CN103553914A - Phenylethyl acetate synthesis method - Google Patents
Phenylethyl acetate synthesis method Download PDFInfo
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- CN103553914A CN103553914A CN201310548335.2A CN201310548335A CN103553914A CN 103553914 A CN103553914 A CN 103553914A CN 201310548335 A CN201310548335 A CN 201310548335A CN 103553914 A CN103553914 A CN 103553914A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/42—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of secondary alcohols or ketones
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a phenylethyl acetate synthesis method which comprises the following steps of enabling benzyl chloride serving as a raw material to react with ethyl acetoacetate under the effect of a catalyst to synthesize benzylacetone; then enabling benzylacetone to react with metachloroperbenzoic acid at room temperature to synthesize phenylethyl acetate; adding acid to a water layer to regulate the pH value to 1-2; crystallizing, filtering and recovering m-chlorobenzoic acid. In the method disclosed by the invention, since benzyl chloride is used as a raw material to synthesize phenylethyl acetate, the cost of the raw material is low, the process is simple, and the product is easy to separate; moreover, heating is not needed in a benzylacetone oxidation process, and recovered m-chlorobenzoic acid can be recycled, thus the energy consumption and production cost can be effectively reduced.
Description
Technical field
The present invention relates to the synthetic method of a kind of synthesis preparation method of spices, particularly a kind of Phenylethyl ethanoate.
Background technology
Phenylethyl ethanoate is the spices that a class has peach fruital, is mainly used in preparing in perfumed soap, daily cosmetics essence, for allocating the odor types such as jasmine, rose, flores aurantii, violet, Tuberose, Flos rosae multiflorae.
The latest result that " aromatotherapy " research obtains shows, high dilution, faint Phenylethyl ethanoate fragrance have calm the nerves, calm, the effect of hypnosis, by E.E.G test, small white mouse " reactivity " experiment etc. has all confirmed this point, therefore, Phenylethyl ethanoate will be expected to more applied aspect " aromatotherapy ", " fragrant health " from now on.
In addition Phenylethyl ethanoate or resin, the fine solvent of ink.
Phenylethyl ethanoate can extract from crude vegetal.Because Phenylethyl ethanoate is natural, exist in Flos micheliae Albae oil and rose oil, complicated component, when extracting from crude vegetal, exists the separated comparatively problem of difficulty.
Also can adopt esterification process synthetic.Phenylethyl ethanoate can be obtained through esterification by acetic acid, diacetyl oxide and phenylethyl alcohol under catalyzer exists.Reaction formula is as follows respectively:
Because the synthetic institute of the esterification process benzene feedstock ethanol price that adopts is higher, acetic anhydride price is also higher and state control is very tight, and acetic acid price is lower, so produce the synthetic route that upper employing acetic acid mostly and phenylethyl alcohol react.Use acetic acid and phenylethyl alcohol heating reflux reaction a few hours under catalyst action, reaction finish by cooling, wash, neutralize, be washed to neutrality, dry after underpressure distillation and obtaining.Because esterification is reversible reaction, yield is not high, so conventionally adopt in reaction and improve yield with excessive acetic acid, after reaction finishes, can produce acid waste water, easily causes environmental problem, must neutralize rear discharge again, consumes again a large amount of alkali, can cause the wasting of resources.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of Phenylethyl ethanoate, not only technological operation is simple for it, and product is easily separated, and can effectively reduce costs and energy consumption.
Its solution is: adopt Benzyl Chloride under catalyst action, to react synthesize benzyl acetone with methyl aceto acetate, then under benzyl acetone and metachloroperbenzoic acid room temperature, react synthesis of acetic acid phenethyl ester.This synthetic method comprises the following steps successively:
1. in reactor, add catalyzer and methyl aceto acetate, be heated with stirring to backflow, drip Benzyl Chloride, back flow reaction 2-6 hour, generates ethyl benzylacetoacetate.After steaming solvent, be chilled to room temperature, add water stirring and dissolving, acid adding is adjusted PH=7, and stratification, separates layer oily matter, and washing, obtains ethyl benzylacetoacetate.
2. in above-mentioned product, add catalyzer, back flow reaction 2-6 hour, has oily matter to generate, and is chilled to 30 ℃ of following acid addings and is adjusted to PH=1-2.Continue reflux 1-4 hour.Normal pressure steams low-boiling-point substance, obtains crude product benzyl acetone.Underpressure distillation, obtains refining benzyl acetone.
3. will refine benzyl acetone, metachloroperbenzoic acid and solvent and add in reactor, room temperature reaction 2-6 hour, is adjusted to PH=7 with alkali, separates oily matter, and washing, steams solvent, refines to obtain Phenylethyl ethanoate.Water layer acid adding is adjusted to PH=1-2, crystallization, filtered and recycled m-chlorobenzoic acid.The m-chlorobenzoic acid reclaiming can be recycled.
Principal reaction is as follows:
Described catalyzer is sodium methylate or methanol solution of sodium methylate or sodium ethylate or alcohol sodium alcohol solution or sodium hydroxide etc.
Described tune pH can be hydrochloric acid or sulfuric acid or phosphoric acid etc. with acid.
Described solvent can be trichloromethane or methylene dichloride or ethylene dichloride etc.
The present invention adopts Benzyl Chloride under catalyst action, to react synthesize benzyl acetone with methyl aceto acetate, then under benzyl acetone and metachloroperbenzoic acid room temperature, reacts synthesis of acetic acid phenethyl ester.Because the present invention adopts Benzyl Chloride, it is raw material synthesis of acetic acid phenethyl ester, it not only selects raw materials cost low, technique is simple, product is easily separated, and in benzyl acetone oxidising process without heating, after m-chlorobenzoic acid reclaims, can return to former metachloroperbenzoic acid producer and recycle, thereby can effectively reduce energy consumption and production cost.
Accompanying drawing explanation
Accompanying drawing is a kind of synthetic method craft schema of Phenylethyl ethanoate.
Embodiment
Below in conjunction with embodiment, describe the specific embodiment of the present invention in detail.
Embodiment 1
In being equipped with the reaction flask of agitator, reflux exchanger, dropping funnel, thermometer, add concentration mass/mass 30% sodium methoxide solution catalyzer 42g, methyl aceto acetate 31g, stirring reaction 15min.Reflux, drips Benzyl Chloride 25.3g, and about 1h adds, and back flow reaction 2h generates ethyl benzylacetoacetate.Be chilled to room temperature, add 100ml water dissolution and stir evenly, concentrated hydrochloric acid is adjusted PH=7, and stratification, separates layer oily matter, and washing, then stratification, obtain product ethyl benzylacetoacetate.
In above-mentioned product, add 60 gram mass concentration 5% sodium hydroxide solutions, make solution be alkalescence, stir lower backflow 2h, have oily matter to generate, be chilled to 40 ℃ and add below concentrated hydrochloric acid to be adjusted to PH=1-2.Continue reflux 1.5h.Normal pressure steams 83 ℃ of following cuts, the cooling rear standing thick reddish-brown oily matter that separates of remainder.By oily matter underpressure distillation, collect the cut of 113-116 ℃ (1.73kpa), obtain 19.2 grams of benzyl acetones, yield 65%.
In 500ml there-necked flask, add 150ml trichloromethane solvent, 15 grams of (content 99%) benzyl acetones, 24.4 grams of (content 85%) metachloroperbenzoic acids, stir lower room temperature reaction 3h, with mass concentration 30% sodium hydroxide solution, be adjusted to neutrality, stratification, separates organic layer, wash 2 times, decompression steams solvent, the 14.7 grams of Phenylethyl ethanoates of re-refining to obtain, yield 90%.Water layer is adjusted PH=3-4 with concentrated hydrochloric acid, standing crystallization, filtered and recycled m-chlorobenzoic acid.The m-chlorobenzoic acid reclaiming can return to former metachloroperbenzoic acid producer and recycle.
Embodiment 2
In being equipped with the reaction flask of agitator, reflux exchanger, dropping funnel, thermometer, add concentration mass/mass 28% sodium methoxide solution catalyzer 45g, methyl aceto acetate 31g, stirring reaction 15min.Reflux, drips Benzyl Chloride 25.3g, and about 1h adds, and back flow reaction 3h generates ethyl benzylacetoacetate.Be chilled to room temperature, add 100ml water dissolution and stir evenly, concentrated hydrochloric acid is adjusted PH=7, and stratification, separates layer oily matter, and washing, then stratification, obtain product ethyl benzylacetoacetate.
In above-mentioned product, add 60 gram mass concentration 5% sodium hydroxide solutions, make solution be alkalescence, stir lower backflow 3h, have oily matter to generate, be chilled to 40 ℃ and add below concentrated hydrochloric acid to be adjusted to PH=1-2.Continue reflux 2h.Normal pressure steams 83 ℃ of following cuts, the cooling rear standing thick reddish-brown oily matter that separates of remainder.By oily matter underpressure distillation, collect the cut of 113-116 ℃ (1.73kpa), obtain 20.1 grams of benzyl acetones, yield 68%.
In 500ml there-necked flask, add 150ml ethylene dichloride solvent, 15 grams of (content 99%) benzyl acetones, 24.4 grams of (content 85%) metachloroperbenzoic acids, stir lower room temperature reaction 3h, with mass concentration 30% sodium hydroxide solution, be adjusted to neutrality, stratification, separates organic layer, wash 2 times, decompression steams solvent, the 15.1 grams of Phenylethyl ethanoates of re-refining to obtain, yield 92%.Water layer is adjusted PH=3-4 with concentrated hydrochloric acid, standing crystallization, filtered and recycled m-chlorobenzoic acid.The m-chlorobenzoic acid reclaiming can return to former metachloroperbenzoic acid producer and recycle.
Claims (4)
1. a synthetic method for Phenylethyl ethanoate, is characterized in that comprising following processing step:
1 >, in reactor, adds catalyzer and methyl aceto acetate, is heated with stirring to backflow, drip Benzyl Chloride, back flow reaction 2-6 hour, generates ethyl benzylacetoacetate, is chilled to room temperature after steaming solvent, add water stirring and dissolving, acid adding is adjusted pH=7, and stratification, separates layer oily matter, washing, obtains ethyl benzylacetoacetate;
2 > add catalyzer in above-mentioned product, and back flow reaction 2-6 hour has oily matter to generate, be chilled to 30 ℃ of following acid addings and be adjusted to PH=1-2, continue reflux 1-4 hour, normal pressure steams low-boiling-point substance, obtain crude product benzyl acetone, underpressure distillation, obtains refining benzyl acetone;
3 > will refine benzyl acetone, metachloroperbenzoic acid and solvent and add in reactor, room temperature reaction 2-6 hour, with alkali, be adjusted to PH=7, separate oily matter, washing, steam solvent, refine to obtain Phenylethyl ethanoate, water layer acid adding is adjusted to PH=1-2, crystallization, filtered and recycled m-chlorobenzoic acid, the m-chlorobenzoic acid of recovery is recycled.
2. the synthetic method of a kind of Phenylethyl ethanoate as claimed in claim 1, is characterized in that described catalyzer is sodium methylate or methanol solution of sodium methylate or sodium ethylate or alcohol sodium alcohol solution or sodium hydroxide.
3. the synthetic method of a kind of Phenylethyl ethanoate as claimed in claim 1, is characterized in that described tune pH value can be hydrochloric acid or sulfuric acid or phosphoric acid with acid.
4. the synthetic method of a kind of Phenylethyl ethanoate as claimed in claim 1, is characterized in that described solvent can be trichloromethane or methylene dichloride or ethylene dichloride.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483290A (en) * | 2019-08-09 | 2019-11-22 | 上海应用技术大学 | A kind of method that copper catalyzes and synthesizes beta-ketoester |
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- 2013-11-08 CN CN201310548335.2A patent/CN103553914A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| 布添垣等: "固体碳酸盐催化烃化反应合成止咳酮的研究(I)", 《暨南大学学报》 * |
| 汪伟亮: "索非那定的合成", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 * |
| 邢其毅等: "《基础有机化学上册》", 30 November 1993 * |
| 邢其毅等: "《基础有机化学下册》", 30 June 1994 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483290A (en) * | 2019-08-09 | 2019-11-22 | 上海应用技术大学 | A kind of method that copper catalyzes and synthesizes beta-ketoester |
| CN110483290B (en) * | 2019-08-09 | 2022-05-31 | 上海应用技术大学 | Method for synthesizing beta-keto ester by copper catalysis |
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Application publication date: 20140205 |