
Background technology
It is one of functional group's conversion reaction important in organic synthesis that alcohol is optionally oxidized to carbonyl compound, this kind of instead Considerable status should be occupied in basic research field and Minute Organic Synthesis.It is oxidized to phase in the world every year by alcohol The carbonyl compound answered is more than million tons, and the selective oxidation of alcohols becomes a permanent theme in chemical research field.Oxygen Change and mostly use inorganic oxidizer such as: chromium reagent, manganese reagent, ruthenium reagent, other transition metal oxide and hypervalent iodine reagent, work The DMSO etc. changed.Although these oxidants are feasible in laboratory scope, but produce a large amount of during actual industrial production Pollutant disagreeableness to environment, and aldehyde is easy to excessively oxidated one-tenth carboxylic acid.Therefore, examine from environmental friendliness and economic aspect Considering, exploitation has the selectivity alcohol method for oxidation efficient, high of application prospect, green non-pollution, substitutes with serious pollution traditional handicraft, Realize chemicals cleaning to produce, there is great academic significance and using value.
In in the past few decades, chemists have been developed for a kind of efficient catalytic system with NO free radical, Representation compound: the catalysis of the oxidant stoichiometrically that 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO) is catalyzed Oxidation system.Deliver from (Marko I E, Science, 1996,274,2044-2046.) such as Marko in 1996 CuCl/phen/DBAD (tert-butyl azodicarboxylate) heterogeneous system can need by selective catalysis the most efficient, high Since oxygen oxidation primary alconol, secondary alcohol, 1-propenol-3 become corresponding aldehydes or ketones with benzylalcohol, TEMPO is catalyst choice with the complex of copper Property catalysis oxidation alcohol research become this catalytic field research focus.(Gamez in the copper complex catalyst system reported P, Chem. Commun., 2003,2414-2415), use bipyridyl, adjacent coffee quinoline (phen) etc. containing bidentate nitrogen ligands more With the coordination compound of CuBr2, then with TEMPO composition catalyst system and catalyzing aerobic oxidation benzyl alcohol, show extraordinary catalysis effect Really, but this oxidation system carries out and uses t-BuOK strong basicity additive the most in organic solvent, and bipyridyl, adjacent coffee quinoline Etc. (phen) nitrogenous bidentate ligand price is high.Based on above-mentioned analysis, this seminar is devoted to the simple part of development structure always With the research that copper complex and TEMPO work in coordination with efficiently catalyzing and oxidizing alcohol.First TEMPO/N, N-dimethyl second is found The nitrogenous bidentate ligand of diamidogen imines and the catalyst system and catalyzing of copper bromide, under conditions of need not add any basic species, almost Quantitatively catalysis oxidation benzylalcohol and 1-propenol-3 become corresponding aldehyde.This catalyst system and catalyzing overcomes the shortcoming adding highly basic in substance system, Have that reaction condition is gentle, part simple, product yield advantages of higher (Gengxiu Zheng, Catalysis Communications, 2011,14,92-95), being expected to open up becomes efficient high selective catalytic oxidation alcohol compound Novel aid catalyst.
In Chinese Patent Application No. 201110047991.5 and 200410003791.X, successfully develop with the 2 of catalytic amount, 2,6,6-tetramethyl piperidine nitrogen oxygen free radicals (TEMPO) are as catalyst, nitrite tert-butyl (TBN) or NaNO2Respectively and bromine The combination such as (iodine) or active bromine such as N-bromo-succinimide (NBS), as promoter, is made with ethyl acetate or dichloromethane Reaction dissolvent, with the oxygen less than 0.5MPa or less than 1.0MPa air be oxidant, can be with highly selective at 0 ~ 100 DEG C The technique that a series of alcohol are oxidized to aldehydes or ketones.But the embodiment gone out given in above-mentioned patent application is it can be seen that made TEMPO/ bromine (or active bromine)/NaNO2The feature of the oxidation system of catalytic molecular oxygen and effect: sodium nitrite, halogen bromine Or active bromine in-convenience in use, dangerous, pressure used is higher, and uses organic solvent.
Summary of the invention
It is an object of the invention to provide one in a mild condition, alkali-free with aluminium oxide as promoter, solvent-free, Without the catalyst system and catalyzing of containing n-donor ligand, the method that aldehydes or ketones prepared by efficient high selectivity air oxidation alcohol.
The catalyst system and catalyzing with aluminium oxide as promoter that the present invention provides, prepared by the highest selective air oxidation alcohol The method of aldehydes or ketones, it is characterised in that: alkali-free, solvent-free, without containing n-donor ligand under conditions of, with air or oxygen for oxidation Agent, with aluminium oxide as promoter, TEMPO, mantoquita are catalyst system and catalyzing, the highest selection Property oxidation alcohol become the new method of aldehydes or ketones;Wherein: alcohol, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, mantoquita mole Ratio is 100:1 ~ 8:1 ~ 3;The pressure of oxygen or air is 0.1 ~ 0.5 MPa;Reaction temperature is 20 ~ 80 DEG C;Response time is 1 ~ 24 hours.
The catalyst system and catalyzing with aluminium oxide as promoter that the present invention provides, efficient high selectivity air oxidation alcohol becomes aldehyde Or the method for ketone, described aluminium oxide is selected from alkali alumina, neutral alumina or acidic alumina, preferably neutral alumina Aluminum.
The catalyst system and catalyzing with aluminium oxide as promoter that the present invention provides, efficient high selectivity air oxidation alcohol becomes aldehyde Or the method for ketone, described mantoquita is selected from sulfate, halide salt or nitrate, preferably copper bromide.
The present invention catalyst system and catalyzing with aluminium oxide as promoter, efficient high selectivity air oxidation alcohol becomes aldehydes or ketones Method, it is characterised in that: described alcohol is selected from benzyl alcohol, to chlorobenzene methanol, to methylbenzyl alcohol, cinnamyl alcohol.
Method for oxidation:
Benzyl alcohol, TEMPO, the mol ratio of mantoquita are 1:0.03:0.02, and air or oxygen with 0.1 ~ 0.2 MPa are Oxidant, reacts 1 ~ 24 hour at 20 ~ 80 DEG C, with highly selective, a series of alcohol can be oxidized to aldehyde and ketone.Reaction terminates After, by ethyl acetate, organic compound is extracted, respectively by water and saline washing organic facies, then be dried with anhydrous magnesium sulfate, so Afterwards organic facies is carried out GC analysis, finally, then obtains product by 300-400 mesh silicagel column drip washing.
The method of aldehyde and ketone is prepared in offer of the present invention, and operation is simple, and catalyst amount is relatively low, be added without any solvent, Alkali and containing n-donor ligand, use safer reagent with lower, and aluminium oxide can reuse, and substrate applicability is wide, and convenient product separation, Do not produce any refuse.
For achieving the above object, the present invention provides a kind of catalytic air or dioxygen oxidation alcohol to prepare the new method of aldehyde and ketone, Based on the reaction substrate of 3mmol, TEMPO (TEMPO) or derivatives thereof of 2 ~ 3mol%, 1 ~ The mantoquita of 2mol%, 0.8 ~ 1 g aluminium oxide, air or oxygen with 0.1 ~ 0.2 MPa are oxidant, anti-at 20 ~ 80 DEG C Answer 1 ~ 24 hour, efficiently highly selective a series of alcohol can be oxidized to aldehyde and ketone.
The present invention is applicable to the high-selectivity oxidation of a series of reactive alcohols and becomes aldehyde and ketone;It is applicable to fragrance benzylalcohol, heteroaryl perfume The efficiently highly selective such as benzylalcohol (containing elements such as O, N, S), fatty alcohol and alicyclic ring alcohol is oxidized to corresponding aldehyde and ketone.
The present invention is applicable to the fine chemicals such as medicine intermediate, agricultural chemicals, spice and chemicals aldehyde and ketone Produce.
Present invention have the advantage that
(1) catalyst system and catalyzing of the present invention is simple, it is not necessary to adds any containing n-donor ligand, solvent and alkali, effectively reduces into This;
(2) aluminium oxide can be with recycled;
(3) reaction condition is gentle, operates easily controllable.In the absence of a solvent, control just can be suitable at room temperature for temperature Profit is carried out.Oxygen pressure is low, and under 0.1MPa air or oxygen, reaction can be smoothed out.Whole process is environmentally friendly, no Exist and pollute;
(4) benzyl alcohol conversion ratio is high, and product benzaldehyde selectivity is good;
(5) post processing is simple, and product yield is high, applied widely.
Detailed description of the invention
Following example are to further illustrate the present invention, but the invention is not limited in this.
Embodiment 1
In the single port bottle of 100mL, by magneton, 3mmol benzyl alcohol, TEMPO, 2mol% copper bromide of 3mol% and 0.8g Neutral alumina put in single port bottle together, by bottleneck preservative film seal (preservative film leaves aperture).Start at the bottom of single port bottle The strength magnetic stirring apparatus in portion is stirred, and starts timing.After reaction terminates, it is extracted with ethyl acetate Organic substance, uses water respectively Washing organic facies with saline, then be dried with anhydrous magnesium sulfate, then organic facies carries out GC analysis, and (benzyl alcohol conversion ratio is 100%, the selectivity of benzaldehyde is 100%), finally, then obtain product by 300-400 mesh silicagel column drip washing, benzaldehyde productivity is 92%。
Embodiment 2
In the 100 mL politef rustless steel autoclaves, by magneton, 3mmol benzyl alcohol, 3mol% TEMPO, 2mol% copper bromide and the neutral alumina of 0.8g, put in reactor together, is passed through oxygen to 0.2MPa, then will It seals.Start still outer bottom strength magnetic stirring apparatus to be stirred, use external oil bath mode of heating, by Temperature Measure Control Instrument control heating rate and reaction temperature, after design temperature 80 DEG C, start timing;In course of reaction, if pressure has decline, i.e. Supplemental oxygen.After reaction terminates, it is extracted with ethyl acetate Organic substance, respectively by water and saline washing organic facies, then uses anhydrous sulfur Acid magnesium is dried, and then organic facies carries out GC analysis (benzyl alcohol conversion ratio is 100%, and the selectivity of benzaldehyde is 100%), After, then obtaining product by 300-400 mesh silicagel column drip washing, benzaldehyde productivity is 90%.
Embodiment 3
Neutral alumina, with embodiment 2, is simply changed into the aluminium oxide having used once oxidation to react, enters by operational approach Row second time recycling, the conversion ratio of benzyl alcohol is 100%, and the selectivity of benzaldehyde is 100%, productivity 88%.
Embodiment 4
Operational approach, with embodiment 1, simply changes neutral alumina into alkali alumina, and the conversion ratio of benzyl alcohol is 94%, The selectivity of benzaldehyde is 100%, productivity 80%.
Embodiment 5
Operational approach, with embodiment 1, simply changes neutral alumina into acidic alumina, and the conversion ratio of benzyl alcohol is 72%, The selectivity of benzaldehyde is 100%, and productivity is 69%.
Embodiment 6
Operational approach with embodiment 1, simply benzyl alcohol is changed into methylbenzyl alcohol, to the conversion ratio of methylbenzyl alcohol be 96%, the selectivity of p-tolyl aldehyde is 100%, productivity 82%.
Embodiment 7
Benzyl alcohol, with embodiment 1, is simply changed into P-methoxybenzyl alcohol, the conversion of P-methoxybenzyl alcohol by operational approach Rate is 87%, and the selectivity of P-methoxybenzal-dehyde is 100%, productivity 77%.
Embodiment 8
Operational approach, with embodiment 1, simply changes benzyl alcohol into cinnamyl alcohol, and the conversion ratio of cinnamyl alcohol is 94%, cinnamic aldehyde Selectivity is 100%, productivity 80%.
Embodiment 9
Benzyl alcohol, with embodiment 1, is simply changed into chlorobenzene methanol by operational approach, and the selectivity to chlorobenzene methanol is 92%, The selectivity of 4-chloro-benzaldehyde is 100%, productivity 78%.
Embodiment 10
Operational approach, with embodiment 1, simply changes copper bromide into copper chloride, and the conversion ratio of benzyl alcohol is 94%, benzaldehyde Selectivity be 100%, productivity 80%.
Embodiment 11
Operational approach, with embodiment 1, simply changes copper bromide into copper sulfate, and the conversion ratio of benzyl alcohol is 95%, benzaldehyde Selectivity be 100%, productivity 83%.
Embodiment 12
Operational approach, with embodiment 1, simply changes copper bromide into copper nitrate, and the conversion ratio of benzyl alcohol is 88%, benzaldehyde Selectivity be 100%, productivity 76%.
Embodiment 13
Operational approach, with embodiment 1, adds organic solvent acetonitrile, and the conversion ratio of benzyl alcohol is 99%, the selection of benzaldehyde Property is 100%, productivity 90%.
Embodiment 14
Operational approach, with embodiment 11, simply changes acetonitrile into methanol, and the conversion ratio of benzyl alcohol is 89%, the choosing of benzaldehyde Selecting Sexual behavior mode is 100%, productivity 80%.
Embodiment 15
Operational approach, with embodiment 12, simply changes acetonitrile into water, and the conversion ratio of benzyl alcohol is 85%, the selection of benzaldehyde Property is 100%, productivity 76%.
The detailed description of the invention of the present invention is described although above-mentioned in conjunction with the embodiments, but not the present invention is protected The restriction of scope, one of ordinary skill in the art should be understood that on the basis of technical scheme, those skilled in the art Need not to pay various amendments or deformation that creative work can make still within protection scope of the present invention.

Claims (5)

1. the catalyst system and catalyzing with aluminium oxide as promoter, efficient high selectivity air oxidation alcohol becomes the side of aldehydes or ketones Method, it is characterised in that: solvent-free, without containing n-donor ligand, alkali-free under conditions of, using air or oxygen as oxidant, with oxygen Change aluminum is promoter, and TEMPO, mantoquita are catalyst system and catalyzing, the highest selective oxidation Alcohol becomes aldehydes or ketones;Wherein: alcohol, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, the mol ratio of mantoquita are 100:1-8:1 ~ 3; The pressure of oxygen or air is 0.1 ~ 0.5MPa;Reaction temperature 20-80 DEG C;Response time 1-24h.
2. the catalyst system and catalyzing with aluminium oxide as promoter as claimed in claim 1, efficient high selectivity air oxidation alcohol becomes Method for aldehydes or ketones, it is characterised in that: described aluminium oxide is selected from alkali alumina, neutral alumina or acidic oxidation Aluminum.
3. the catalyst system and catalyzing with aluminium oxide as promoter as claimed in claim 1, efficient high selectivity air oxidation alcohol becomes Method for aldehydes or ketones, it is characterised in that: described aluminium oxide can reuse 5 times.
4. the catalyst system and catalyzing with aluminium oxide as promoter as claimed in claim 1, efficient high selectivity air oxidation alcohol becomes Method for aldehydes or ketones, it is characterised in that: the described mantoquita as one of promoter is selected from sulfate, halide salt or nitric acid Salt.
5. the catalyst system and catalyzing with aluminium oxide as promoter as claimed in claim 1, efficient high selectivity air oxidation alcohol becomes Method for aldehydes or ketones, it is characterised in that: described alcohol is selected from benzyl alcohol, to chlorobenzene methanol, to methylbenzyl alcohol, cinnamyl alcohol.
CN201410389855.8A 2014-08-11 2014-08-11 A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide Expired - Fee Related CN104193600B (en)

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CN105198843B (en) * 2015-09-25 2018-01-23 济南大学 The One-step Synthesis method of 2 (base of furans 2) 2 Oxoacetic Acids
CN105837416B (en) * 2016-04-21 2018-01-12 荆楚理工学院 A kind of method that copper complex catalyzing alcohols selective oxidation prepares aldehydes or ketones
CN107805190B (en) * 2017-11-07 2020-11-24 江苏师范大学 Method for preparing benzaldehyde by air oxidation of benzyl alcohol without solvent system
CN108722490B (en) * 2018-05-22 2020-07-10 北京理工大学 Metal-bipyridinium photocatalyst, preparation method and application thereof
CN111484404A (en) * 2019-01-29 2020-08-04 复旦大学 Method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidant under catalysis of copper and application

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