CN104193600A - Method for preparing aldehyde or ketone from air oxidized alcohol by using aluminum oxide as co-catalyst - Google Patents
Method for preparing aldehyde or ketone from air oxidized alcohol by using aluminum oxide as co-catalyst Download PDFInfo
- Publication number
- CN104193600A CN104193600A CN201410389855.8A CN201410389855A CN104193600A CN 104193600 A CN104193600 A CN 104193600A CN 201410389855 A CN201410389855 A CN 201410389855A CN 104193600 A CN104193600 A CN 104193600A
- Authority
- CN
- China
- Prior art keywords
- aluminum oxide
- promotor
- alcohol
- aldehydes
- ketones
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention provides a novel method for preparing aldehyde or ketone from air oxidized alcohol with high efficiency and high selectivity by using a novel catalytic system which adopts aluminum oxide as a co-catalyst. The method is characterized in that in the absence of a solvent, a nitrogen-containing ligand or alkali, by 3mmol of substrate benzyl alcohol, 2-3mol% of 2,2,6,6-tetramethyl-piperidine-N-oxyl free radical or derivative thereof is used as a main catalyst, 1-2mol% of copper salt and 0.8-1g of aluminum oxide are adopted, the pressure of oxygen or air is 0.1-0.5MPa, the reaction temperature is 20-80 DEG C, the reaction time is 1-24 hours, the conversion rate of the benzyl alcohol is 100 percent, the selectivity of product benzaldehyde is 100 percent, and the yield is 92 percent. The simple catalytic system provided by the invention has the advantages of high activity, low price, simple and feasible operation and mild catalytic reaction condition, and the method is capable of easily separating and recycling aluminum oxide, does not produce pollution, and is easy for industrial production, thus being a method for preparing aldehyde.
Description
Technical field
The present invention relates to a kind of with Al
2o
3, TEMPO and CuBr
2for new catalyst system, efficient highly selective catalytic air oxidation alcohol is prepared the method for aldehyde and ketone, be specifically related to using air or oxygen as oxygenant by the novel method that is oxidized to aldehydes or ketones of the efficient highly selective of alcohol.
Background technology
It is one of functional group's conversion reaction important in organic synthesis that alcohol is optionally oxidized to carbonyl compound, and this class reaction occupies considerable status in fundamental research field and Minute Organic Synthesis.By alcohol, be oxidized to corresponding carbonyl compound in the world every year and surpass 1,000,000 tons, the selective oxidation of alcohols becomes a permanent theme in chemical research field.Oxidation mostly adopts inorganic oxidizer as the DMSO of chromium reagent, manganese reagent, ruthenium reagent, other transition metal oxide and high price iodine reagent, activation etc.Although these oxygenants are feasible in laboratory scope, in actual industrial production process, produce in a large number to the disagreeableness pollutent of environment, and aldehyde is easy to excessively oxidated one-tenth carboxylic acid.Therefore, from environmental friendliness and economic aspect, consider, exploitation has efficient, the highly selective alcohol method for oxidation of application prospect, green non-pollution, substitutes with serious pollution traditional technology, realizes chemical cleaner production, has great academic significance and using value.
In the past few decades, chemists have developed a kind of efficient catalytic system with nitroxyl free radical, representation compound: the catalytic oxidation system with stoichiometric oxygenant of TEMPO (TEMPO) catalysis.From (Marko I E such as Marko in 1996, Science, 1996,274, since CuCl/phen/DBAD 2044-2046.) delivering (tert-butyl azodicarboxylate) heterogeneous system is can be under mild conditions efficient, highly selective catalytic aerobic oxidation primary alconol, secondary alcohol, vinyl carbinol become corresponding aldehydes or ketones with benzylalcohol, the mixture of TEMPO and copper is that the research of catalyst selectivity catalyzed oxidation alcohol becomes the focus that this catalytic field is studied.(Gamez P in the copper complex catalyst system of having reported, Chem. Commun., 2003,2414-2415), dipyridyl, the adjacent phenanthrolines (phen) etc. of adopting containing the title complex of bidentate nitrogen ligands and CuBr2 more, the catalyst system aerobic oxidation phenylcarbinol forming with TEMPO again, show extraordinary catalytic effect, but this oxidation system all carries out and adopts t-BuOK strong basicity additive in organic solvent, and the nitrogenous bitooth ligand price such as dipyridyl, adjacent phenanthroline (phen) is high.Based on above-mentioned analysis, this seminar is devoted to the research of the simple part of development structure and copper complex and the collaborative efficiently catalyzing and oxidizing alcohol of TEMPO always.First find TEMPO/N at home and abroad, the catalyst system of the nitrogenous bitooth ligand of N-dimethyl-ethylenediamine imines class and cupric bromide, is not needing to add under the condition of any alkaline substance, and almost quantitatively catalyzed oxidation benzylalcohol and vinyl carbinol become corresponding aldehyde.This catalyst system has overcome the shortcoming that adds highly basic in former system, have that reaction conditions gentleness, part are simple, product yield advantages of higher (Gengxiu Zheng, Catalysis Communications, 2011,14,92-95), be expected to the Novel aid catalyzer that developing becomes efficient highly selective compounds with catalytic oxidation of alcohol.
In Chinese Patent Application No. 201110047991.5 and 200410003791.X, successfully developed and usingd the TEMPO (TEMPO) of catalytic amount as catalyzer, nitrite tert-butyl (TBN) or NaNO
2respectively and bromine (iodine) or active bromine if the combinations such as N-bromo-succinimide (NBS) are as promotor, with ethyl acetate or methylene dichloride, make reaction solvent, use lower than the oxygen of 0.5MPa or be oxygenant lower than 1.0MPa air, at 0 ~ 100 ℃, can a series of alcohol be oxidized to the technique of aldehydes or ketones by highly selective.Yet embodiment given from above-mentioned patent application can find out, TEMPO/ bromine (or active bromine)/NaNO using
2the feature of the oxidation system of catalytic molecular oxygen and effect: the use of Sodium Nitrite, halogen bromine or active bromine is inconvenient, dangerous, and pressure used is higher, and with an organic solvent.
Summary of the invention
The object of the present invention is to provide a kind of under mild conditions, the alkali-free that the aluminum oxide of take is promotor, solvent-free, without the novel catalyst of containing n-donor ligand, efficient highly selective atmospheric oxidation alcohol is prepared the novel method of aldehydes or ketones.
Provided by the inventionly take the novel catalyst that aluminum oxide is promotor, the atmospheric oxidation alcohol of efficient highly selective is prepared the method for aldehydes or ketones, it is characterized in that: under alkali-free, solvent-free, condition without containing n-donor ligand, take air or oxygen as oxygenant, take aluminum oxide as promotor, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical or 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical derivative, mantoquita are catalyst system, and the oxidation alcohol of efficient highly selective becomes the novel method of aldehydes or ketones; Wherein: the mol ratio of alcohol, TEMPO and derivative thereof, mantoquita is 100:1 ~ 8:1 ~ 3; The pressure of oxygen or air is 0.1 ~ 0.5 MPa; Temperature of reaction is 20 ~ 80 ℃; Reaction times is 1 ~ 24 hour.
Provided by the inventionly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, and described aluminum oxide is selected from alkali alumina, neutral alumina or acidic alumina, preferably neutral alumina.
Provided by the inventionly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, and described mantoquita is selected from vitriol, halide salt or nitrate, preferably cupric bromide.
Provided by the inventionly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, described 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO) derivative is 4-hydroxyl-2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, 4-methoxyl group-2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical or 4-acetamido-2,2, one or more in 6,6-tetramethyl piperidine nitrogen oxygen free radical.TEMPO derivative, is called for short TEMPO.
Provided by the inventionly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, and described alcohol has following structure:
Wherein: R
1for aromatic base or thiazolinyl; R
2for hydrogen or alkyl.
Preferably, R1 is selected from: phenyl, substituted-phenyl, styryl; R2 is selected from: hydrogen.As phenylcarbinol, substituted benzyl alcohol, styryl carbinol.
Method for oxidation:
The mol ratio of phenylcarbinol, TEMPO, mantoquita is 1:0.03:0.02, with air or the oxygen of 0.1 ~ 0.2 MPa, is oxygenant, reacts 1 ~ 24 hour at 20 ~ 80 ℃, can highly selective a series of alcohol be oxidized to aldehyde and ketone.After reaction finishes, by ethyl acetate, organic compound is extracted, difference water and salt water washing organic phase, then use anhydrous magnesium sulfate drying, and then organic phase is carried out to GC analysis, last, then obtain product by the drip washing of 300-400 order silicagel column.
The invention provides and prepare the method for aldehyde and ketone operation is simple, catalyst levels is lower, does not add any solvent, alkali and containing n-donor ligand, adopt safer reagent with lower, aluminum oxide can reuse, and substrate suitability is wide, and convenient product separation, does not produce any refuse.
For achieving the above object, the invention provides a kind of catalytic air or dioxygen oxidation alcohol and prepare the novel method of aldehyde and ketone, by the reaction substrate of 3mmol, 2,2 of 2 ~ 3mol%, 6,6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO) or derivatives thereof, the mantoquita of 1 ~ 2mol%, 0.8 ~ 1 g aluminum oxide, be oxygenant with air or the oxygen of 0.1 ~ 0.2 MPa, at 20 ~ 80 ℃, react 1 ~ 24 hour, efficiently highly selective is oxidized to aldehyde and ketone a series of alcohol.
The high-selectivity oxidation that the present invention is applicable to a series of reactive alcohols becomes aldehyde and ketone; Be applicable to the efficient highly selectives such as fragrant benzylalcohol, assorted fragrant benzylalcohol (containing O, N, the elements such as S), fatty alcohol and alicyclic ring alcohol and be oxidized to corresponding aldehyde and ketone.
The present invention is applicable to the production of the fine chemicals such as medicine intermediate, agrochemicals, spices and chemical aldehyde and ketone.
Tool of the present invention has the following advantages:
(1) catalyst system of the present invention is simple, does not need to add any containing n-donor ligand, solvent and alkali, effectively reduces cost.
(2) aluminum oxide can recycled.
(3) reaction conditions is gentle, and operation is easy to control.Under solvent-free condition, temperature is controlled at normal temperature and just can carries out smoothly.Oxygen pressure is low, and under 0.1MPa air or oxygen, reaction can be carried out smoothly.Whole process is environmentally friendly, does not have pollution.
(4) phenylcarbinol transformation efficiency is high, and product phenyl aldehyde selectivity is good.
(5) aftertreatment is simple, and product yield is high, applied widely.
Embodiment
Following examples are to further illustrate of the present invention, but the present invention is not limited thereto.
Embodiment 1
In the single port bottle of 100mL, together with the neutral alumina of the TEMPO of magneton, 3mmol phenylcarbinol, 3mol%, 2mol% cupric bromide and 0.8g, drop in single port bottle, by preservative film sealing (preservative film leaves aperture) for bottleneck.The powerful magnetic stirring apparatus that starts single port bottle bottom stirs, and starts timing.After reaction finishes, be extracted with ethyl acetate organism, difference water and salt water washing organic phase, use again anhydrous magnesium sulfate drying, then organic phase is carried out to GC analysis (phenylcarbinol transformation efficiency is 100%, and the selectivity of phenyl aldehyde is 100%), last, by the drip washing of 300-400 order silicagel column, obtain product again, phenyl aldehyde productive rate is 92%.
Embodiment 2
In 100 mL tetrafluoroethylene stainless steel autoclaves, the neutral alumina by the TEMPO of magneton, 3mmol phenylcarbinol, 3mol%, 2mol% cupric bromide and 0.8g, drops in reactor together, passes into oxygen to 0.2MPa, then by its sealing.Start the powerful magnetic stirring apparatus of still outer bottom and stir, adopt external oil bath type of heating, by temperature measuring and controlling instrument, control temperature rise rate and temperature of reaction, after 80 ℃ of design temperatures, start timing; In reaction process, if pressure has decline, i.e. supplemental oxygen.After reaction finishes, be extracted with ethyl acetate organism, difference water and salt water washing organic phase, use again anhydrous magnesium sulfate drying, then organic phase is carried out to GC analysis (phenylcarbinol transformation efficiency is 100%, and the selectivity of phenyl aldehyde is 100%), last, by the drip washing of 300-400 order silicagel column, obtain product again, phenyl aldehyde productive rate is 90%.
Embodiment 3
Working method, with embodiment 2, just changes neutral alumina into the aluminum oxide of using once oxidation reaction, reuses for the second time, and the transformation efficiency of phenylcarbinol is 100%, and the selectivity of phenyl aldehyde is 100%, productive rate 88%.
Embodiment 4
Working method, with embodiment 1, just changes neutral alumina into alkali alumina, and the transformation efficiency of phenylcarbinol is 94%, and the selectivity of phenyl aldehyde is 100%, productive rate 80%.
Embodiment 5
Working method, with embodiment 1, just changes neutral alumina into acidic alumina, and the transformation efficiency of phenylcarbinol is 72%, and the selectivity of phenyl aldehyde is 100%, and productive rate is 69%.
Embodiment 6
Working method, with embodiment 1, just changes phenylcarbinol to methylbenzyl alcohol into, to the transformation efficiency of methylbenzyl alcohol, is 96%, and the selectivity of p-tolyl aldehyde is 100%, productive rate 82%.
Embodiment 7
Working method, with embodiment 1, just changes phenylcarbinol into p-methoxybenzyl alcohol, and the transformation efficiency of p-methoxybenzyl alcohol is 87%, and the selectivity of aubepine is 100%, productive rate 77%.
Embodiment 8
Working method, with embodiment 1, just changes phenylcarbinol into styryl carbinol, and the transformation efficiency of styryl carbinol is 94%, and the selectivity of phenylacrolein is 100%, productive rate 80%.
Embodiment 9
Working method, with embodiment 1, just changes phenylcarbinol to chlorobenzene methanol into, to the selectivity of chlorobenzene methanol, is 92%, and the selectivity of 4-chloro-benzaldehyde is 100%, productive rate 78%.
Embodiment 10
Working method, with embodiment 1, just changes cupric bromide into cupric chloride, and the transformation efficiency of phenylcarbinol is 94%, and the selectivity of phenyl aldehyde is 100%, productive rate 80%.
Embodiment 11
Working method, with embodiment 1, just changes cupric bromide into copper sulfate, and the transformation efficiency of phenylcarbinol is 95%, and the selectivity of phenyl aldehyde is 100%, productive rate 83%.
Embodiment 12
Working method, with embodiment 1, just changes cupric bromide into cupric nitrate, and the transformation efficiency of phenylcarbinol is 88%, and the selectivity of phenyl aldehyde is 100%, productive rate 76%.
Embodiment 13
Working method, with embodiment 1, adds organic solvent acetonitrile, and the transformation efficiency of phenylcarbinol is 99%, and the selectivity of phenyl aldehyde is 100%, productive rate 90%.
Embodiment 14
Working method, with embodiment 11, just changes acetonitrile into methyl alcohol, and the transformation efficiency of phenylcarbinol is 89%, and the selectivity selectivity of phenyl aldehyde is 100%, productive rate 80%.
Embodiment 15
Working method, with embodiment 12, just changes acetonitrile into water, and the transformation efficiency of phenylcarbinol is 85%, and the selectivity of phenyl aldehyde is 100%, productive rate 76%.
Although above-mentioned, the specific embodiment of the present invention is described in conjunction with the embodiments; but be not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various modifications that creative work can make or distortion still in protection scope of the present invention.
Claims (9)
1. the novel catalyst that the aluminum oxide of take is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: under solvent-free, condition without containing n-donor ligand, alkali-free, using air or oxygen as oxygenant, take aluminum oxide as promotor, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical or 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical derivative, mantoquita are catalyst system, and the oxidation alcohol of efficient highly selective becomes aldehydes or ketones; Wherein: the mol ratio of alcohol, TEMPO and derivative thereof, mantoquita is 100:1-8:1 ~ 3; The pressure of oxygen or air is 0.1 ~ 0.5 MPa; Temperature of reaction 20-80 ℃; Reaction times is 1-24 hour.
2. as claimed in claim 1ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: described aluminum oxide is selected from alkali alumina, neutral alumina or acidic alumina.
3. as claimed in claim 2ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: the preferred neutral alumina of described aluminum oxide.
4. as claimed in claim 1ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: described aluminum oxide can be reused 5 times.
5. as claimed in claim 1ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: the described mantoquita as one of promotor is selected from vitriol, halide salt or nitrate.
6. as claimed in claim 5ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: described mantoquita is selected from cupric bromide.
7. as claimed in claim 1ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: described 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical derivative is 4-hydroxyl-2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, 4-methoxyl group-2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, 4-acetamido-2,2, one or more in 6,6-tetramethyl piperidine nitrogen oxygen free radical.
8. as claimed in claim 1ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: described alcohol has following structure: wherein: R1 is aromatic base or thiazolinyl; R2 is hydrogen or alkyl.
9. as claimed in claim 1ly take the novel catalyst that aluminum oxide is promotor, efficient highly selective atmospheric oxidation alcohol becomes the novel method of aldehydes or ketones, it is characterized in that: described alcohol is selected from phenylcarbinol, to chlorobenzene methanol, to methylbenzyl alcohol, p-methoxybenzyl alcohol, styryl carbinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410389855.8A CN104193600B (en) | 2014-08-11 | 2014-08-11 | A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410389855.8A CN104193600B (en) | 2014-08-11 | 2014-08-11 | A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104193600A true CN104193600A (en) | 2014-12-10 |
| CN104193600B CN104193600B (en) | 2016-08-17 |
Family
ID=52079013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410389855.8A Expired - Fee Related CN104193600B (en) | 2014-08-11 | 2014-08-11 | A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104193600B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198843A (en) * | 2015-09-25 | 2015-12-30 | 济南大学 | One-pot synthesizing method of 2-(furan-2-yl)-2-glyoxalic acid |
| CN105837416A (en) * | 2016-04-21 | 2016-08-10 | 荆楚理工学院 | Method for preparing aldehyde or ketone by alcohol selective oxidation under catalysis of copper complex |
| CN107805190A (en) * | 2017-11-07 | 2018-03-16 | 江苏师范大学 | A kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system |
| CN108722490A (en) * | 2018-05-22 | 2018-11-02 | 北京理工大学 | A kind of metal bipyridine salt photochemical catalyst, preparation method and applications |
| CN109232308A (en) * | 2018-09-26 | 2019-01-18 | 河南师范大学 | A method of imines is prepared using copper catalyst catalytic amine and alcohol cross-coupling |
| CN110975936A (en) * | 2019-11-11 | 2020-04-10 | 桂林理工大学 | Copper-based catalytic system for efficiently catalyzing and oxidizing alcohol at room temperature without solvent and method thereof |
| WO2020156238A1 (en) * | 2019-01-29 | 2020-08-06 | 复旦大学 | Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol by using oxygen as oxidant, and application thereof |
| CN113968832A (en) * | 2021-10-19 | 2022-01-25 | 安徽金禾实业股份有限公司 | Preparation method of 2-acetylfuran |
| CN115215737A (en) * | 2022-07-21 | 2022-10-21 | 嘉兴学院 | Method for preparing aldehyde or ketone by selective oxidation of alcohol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307839A (en) * | 2009-02-06 | 2012-01-04 | 赢创德固赛有限责任公司 | Method for producing aldehydes and ketones from primary and secondary alcohols |
-
2014
- 2014-08-11 CN CN201410389855.8A patent/CN104193600B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307839A (en) * | 2009-02-06 | 2012-01-04 | 赢创德固赛有限责任公司 | Method for producing aldehydes and ketones from primary and secondary alcohols |
Non-Patent Citations (1)
| Title |
|---|
| QIUFEN WANG,ET AL.: "Base-free copper-catalyzed aerobic oxidation of benzylic alcohols with N-benzylidene-N,N-dimethylthane-1,2-diamine and TEMPO", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198843A (en) * | 2015-09-25 | 2015-12-30 | 济南大学 | One-pot synthesizing method of 2-(furan-2-yl)-2-glyoxalic acid |
| 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 |
| CN105837416A (en) * | 2016-04-21 | 2016-08-10 | 荆楚理工学院 | Method for preparing aldehyde or ketone by alcohol selective oxidation under catalysis of copper complex |
| 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 |
| CN107805190A (en) * | 2017-11-07 | 2018-03-16 | 江苏师范大学 | A kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system |
| CN108722490B (en) * | 2018-05-22 | 2020-07-10 | 北京理工大学 | Metal-bipyridinium photocatalyst, preparation method and application thereof |
| CN108722490A (en) * | 2018-05-22 | 2018-11-02 | 北京理工大学 | A kind of metal bipyridine salt photochemical catalyst, preparation method and applications |
| CN109232308A (en) * | 2018-09-26 | 2019-01-18 | 河南师范大学 | A method of imines is prepared using copper catalyst catalytic amine and alcohol cross-coupling |
| CN109232308B (en) * | 2018-09-26 | 2022-11-29 | 河南师范大学 | Method for preparing imine by catalyzing amine and alcohol cross coupling by using copper catalyst |
| WO2020156238A1 (en) * | 2019-01-29 | 2020-08-06 | 复旦大学 | Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol by using oxygen as oxidant, and application thereof |
| CN110975936A (en) * | 2019-11-11 | 2020-04-10 | 桂林理工大学 | Copper-based catalytic system for efficiently catalyzing and oxidizing alcohol at room temperature without solvent and method thereof |
| CN110975936B (en) * | 2019-11-11 | 2023-01-03 | 桂林理工大学 | Copper-based catalytic system for efficiently catalyzing and oxidizing alcohol at room temperature without solvent and method thereof |
| CN113968832A (en) * | 2021-10-19 | 2022-01-25 | 安徽金禾实业股份有限公司 | Preparation method of 2-acetylfuran |
| CN113968832B (en) * | 2021-10-19 | 2024-01-09 | 安徽金禾实业股份有限公司 | Preparation method of 2-acetyl furan |
| CN115215737A (en) * | 2022-07-21 | 2022-10-21 | 嘉兴学院 | Method for preparing aldehyde or ketone by selective oxidation of alcohol |
| CN115215737B (en) * | 2022-07-21 | 2023-06-27 | 嘉兴学院 | Method for preparing aldehyde or ketone by alcohol selective oxidation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104193600B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104193600A (en) | Method for preparing aldehyde or ketone from air oxidized alcohol by using aluminum oxide as co-catalyst | |
| Cao et al. | Aerobic oxidation catalysis with stable radicals | |
| Patil et al. | Catalytic methods for imine synthesis | |
| CN101148400A (en) | Method for preparing aldehydes and ketones by using oxygen gas to oxidize alcohols | |
| Ballini et al. | Synthetic procedures for the preparation of nitroalkanes | |
| Huple et al. | Gold‐Catalyzed Oxidative Cycloadditions to Activate a Quinoline Framework | |
| CN105152922A (en) | Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination | |
| CN105061185A (en) | Method for catalytic synthesis of benzoic acid by use of anthraquinone under lighting condition | |
| EP3572394A1 (en) | Visible light catalysed saturated carbon hydrogen bond direct oxidation method | |
| Guan et al. | Practical organic solvent-free Cu (OAc) 2/DMAP/TEMPO-catalyzed aldehyde and imine formation from alcohols under air atmosphere | |
| CN107626349B (en) | Catalyst for preparing benzyl alcohol, benzaldehyde and benzoic acid and method for preparing benzyl alcohol, benzaldehyde and benzoic acid | |
| Ghaffari Khaligh | Recently applications of tert-butyl nitrite in organic synthesis-Part I | |
| CN106866326A (en) | Method for preparing nitrile from primary alcohol | |
| CN101830783B (en) | Method for preparing aldehyde by oxidizing alcohol with oxygen in presence of Schiff-base complex catalyst | |
| CN108503545B (en) | Method for preparing phenylacetate by catalytic oxidation of mandelate | |
| CN104447434A (en) | Method for synthesis of p-carboxybenzene sulfonamide through catalytic oxidation | |
| CN1835800B (en) | Oxidation catalyst | |
| Shakir et al. | A convenient alternative for the selective oxidation of alcohols by silica supported TEMPO using dioxygen as the final oxidant | |
| Le et al. | Synthesis of triphenylpyridines via an oxidative cyclization reaction using Sr-doped LaCoO 3 perovskite as a recyclable heterogeneous catalyst | |
| CN108191619A (en) | A kind of catalysis process of molecular oxygen oxidation alcohol compound aldehyde/ketone | |
| CN107602393B (en) | Method for directly oxidizing benzylic C-H bond into ketone or acid | |
| JP2008534577A (en) | Method for producing p-toluic acid by liquid phase oxidation of p-xylene in water | |
| CN109134538B (en) | Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof | |
| CN104151118B (en) | A kind of alcohol selective oxidation prepares the method for aldehydes or ketones | |
| CN101632941B (en) | Catalyst for preparing aldehydes or ketones by selective oxidation of alcohols with molecular oxygen and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20190811 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |