CN101125806A - Preparation method for acetophenone - Google Patents
Preparation method for acetophenone Download PDFInfo
- Publication number
- CN101125806A CN101125806A CNA2007100465441A CN200710046544A CN101125806A CN 101125806 A CN101125806 A CN 101125806A CN A2007100465441 A CNA2007100465441 A CN A2007100465441A CN 200710046544 A CN200710046544 A CN 200710046544A CN 101125806 A CN101125806 A CN 101125806A
- Authority
- CN
- China
- Prior art keywords
- alpha
- phenyl ketone
- methyl phenyl
- hypnone
- reactor
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of hypnone, in particular to a method for preparing hypnone by direct photooxidation under the condition with Alpha-vinyltoluene and without catalyst. The invention belongs to the technical field of organic synthesis application. The Alpha-vinyltoluene and acetonitrile with the volume ratio of 1: (0.4 to 100) are put into a light reactor and stirred. The hypnone is prepared after putting through condensed water into a reactor casing and adjusting the flow rate, maintaining reaction temperature to be room temperature, inletting oxygen into the reactor with the flow rate of 2 to 15ml/min, lighting a 125w medium pressure mercury lamp and reacting for 0.5 to 20 hour(s). The method can be used for synthesizing hypnone directly at room temperature without catalysts so as to reduce synthesis cost; furthermore, the method has the advantages of less toxicity and being environment protective.
Description
Technical field
The present invention relates to a kind of preparation method of methyl phenyl ketone, relate in particular to the method that the direct sunshine oxidation under the condition of catalyst-free of a kind of alpha-methyl styrene prepares methyl phenyl ketone, belong to the organic synthesis applied technical field.
Background technology
Methyl phenyl ketone is a kind of organic products commonly used, as important intermediate, can be used for making perfumed soap and cigarette, also can be used as the solvent of ether of cellulose, cellulose ester and resin etc., and the softening agent of plastics etc. has a wide range of applications.
Traditional methyl phenyl ketone synthetic method has multiple.Mainly containing with benzene is raw material, utilizes the Friedel-Crafts homogeneous reaction, as: benzene and diacetyl oxide be synthetic methyl phenyl ketone under Catalyzed by Anhydrous Aluminium Chloride, is raw material with benzene, diacetyl oxide and ethyl acetate perhaps, synthesizes methyl phenyl ketone etc. under Catalyzed by Anhydrous Aluminium Chloride.The method of these synthetic methyl phenyl ketones, toxic side effect is big, and is big to catalyst levels, and product is difficult to be separated.In addition, gas-solid catalysis is arranged, as: benzene and aceticanhydride are the synthetic methyl phenyl ketone of catalyzer with H-ZSM-25 load cerium oxide, perhaps in the methyl benzoate hydrogenation, synthesize methyl phenyl ketone with cerium oxide as hydrogenation catalyst.The system of gas-solid catalysis is had relatively high expectations to catalyst quality, and has the difficult isolating problem of product equally.Alpha-methyl styrene is at NaIO
4, N
2O
4, I
2, HNO
2Deng high price non-metal oxidant or KMnO
4, RuCl
3, OsO
4, TiO
2Deng also oxidable generation methyl phenyl ketone under the high price burning agent effect.Also there is the difficult isolating shortcoming of product in this class reaction product.Alpha-methyl styrene is at high temperature done reaction with ozone also can synthesize methyl phenyl ketone, but its temperature of reaction height, and the cost of ozone raw material is higher.In addition, utilize photochemical reaction also can prepare methyl phenyl ketone, as: alpha-methyl styrene is the synthetic methyl phenyl ketone of oxygenant illumination reaction with oxygen or hydrogen peroxide under the effect of catalyzer, catalyzer mainly contains Cr-HMS, Cr-ZSM-5, Cr-SiO
2, Cr-MCM-41, TiO
2(oxyvanadium compound)-MCM-41 (X type and Y zeolite) equimolecular sieve appendix metal or metal oxide, Resorcinol series, (TPPFe)
2, photosensitizers, AcrH
+, TPT etc.The required Preparation of Catalyst cost of this type of photochemical reaction is higher and the catalyzer repeating utilization factor is low.
Summary of the invention
Purpose of the present invention is providing a kind of reaction conditions gentleness, and catalyst-free is simple to operate, with low cost, and the preparation method of the higher methyl phenyl ketone of selectivity and productive rate.
At the deficiency that prior art exists, big as toxic side effect, the catalyst preparation process complexity, repeating utilization factor is low, and reaction cost is high.The objective of the invention is to utilize photochemical reaction, is raw material with the alpha-methyl styrene, is light source with the medium pressure mercury lamp, does not use catalyzer, and methyl phenyl ketone is synthesized in the oxidation of room temperature direct sunshine.
Goal of the invention of the present invention can also be achieved through the following technical solutions:
With volume ratio is 1: the alpha-methyl styrene of (0.4～100) and acetonitrile place the photoreactor device, open magnetic stirrer, reactor jacket is connected water of condensation, regulates flow, to keep the constant in room temperature of temperature of reaction, through-current capacity is the oxygen of 2～15ml/min in solution.Open the 125w medium pressure mercury lamp and react, reacted 0.5～12 hour, close the light source stopped reaction.The used photoreactor of the present invention is common photoreactor.Acetonitrile is a solvent
Make interior mark with toluene, product is carried out the GC assay determination.Operation steps is: gets this solution and carries out the GC analysis, and temperature programming control column temperature, condition is as follows: keep 2min under 100 ℃ of temperature, be warming up to 300 ℃ with 20 ℃/min behind the 2min, kept one minute, the vaporizer temperature is 300 ℃, and detector temperature is 300 ℃.Product content calculates with the peak area normalization method.The correction factor of elder generation's assaying reaction thing and product is a solvent with ethanol, and 5 in the standardized solution of preparation alpha-methyl styrene and methyl phenyl ketone is measured, and the ratio that obtains alpha-methyl styrene and methyl phenyl ketone correction factor is 0.85.
Advantage of the present invention is:
1. the present invention adopts photochemical reaction, need not the directly synthetic methyl phenyl ketone of catalyzer room temperature, has reduced synthetic cost.
2. the alpha-methyl styrene photochemical reaction prepares methyl phenyl ketone, and synthetic method is simple, and generated time is short, and is easy to operate, and this synthetic normal-temperature reaction, method are simple, catalyst-free, and selectivity and productive rate are higher, and environmentally friendly.
The used raw material of 3 the present invention is chosen the byproduct alpha-methyl styrene of petrochemical complex, not only obtain easily, and toxicity is less, and is environmentally friendly.
Embodiment
Embodiment 1
The acetonitrile of 0.2ml alpha-methyl styrene and 20ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 2ml/min oxygen, opens the 125w medium pressure mercury lamp, 0.5 hour reaction times, add toluene and do interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 2.79%, and selectivity is 79.68%.
Embodiment 2
The acetonitrile of 1.5ml alpha-methyl styrene and 40ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 2 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 6.44%, and selectivity is 67.89%.
Embodiment 3
The acetonitrile of 1.5ml alpha-methyl styrene and 40ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 3 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 41.63%, and selectivity is 74.49%.
Embodiment 4
The acetonitrile of 1.5ml alpha-methyl styrene and 40ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 4 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 66.74%, and selectivity is 76.42%.
Embodiment 5
The acetonitrile of 1.5ml alpha-methyl styrene and 40ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 5 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 67.70%, and selectivity is 79.49%.
Embodiment 6
The acetonitrile of 1.5ml alpha-methyl styrene and 40ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 12 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 75.94%, and selectivity is 91.79%.
Embodiment 7
The acetonitrile of 3ml alpha-methyl styrene and 60ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, open the 125w medium pressure mercury lamp, in 6 hours reaction times, the toluene of adding is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 73.61%, and selectivity is 90.42%.
Embodiment 8
The acetonitrile of 2.5ml alpha-methyl styrene and 40ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 6 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 63.89%, and selectivity is 79.74%.
Embodiment 9
The acetonitrile of 1.5ml alpha-methyl styrene and 20ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 6 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 58.71%, and selectivity is 76.46%.
Embodiment 10
The acetonitrile of 3.5ml alpha-methyl styrene and 40ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 8ml/min oxygen, opens the 125w medium pressure mercury lamp, 6 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 40.60%, and selectivity is 73.24%.
Embodiment 11
The acetonitrile of 8ml alpha-methyl styrene and 80ml is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 15ml/min oxygen, opens the 125w medium pressure mercury lamp, 6 hours reaction times, the toluene that adds is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 34.58%, and selectivity is 82.16%.
Embodiment 12
The 40ml alpha-methyl styrene is added in the photoreactor device, stir, logical water of condensation, through-current capacity is a 15ml/min oxygen, open the 125w medium pressure mercury lamp, in 6 hours reaction times, the toluene of adding is done interior mark, make GC and analyze, the productive rate of methyl phenyl ketone is 14.58%, and selectivity is 55.16%
Claims (2)
1. the preparation method of a methyl phenyl ketone, it is characterized in that alpha-methyl styrene is placed photoreactor, stir, connect water of condensation in reactor jacket and regulate flow, the maintenance temperature of reaction is a room temperature, with the flow aerating oxygen of 2～15ml/min, opens the 125w medium pressure mercury lamp in reactor, reacted 0.5～12 hour, and got methyl phenyl ketone.
2. the preparation method of a methyl phenyl ketone, it is characterized in that with volume ratio be 1: the alpha-methyl styrene and the acetonitrile of (0.4～100) place photoreactor, stir, connect water of condensation in reactor jacket and regulate flow, the maintenance temperature of reaction is a room temperature, with the flow aerating oxygen of 2～15ml/min, opens the 125w medium pressure mercury lamp in reactor, reacted 0.5～12 hour, and got methyl phenyl ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100465441A CN100522911C (en) | 2007-09-27 | 2007-09-27 | Preparation method for acetophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100465441A CN100522911C (en) | 2007-09-27 | 2007-09-27 | Preparation method for acetophenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101125806A true CN101125806A (en) | 2008-02-20 |
| CN100522911C CN100522911C (en) | 2009-08-05 |
Family
ID=39093958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100465441A Expired - Fee Related CN100522911C (en) | 2007-09-27 | 2007-09-27 | Preparation method for acetophenone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100522911C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983396A (en) * | 2017-12-08 | 2018-05-04 | 哈尔滨师范大学 | The process for catalytic synthesis of acetophenone |
| CN109232208A (en) * | 2018-11-05 | 2019-01-18 | 中国石油化工股份有限公司 | A kind of method that hydrotalcite catalyzed styrene oxide generates acetophenone |
| CN113429272A (en) * | 2021-06-21 | 2021-09-24 | 杭州师范大学 | Aryl aldehyde ketone and synthetic method thereof |
| CN114736088A (en) * | 2022-03-30 | 2022-07-12 | 西安医学院 | Method for oxidative cracking of olefin into ketone by photocatalysis |
| CN116239435A (en) * | 2023-03-17 | 2023-06-09 | 华东师范大学 | Construction method and application of catalyst-free 185nm photochemical reaction system |
| CN116253607A (en) * | 2023-03-17 | 2023-06-13 | 华东师范大学 | Construction method and application of catalyst-free 172nm photochemical reaction system |
-
2007
- 2007-09-27 CN CNB2007100465441A patent/CN100522911C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983396A (en) * | 2017-12-08 | 2018-05-04 | 哈尔滨师范大学 | The process for catalytic synthesis of acetophenone |
| CN109232208A (en) * | 2018-11-05 | 2019-01-18 | 中国石油化工股份有限公司 | A kind of method that hydrotalcite catalyzed styrene oxide generates acetophenone |
| CN113429272A (en) * | 2021-06-21 | 2021-09-24 | 杭州师范大学 | Aryl aldehyde ketone and synthetic method thereof |
| CN114736088A (en) * | 2022-03-30 | 2022-07-12 | 西安医学院 | Method for oxidative cracking of olefin into ketone by photocatalysis |
| CN116239435A (en) * | 2023-03-17 | 2023-06-09 | 华东师范大学 | Construction method and application of catalyst-free 185nm photochemical reaction system |
| CN116253607A (en) * | 2023-03-17 | 2023-06-13 | 华东师范大学 | Construction method and application of catalyst-free 172nm photochemical reaction system |
| CN116239435B (en) * | 2023-03-17 | 2024-07-30 | 华东师范大学 | Construction method and application of catalyst-free 185nm photochemical reaction system |
| CN116253607B (en) * | 2023-03-17 | 2024-07-30 | 华东师范大学 | Construction method and application of catalyst-free 172nm photochemical reaction system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100522911C (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100522911C (en) | Preparation method for acetophenone | |
| Biella et al. | Selectivity control in the oxidation of phenylethane-1, 2-diol with gold catalyst | |
| Selvakumar et al. | Benzylsulfonic acid functionalized mesoporous Zr-TMS catalysts: An efficient and recyclable catalyst for the preparation of coumarin derivatives by Pechmann condensation reaction | |
| Gaspa et al. | Visible light-induced transformation of aldehydes to esters, carboxylic anhydrides and amides | |
| CN106866360B (en) | Method for preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural | |
| WO2007004442A1 (en) | Process for production of substituted cyclopentanone | |
| Liu et al. | Chemical kinetics of hydroxylation of phenol catalyzed by TS-1/diatomite in fixed-bed reactor | |
| Takei et al. | CeO2-supported Pd (II)-on-Au nanoparticle catalyst for aerobic selective α, β-desaturation of carbonyl compounds applicable to cyclohexanones | |
| CN114920908B (en) | Fluorenone-containing organic conjugated polymer and application thereof in synthesis of alpha-ketoester | |
| Shen et al. | Enhanced catalytic performance of porphyrin cobalt (II) in the solvent-free oxidation of cycloalkanes (C5~ C8) with molecular oxygen promoted by porphyrin zinc (II) | |
| CN103787857A (en) | Method for synthesizing cyclohexenone through catalytic oxidation of cyclohexene | |
| CN101497562B (en) | Method for producing light-stability agent benzophenone | |
| CN112062707B (en) | Hydrocarbon bond activation method of nonmetal participating inert alkane | |
| Kurasawa et al. | Bioinspired total synthesis of delitschiapyrone A | |
| CN107353176B (en) | Method for catalytically converting cyano into deuterated methyl, aromatic deuterated methyl compound prepared by method and application of aromatic deuterated methyl compound | |
| CN108191635A (en) | A kind of method that catalysis oxidation prepares gluconic acid | |
| JPWO2005073156A1 (en) | Process for producing optically active hydroxymethylated compounds | |
| CN102060659A (en) | Method for preparing homoallylic alcohol | |
| CN107952459B (en) | Method for synthesizing macrocyclic ketene, catalyst and application thereof | |
| CN111100101B (en) | Catalytic synthesis method of 3-benzofuranone compounds | |
| CN107915610B (en) | Preparation method of cyclopentadecanone | |
| Wang et al. | Synthesis of rare earth metal complexes incorporating amido and enolate mixed ligands: Characterization and reactivity | |
| CN101967102A (en) | Synthesizing method of N,N-diethyl-3,7-dimethyl-(E)-2,6-octadiene-1-amine | |
| CN108264449B (en) | Preparation method of 2, 6-diethyl-4-methylphenol | |
| Kurbah et al. | Supramolecular bimetallic vanadium (V) complex driven by hydrogen bonding and O∙∙∙ O chalcogen bonding interaction: Oxidation of cyclohexane and its application toward CH bond activation |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20130927 |