CN100355941C - Out of tank type electrochemical synthesizing method of p-methoxy phenylacetone - Google Patents
Out of tank type electrochemical synthesizing method of p-methoxy phenylacetone Download PDFInfo
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- CN100355941C CN100355941C CNB200510025399XA CN200510025399A CN100355941C CN 100355941 C CN100355941 C CN 100355941C CN B200510025399X A CNB200510025399X A CN B200510025399XA CN 200510025399 A CN200510025399 A CN 200510025399A CN 100355941 C CN100355941 C CN 100355941C
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Abstract
The present invention relates to an external tank electrochemical synthesizing method of p-methoxy phenylacetone, which belongs to the technical field of electrochemistry. In a two chamber electrolytic tank, a platinum wire is used as an anode, a stainless steel sheet is used as a cathode, acetic acid-acetic anhydride is used as a solvent, and potassium acetate is used as supporting electrolyte. At a certain temperature, lead acetate is used as a reactant, electrolysis is carried out in constant current density, and lead tetraacetate is obtained. After the electrolysis ends, the obtained lead tetraacetate is added to anethole. After reactions end, organic products are obtained. The product of the p-methoxy phenylacetone is obtained by sulfuric acid hydrolysis and ether extraction, and the lead acetate obtained after treatment can be recovered and reutilized. The yield of the synthesizing method is from 52 to 62%, and the present invention has the advantages of simply and easily obtained reaction raw materials, low price, green reaction processes, simple, convenient and safe operation, high yield and low cost and is a technological route with a high added value.
Description
Technical field
The present invention relates to a kind of outer formula electrochemical method for synthesizing of groove of p-methoxy phenyl acetone, belong to technical field of electrochemistry.
Background technology
P-methoxy phenyl acetone, molecular formula C
10H
12O
2Boiling point 266-268 ℃, relative density 1.067, it is the important synthetic intermediate of the particularly synthetic Altace Ramipril of agricultural chemicals, medicine, antidepressant drug etc., as being that the 4-methoxyl group-N-methyl-amphetamines of intermediate preparation can be used as central nervous system stimulant when treatment narcolepsy and the depression with it, widely use in Europe now.
Though p-methoxy phenyl acetone is unusual useful as intermediates, in actual industrial production, do not find very satisfied preparation technology so far yet.
1, English Patent No.1119612 uses Peracetic Acid oxidation 1-(4-p-methoxy-phenyl) propylene, oxidation products acidic substance such as ZnCl
2Obtain p-methoxy phenyl acetone after the reaction, shortcoming is low at acid treatment process productive rate, and the raw material peralcohol explodes easily, and operation must be extremely careful.
2, U.S. JACS; 77; 700 (1955) use 4-p-methoxy-phenyl acetonitrile to use the sodium ethylate reaction in ethyl acetate, obtain containing the precursor compound of ethanoyl, and hydrolysis obtains p-methoxy phenyl acetone then; shortcoming is owing to used sodium ethylate; whole reaction system must dewater in strictness, and the productive rate of hydrolysing step is lower, and preparation must add the step of synthesis material 4-p-methoxy-phenyl acetonitrile; synthetic route is long, and operation steps is many.
3, U.S. Pat 4,638,094 utilizes 3-(4-p-methoxy-phenyl) propylene and the reaction of alkyl nitrous acid ester, the compound that in reaction system, adds alcohol, palladium catalyst and amine or copper simultaneously, then to above-mentioned product be hydrolyzed react final product, productive rate is higher, but reaction system is formed complexity, catalyzer costliness.
4, French Patent FR1,450,200 use 4-methoxybenzaldehyde and α-Lv Bingsuan ester to react under the alkaline condition, and product is handled under strong acid condition and obtained p-methoxy phenyl acetone then, and shortcoming is starting material 4-methoxybenzaldehyde and α-Lv Bingsuan ester costliness and is difficult to obtain.
5, U.S. Pat 4,967, and 009 utilizes 2-(4-p-methoxy-phenyl) propylene and iodosobenzen ediacetate to react in Glacial acetic acid obtains p-methoxy phenyl acetone, and shortcoming is that productive rate is low.
At present, do not see the report of the synthetic p-methoxy phenyl acetone of electrochemical method both at home and abroad as yet.
Summary of the invention
The object of the present invention is to provide a kind of outer formula electrochemical method for synthesizing of groove of p-methoxy phenyl acetone.This method has that equipment requirements is simple, raw material is easy to get, process greenization, free from environmental pollution, reaction are carried out at normal temperatures and pressures, and is easy to operate and safe, productive rate is high and the advantage of suitable suitability for industrialized production, is a kind of synthesis route of high added value.
Technical scheme of the present invention is in the two chamber-type electrolyzer, makes anode with platinum filament, and stainless steel substrates is made negative electrode, acetic acid-acetic anhydride is made solvent, and Potassium ethanoate is made supporting electrolyte, at a certain temperature, make reactant with plumbic acetate, the constant current density electrolysis obtains lead tetra-acetate, after stopping electrolysis, the gained lead tetra-acetate is added in the methyl allylphenol, after reaction finishes, obtain organic product, through sulphuric acid hydrolysis, extracted with diethyl ether, obtain product, p-methoxy phenyl acetone.The mineral products plumbic acetate that obtains after the processing can reclaim again and utilize.The productive rate of described synthetic method is 52～62%.
Now describe technical scheme of the present invention in detail.
The outer formula electrochemical method for synthesizing of a kind of groove of p-methoxy phenyl acetone is characterized in that the concrete operations step:
The first step equipment is prepared
Electrolyzer has two Room: anolyte compartment and cathode compartment, the barrier film between two Room are the glass core, and anode is a platinum filament, and negative electrode is a stainless steel substrates;
The preparation of the second one-step electrolysis liquid
The Potassium ethanoate of the acetic acid of 20 parts of weight-acetic anhydride solution, 1～5 part of weight and the plumbic acetate of 1～5 part of weight mix, 80 ℃ were refluxed 6 hours down, get anolyte, inject described anolyte compartment, the Potassium ethanoate of the acetic acid of 20 parts of weight-acetic anhydride solution and 5 parts of weight mixes, 80 ℃ were refluxed 6 hours down, get catholyte, inject described cathode compartment, Potassium ethanoate is a supporting electrolyte, in acetic acid-acetic anhydride solution, the volume ratio of acetic acid and acetic anhydride is 1: 1;
The methyl allylphenol oxidation of the 3rd step
Under normal pressure and 20～60 ℃, the constant current density electrolysis obtains lead tetra-acetate in described anolyte compartment, and current density is 5～15mA/cm
2, stop electrolysis after, under normal pressure and 40～80 ℃, the electrolytic solution that the anolyte compartment is included lead tetra-acetate joins in the methyl allylphenol of 0.4 part of weight, reacts 10～30 hours;
The 4th step sulphuric acid hydrolysis
The reaction in the 3rd step adds entry in the anolyte in described anolyte compartment after finishing, extracted with diethyl ether organic product three times, and the combined ether layer, saturated aqueous solution of sodium bicarbonate washing ether layer is not to there being bubble, and ether is removed in decompression, and the organic product that obtains joins H
2SO
4In the solution, 60～100 ℃ of following hydrolysis 3～10 hours, the add-on of water is 20 parts of weight, the consumption of ether is each 10 parts of weight, H
2SO
4The concentration of solution is 20～60%;
The 5th step aftertreatment
The 4th step was carried out conventional aftertreatment: extracted with diethyl ether organic product three times, combined ether layer after finishing, saturated aqueous solution of sodium bicarbonate washing ether layer is not to there being bubble, and dried over mgso reduces pressure and removes ether, obtain the product of 0.16～0.35 part of weight, p-methoxy phenyl acetone.
In the 3rd step, the oxidizing reaction of methyl allylphenol occurs in outside the groove; In the 4th step, productive rate is 52～62%.
Principle of work of the present invention: in the 3rd step, plumbic acetate generates lead tetra-acetate on anode, and lead tetra-acetate generates acetate compound at groove external oxidation methyl allylphenol.Acetate compound sulphuric acid hydrolysis in the 4th step and the aftertreatment in the 5th step obtain product, p-methoxy phenyl acetone.
Being further characterized in that of technical scheme of the present invention, operation steps also contains the 6th step plumbic acetate and recycles: with the lead acetate water solution decompression evaporate to dryness of the 4th step gained, acetic acid-dissolving of acetic anhydride solution and backflow with 20 parts of weight, can be used as anolyte reuses, in acetic acid-acetic anhydride solution, the volume ratio of acetic acid and acetic anhydride is 1: 1.
Compare with background technology, the invention has the advantages that:
1, reaction raw materials is simple and easy to, low price.
2, adopt electrochemical method, the pollution of toxic compounds to environment avoided in the process greenization.
3, reaction is carried out at normal temperatures and pressures, and is easy to operate and safe.
4, productive rate height, cost is low, is a kind of operational path of high added value.
Embodiment
Now further specify technical scheme of the present invention by embodiment.All embodiment operate according to the operation steps of described synthetic method fully.
Embodiment 1
In second step, 20g acetic acid: the volume ratio of acetic anhydride be 1: 1 acetic acid-: acetic anhydride solvent, 1g Potassium ethanoate are that supporting electrolyte and 5g plumbic acetate mix, 80 ℃ were refluxed 6 hours down, get anolyte, inject described anolyte compartment, 20g acetic acid: the volume ratio of acetic anhydride be 1: 1 acetic acid-: acetic anhydride solvent and 5g Potassium ethanoate are that supporting electrolyte mixes, and 80 ℃ were refluxed 6 hours down, get catholyte, inject described cathode compartment;
In the 3rd step, under 20 ℃, current density is 5mA/cm
2, energising amount 5.4 * 10
-3F, stop electrolysis after, under normal pressure and 40 ℃, the electrolytic solution that the anolyte compartment is included lead tetra-acetate joins in the 0.4g methyl allylphenol, reacts 30 hours;
In the 4th step, 100 ℃ of following hydrolysis 10 hours, the add-on of water is 20g, the consumption of ether is each 10g, H
2SO
4The concentration of solution is 20%;
In the 5th step, obtain product, p-methoxy phenyl acetone 0.224g;
In the 6th step, plumbic acetate is recycled.
In the 5th step, productive rate is 56.1%.
Embodiment 2
In second step, 20g acetic acid: the volume ratio of acetic anhydride be 1: 1 acetic acid-: acetic anhydride solvent, 3g Potassium ethanoate are that supporting electrolyte and 3g plumbic acetate mix, and 80 ℃ were refluxed 6 hours down, anolyte, inject described anolyte compartment, all the other are with second step of embodiment 1;
In the 3rd step, under 40 ℃, current density is 10mA/cm
2, energising amount 5.4 * 10
-3F, stop electrolysis after, under normal pressure and 60 ℃, the electrolytic solution that the anolyte compartment is included lead tetra-acetate joins in the 0.4g methyl allylphenol, reacts 20 hours;
In the 4th step, 80 ℃ of following hydrolysis 7 hours, H
2SO
4The concentration of solution is 40%;
In the 5th step, obtain product, p-methoxy phenyl acetone 0.247g;
In the 6th step, plumbic acetate is recycled.
In the 5th step, productive rate is 61.9%.
Embodiment 3
In second step, 20g acetic acid: the volume ratio of acetic anhydride be 1: 1 acetic acid-: acetic anhydride solvent, 5g Potassium ethanoate are that supporting electrolyte and 1g plumbic acetate mix, and 80 ℃ were refluxed 6 hours down, anolyte, inject described anolyte compartment, all the other are with second step of embodiment 1;
In the 3rd step, under 60 ℃, current density is 15mA/cm
2, energising amount 5.4 * 10
-3F, stop electrolysis after, under normal pressure and 80 ℃, the electrolytic solution that the anolyte compartment is included lead tetra-acetate joins in the 0.4g methyl allylphenol, reacts 10 hours;
In the 4th step, 60 ℃ of following hydrolysis 10 hours, H
2SO
4The concentration of solution is 60%;
In the 5th step, obtain product, p-methoxy phenyl acetone 0.21g;
In the 6th step, plumbic acetate is recycled.
In the 5th step, productive rate is 52.8%.
Claims (2)
1, the outer formula electrochemical method for synthesizing of a kind of groove of p-methoxy phenyl acetone is characterized in that the concrete operations step:
The first step equipment is prepared
Electrolyzer has two Room: anolyte compartment and cathode compartment, the barrier film between two Room are the glass core, and anode is a platinum filament, and negative electrode is a stainless steel substrates;
The preparation of the second one-step electrolysis liquid
The Potassium ethanoate of the acetic acid of 20 parts of weight-acetic anhydride solution, 1～5 part of weight and the plumbic acetate of 1～5 part of weight mix, 80 ℃ were refluxed 6 hours down, get anolyte, inject described anolyte compartment, the Potassium ethanoate of the acetic acid of 20 parts of weight-acetic anhydride solution and 5 parts of weight mixes, 80 ℃ were refluxed 6 hours down, get catholyte, inject described cathode compartment, Potassium ethanoate is a supporting electrolyte, in acetic acid-acetic anhydride solution, the volume ratio of acetic acid and acetic anhydride is 1: 1;
The methyl allylphenol oxidation of the 3rd step
Under normal pressure and 20～60 ℃, the constant current density electrolysis obtains lead tetra-acetate in described anolyte compartment, and current density is 5～15mA/cm
2, stop electrolysis after, under normal pressure and 40～80 ℃, the electrolytic solution that the anolyte compartment is included lead tetra-acetate joins in the methyl allylphenol of 0.4 part of weight, reacts 10～30 hours;
The 4th step sulphuric acid hydrolysis
The reaction in the 3rd step adds entry in the anolyte in described anolyte compartment after finishing, extracted with diethyl ether organic product three times, and the combined ether layer, saturated aqueous solution of sodium bicarbonate washing ether layer is not to there being bubble, and ether is removed in decompression, and the organic product that obtains joins H
2SO
4In the solution, 60～100 ℃ of following hydrolysis 3～10 hours, the add-on of water is 20 parts of weight, the consumption of ether is each 10 parts of weight, H
2SO
4The concentration of solution is 20～60%;
The 5th step aftertreatment
The 4th step was carried out conventional aftertreatment: extracted with diethyl ether organic product three times, combined ether layer after finishing, saturated aqueous solution of sodium bicarbonate washing ether layer is not to there being bubble, and dried over mgso reduces pressure and removes ether, obtain the product of 0.16～0.35 part of weight, p-methoxy phenyl acetone.
2, the outer formula electrochemical method for synthesizing of the groove of p-methoxy phenyl acetone according to claim 1, it is characterized in that, operation steps also contains the 6th step plumbic acetate and recycles: with the lead acetate water solution decompression evaporate to dryness of the 4th step gained, acetic acid-dissolving of acetic anhydride solution and backflow with 20 parts of weight, can be used as anolyte reuses, in acetic acid-acetic anhydride solution, the volume ratio of acetic acid and acetic anhydride is 1: 1.
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| CNB200510025399XA CN100355941C (en) | 2005-04-26 | 2005-04-26 | Out of tank type electrochemical synthesizing method of p-methoxy phenylacetone |
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| CN100355941C true CN100355941C (en) | 2007-12-19 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230893A (en) * | 1979-09-13 | 1980-10-28 | Merck & Co., Inc. | 1,1-Di(4-hydroxy-3-methoxyphenyl)-2-alkoxypropane |
| US4967009A (en) * | 1988-07-08 | 1990-10-30 | Nippon Petrochemicals Co., Ltd. | Method for oxidizing unsaturated aromatic compounds |
-
2005
- 2005-04-26 CN CNB200510025399XA patent/CN100355941C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230893A (en) * | 1979-09-13 | 1980-10-28 | Merck & Co., Inc. | 1,1-Di(4-hydroxy-3-methoxyphenyl)-2-alkoxypropane |
| US4967009A (en) * | 1988-07-08 | 1990-10-30 | Nippon Petrochemicals Co., Ltd. | Method for oxidizing unsaturated aromatic compounds |
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