CN103030557A - Method for generating phenylacetate by acetophenone in one step - Google Patents
Method for generating phenylacetate by acetophenone in one step Download PDFInfo
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- CN103030557A CN103030557A CN2013100073722A CN201310007372A CN103030557A CN 103030557 A CN103030557 A CN 103030557A CN 2013100073722 A CN2013100073722 A CN 2013100073722A CN 201310007372 A CN201310007372 A CN 201310007372A CN 103030557 A CN103030557 A CN 103030557A
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- phenylacetate
- phenyl ketone
- methyl phenyl
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Abstract
The invention relates to a method for preparing phenylacetate by acetophenone through direct oxidation in one step. Acetophenone is used as a raw material, hydrogen peroxide is used as an oxidant, formic acid is used as a solvent, and a copper complex is used as a catalyst. The method for synthesizing phenylacetate in one step is characterized in that the phenylacetate yield is high, the conversion rate and selectivity can reach 100%, the reaction condition is mild, the catalyst is simple to prepare, and the raw material is cheap and obtained easily, so that the method is a green synthetic method which is less in investment consumption, high in yield and simple and feasible.
Description
Technical field
The present invention relates to a kind of method that is generated phenylacetate by one step of methyl phenyl ketone.
Background technology
Phenylacetate also can be used as important fine chemistry industry and medicine intermediate at industrial general intermediate as solvent and organic synthesis.Phenylacetate can obtain hydroxy acetophenone (mixture of o-hydroxyacetophenone and parahydroxyacet-ophenone) through conversion reaction, can be used for treating the diseases such as acute and chronic icterohepatitis, cholecystitis, and o-hydroxyacetophenone wherein is synthetic I
AThe important intermediate of class anti-arrhythmic propafenone hydrochloride (propafenone hydrochloride).
The method of industrial synthesis of acetic acid phenyl ester normally adopts phenol and the reaction of certain density sodium hydroxide to generate sodium phenylate, and then the dropping diacetyl oxide further reacts, and then through a plurality of steps such as washing, neutralization, drying, rectifying, make with about 93% yield.This method can cause the corrosion of equipment owing to using sodium hydroxide solution, causes environmental pollution.Make simultaneously the shortcomings such as utilization ratio reduction of equipment.Another kind method is to be contracted take phosphoric acid as catalyzer and reacted by phenol and diacetyl oxide to prepare phenylacetate, and product yield is 91%.The main raw material diacetyl oxide of these two kinds of methods is raw materials of preparation drugs, has become one of medicine of national restrict sales.The steps such as resulting reaction product all need be washed in addition, alkali cleaning, a large amount of phenolic wastewater of generation is not easy to process, and problem of environmental pollution is outstanding.Also someone improves now, by the contracting of phenol and phenyllacetyl chloride acidylate and and get, reaction is carried out in the aqueous solution of sodium hydroxide, because hydrolysis reaction easily occurs phenyllacetyl chloride, needs the excessive phenyllacetyl chloride of use, even so, the yield of product is also very low.Therefore also have the direct acidylate method of selection to make phenylacetate, just Acetyl Chloride 98Min. and phenol all are toxic, deal with pretty troublesomely, and problem of environmental pollution is outstanding.The ionic liquid that Li Liang skills in 2010 etc. have generated under patent ZL201010154485.1 has proposed with the condition of zwitter-ion at the vitriol oil is as catalyzer, catalysis of phenol and acetic acidreaction generate phenylacetate, high in temperature when just separating, the vitriol oil is easily with organic carbon, and this condition cost is high, and problem of environmental pollution still can't be eliminated.
Under certain catalyzer, produce phenylacetate with suitable oxygenant oxidation step methyl phenyl ketone, have the outstanding advantages such as cost is low, route is short, Atom economy is high, simple to operate, pollution-free.Be considered to be hopeful most the clean preparation method that the fortified phenol legal system is got a kind of Green Chemistry of phenylacetate.The oxygenant that adopts is the Green Oxidant hydrogen peroxide of generally acknowledging.The transformation efficiency of methyl phenyl ketone reaches 100% under catalytic condition, and selectivity also reaches 100%, all generates phenylacetate.And product and catalyst separating convenience, the catalyzer good reproducibility.
Summary of the invention
The objective of the invention is to adopt cheap methyl phenyl ketone is raw material, and the peroxidation agent is oxygenant, provides that a kind of working method is simple, reaction conditions is gentle, a step of with low cost, high conversion and highly selective produces the method for phenylacetate.
As raw material, hydrogen peroxide is as oxygenant with methyl phenyl ketone in the present invention, and metal copper complexes is catalyzer.Solvent is acetonitrile, Isosorbide-5-Nitrae-dioxane, formic acid, acetic acid, uncle's butyric acid, a kind of among the DMSO.Press concentration ratio methyl phenyl ketone: metal copper complexes=20:0.1 ~ 0.3, metal copper complexes: hydrogen peroxide: solvent=0.1:1 ~ 4:110 ~ 150.Under normal pressure, under 20 ~ 70 ° of C conditions, the first reaction in solvent of hydrogen peroxide and copper complex generates active specy, then adds methyl phenyl ketone stirring reaction 0.5 ~ 8h, and then distillation steams solvent, collects the phenylacetate of 190 ° of C ~ 195 ° C cuts.
Metal copper complexes is the preparation process of catalyzer: the 41.16ml methyl ethyl diketone is dissolved in the single port flask that fills the 50ml dehydrated alcohol, is positioned in the frozen water and cools off; The 13.36ml anhydrous ethylenediamine is dissolved in the 13.5ml dehydrated alcohol, and then cooling slowly dropwise joins in the mentioned solution, generates immediately the yellow-white throw out, and temperature of reaction maintains 2 ~ 5 ℃, stirs, and reacts 1 hour.Room temperature is placed and is spent the night.Reaction soln decompression rotary evaporation is placed and is filtered, yellow crystals toluene and CCl
4Recrystallization twice gets clear crystal Isosorbide-5-Nitrae-N respectively, two (methyl ethyl diketone) quadrol parts of N-, productive rate 70%.2g Cu (CH
3COO)
2H
2O joins in the 500ml flask, puts into 150ml Isosorbide-5-Nitrae-dioxane solution, is warming up to 80 ℃ of dissolvings.Then slowly add 2.5 ~ 4.5g Isosorbide-5-Nitrae-N, two (methyl ethyl diketone) quadrol parts of N-stir, and solution continues to stir immediately by blue purpling look, heats up.Holding temperature about 45 min about 100 ℃ add water 200 ml, and solution is dark purple black, and room temperature was placed after one day, had the needle-like crystal of light cyan to separate out.Filter, successively use sherwood oil, the ether recrystallization gets silver-colored cyan needle-like crystal.
Anal.?Calcd.?For?C
12H
8O
2N
2Cu:?C,?50.4;?H,?6.3;?N,?9.81%.?Found:?C,?49.5;?H,?6.6;?N?9.78%.
In the catalyst system of the present invention, best solvent is formic acid, optimum methyl phenyl ketone is methyl phenyl ketone: copper complex=15:0.1 ~ 0.3 with the ratio of copper complex, and the molar ratio of optimum copper complex and hydrogen peroxide and solvent is copper complex: hydrogen peroxide: solvent=0.1:1 ~ 4:120 ~ 135.Optimum temperature of reaction is 20 ~ 40 ° of C.
The present invention produces phenylacetate with methyl phenyl ketone one step method except have reaction raw materials cheap, be easy to get, process safety, product are easy to separate, generate the advantages such as water, environmental sound behind the hydroperoxidation, also have following outstanding characteristics:
(1) reaction conditions is gentle, just can carry out at normal temperatures;
(2) yield of phenylacetate is high, reaches 100%, the transformation efficiency 100% of methyl phenyl ketone;
(3) preparation method of catalyzer is simple, cost is low;
(4) added solvent and catalyzer are all recyclable in the reaction process, reuse.
The present invention has good economic benefit and considerable prospects for commercial application.
Embodiment
Embodiment 1 gets respectively copper complex 0.11g and is dissolved in 5ml formic acid, Isosorbide-5-Nitrae-dioxane, acetonitrile among the DMSO, then adds hydrogen peroxidase 10 .02ml, react 0.5h at normal temperatures after, add methyl phenyl ketone 0.05ml, reaction 8h.Obtain the transformation efficiency of the yield methyl phenyl ketone of phenylacetate in different solvents, the results are shown in Table one.
Table one different solvents is on the impact of the transformation efficiency of phenylacetate yield methyl phenyl ketone
| Solvent | Formic acid | Isosorbide-5-Nitrae-dioxane | Acetonitrile | DMSO |
| Phenylacetate yield % | 100 | 64 | 79 | 58 |
| Acetophenone conversion % | 100 | 75 | 88 | 70 |
Embodiment 2 gets respectively copper complex 0.11g and is dissolved in the 5ml formic acid, then adds hydrogen peroxidase 10 .02ml, react 0.5h at normal temperatures after, add methyl phenyl ketone 0.05ml and continue reaction, get the solution of different time sections in the reaction process and test.Obtain the transformation efficiency of the yield methyl phenyl ketone of phenylacetate when different time, the results are shown in Table two.
The yield of table two different time phenylacetate in formic acid and the transformation efficiency of methyl phenyl ketone
| Reaction times (h) | 2 | 4 | 6 | 8 |
| Phenylacetate yield % | 34 | 68 | 86 | 100 |
| Acetophenone conversion % | 35 | 68 | 88 | 100 |
Embodiment 3 gets respectively copper complex 0.11g and is dissolved in the 5ml formic acid, then adds hydrogen peroxidase 10 .02 ~ 0.06ml, react 0.5h at normal temperatures after, add methyl phenyl ketone 0.05ml and continue reaction, get the different solution of content of hydrogen peroxide behind the reaction 1h and test.Obtain the transformation efficiency of the yield methyl phenyl ketone of phenylacetate in the different solution of content of hydrogen peroxide, the results are shown in Table three.
The yield of phenylacetate and the transformation efficiency of methyl phenyl ketone in the different solution of table three content of hydrogen peroxide
| Content of hydrogen peroxide (ml) | 0.02 | 0.04 | 0.05 | 0.06 |
| Phenylacetate yield % | 17 | 42 | 61 | 79 |
| Acetophenone conversion % | 19 | 42 | 61 | 79 |
Claims (5)
1. method that is generated phenylacetate by methyl phenyl ketone one step.As raw material, hydrogen peroxide is as oxygenant with methyl phenyl ketone, and metal copper complexes is catalyzer.Solvent is acetonitrile, Isosorbide-5-Nitrae-dioxane, formic acid, acetic acid, uncle's butyric acid, a kind of among the DMSO.Press concentration ratio methyl phenyl ketone: copper complex=15:0.1 ~ 0.3, copper complex: hydrogen peroxide: solvent=0.1:1 ~ 4:110 ~ 150.Under normal pressure, under 20 ~ 70 ° of C conditions, the first reaction in solvent of hydrogen peroxide and copper complex generates active specy, then adds methyl phenyl ketone stirring reaction 0.5 ~ 8h, and then distillation steams solvent, collects the phenylacetate of 190 ° of C ~ 195 ° C cuts.
2. the catalyst system of claim 1 is characterized in that copper complex and hydrogen peroxide make the active catalytic species in solvent, and these species with this understanding can stable existence.
3. method according to claim 1 is characterized in that methyl phenyl ketone: copper complex=15:0.1 ~ 0.3.
4. method according to claim 1 is characterized in that copper complex: hydrogen peroxide: solvent=0.1:1 ~ 4:120 ~ 135.
5. method according to claim 1, its characteristic temperature is at 20 ~ 40 ° of C.
6. method according to claim 1, its feature solvent is formic acid.
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| CN201310007372.2A CN103030557B (en) | 2013-01-09 | 2013-01-09 | Method for generating phenylacetate by acetophenone in one step |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078594A (en) * | 2019-04-19 | 2019-08-02 | 新昌县泰如科技有限公司 | A kind of synthetic method of p-hydroxyphenylethanol |
| CN113582934A (en) * | 2021-08-02 | 2021-11-02 | 昆明理工大学 | Preparation method and application of Pentane metal-free homogeneous catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372458A (en) * | 2008-10-06 | 2009-02-25 | 浙江大学 | Method for synthesizing acylated enamine without catalyst or solvent |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372458A (en) * | 2008-10-06 | 2009-02-25 | 浙江大学 | Method for synthesizing acylated enamine without catalyst or solvent |
Non-Patent Citations (3)
| Title |
|---|
| G. R. CLARK ET AL.: "The colour isomerism and structure of some copper co-ordination compounds. Part XV. The crystal structure of NN-ethylene-bis(acetylacetoneiminato)copper(II) hemihydrate", 《INORG. PHYS. THEOR.》 * |
| 李建梅 等: "芳香酮在过氧甲酸/甲酸体系中的选择性氧化研究", 《中国化学会成立80周年第十六届全国化学热力学和热分析学会会议论文集》 * |
| 李秀荣 等: "Baeyer villiger氧化反应催化体系的研究新进展", 《石油化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078594A (en) * | 2019-04-19 | 2019-08-02 | 新昌县泰如科技有限公司 | A kind of synthetic method of p-hydroxyphenylethanol |
| CN110078594B (en) * | 2019-04-19 | 2022-07-15 | 新昌县泰如科技有限公司 | Synthetic method of p-hydroxyphenylethanol |
| CN113582934A (en) * | 2021-08-02 | 2021-11-02 | 昆明理工大学 | Preparation method and application of Pentane metal-free homogeneous catalyst |
| CN113582934B (en) * | 2021-08-02 | 2024-01-09 | 昆明理工大学 | Preparation method and application of Pentane metal-free homogeneous catalyst |
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