CN1050869A - α, the synthetic method of beta-unsaturated acid - Google Patents
α, the synthetic method of beta-unsaturated acid Download PDFInfo
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- CN1050869A CN1050869A CN 90106186 CN90106186A CN1050869A CN 1050869 A CN1050869 A CN 1050869A CN 90106186 CN90106186 CN 90106186 CN 90106186 A CN90106186 A CN 90106186A CN 1050869 A CN1050869 A CN 1050869A
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Abstract
The present invention is α, the improvement of β-unsaturated acid synthetic method.A kind of aldehyde and a kind of acid are mixed by a certain percentage, add an amount of solvent, the mixed solution that splashes into small amount of acid and this solvent is made contact substance, the reaction of enough time is carried out in heating, again segregation in the reactant impouring frozen water is obtained α, the beta-unsaturated acid crude product gets its elaboration through recrystallization.This law is applied in the production of raw material 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID in the medicine industry, has got rid of use pyridine and piperidines and made solvent and contact substance, raw material is easy to get, cost reduces by 50～60%, reduce environmental pollution, improve yield 28.5%, be fit to mass production in batch.
Description
The present invention relates to vitochemical general method, particularly α, the improvement of the synthetic method of beta-unsaturated acid.
At Indian J.Chem 1965; 3(7): disclose " Use of Sulphuric Acid as a Condensing Reagent " in 323, this short essay has been introduced with sulfuric acid and has been made nine kinds of α of condensing agent preparation, the method of beta-unsaturated acid, its logical method is that corresponding aldehyde 0.02 mol mixes with propanedioic acid 0.03 mol, add 8 of the vitriol oils, be warmed up to 45 ℃ after the mixing, reaction mixture is put in the water-bath and is heated 60-70 ℃, reacted 15-20 minute, after 10-15 minute, produce a large amount of bubbles, stop heating, after the cooling, the product water treatment is filtered, and uses ethyl alcohol recrystallization, get corresponding α, beta-unsaturated acid.3-methoxyl group-4-hydroxyl-the TRANSCINNAMIC ACID of being given an example in the text, its yield are 68%.The weak point of this method is: 1, this is a solid state reaction, be difficult for mixing, 2, the vitriol oil directly joins in the solid mixture, make local overrich easily, produce side reactions such as carbonization, 3, add the vitriol oil after, moment produces a large amount of bubbles, reactant is gone out, 4, for these reasons, be not suitable for mass production.
At present, synthesis material 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID in the medicine industry at home is as " Chongqing medicines " 1978; (1): introduced in 21～22, its synthetic key step is: corresponding aldehyde (3-methoxyl group-4-hydroxyl-phenyl aldehyde) 1 mol is mixed with propanedioic acid 2 mol, add dry pyridine and piperidines, reacting by heating is 1 hour in oil bath, cooling is in the mixture of impouring trash ice and concentrated hydrochloric acid, with the precipitation suction filtration of separating out, wash, drain, get 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID crude product, behind ethyl alcohol recrystallization, get elaboration.The weak point of this method is: 1, cost height, yield low (yield of top condition only is 48.6%), and 2, owing to use great pyridine of stink and piperidines to make solvent and contact substance, thereby environmental pollution is bigger.
Purpose of the present invention provides a kind of improved α in order to overcome above-mentioned weak point of the prior art just, and the synthetic method of beta-unsaturated acid can reduce cost it, improves yield, reduces environmental pollution, is fit to mass production in batch.
The object of the present invention is achieved like this: a kind of aldehyde of raw material and a kind of acid are pressed 1: 1～3.5 mixed in molar ratio, add an amount of solvent, drip the mixing solutions of a small amount of contact substance-acid and this solvent, reaction mixture is heated to 40～70 ℃, stirring reaction 0.5～3.5 hour, in reactant impouring frozen water, suction filtration gets α, the beta-unsaturated acid crude product, use ethyl alcohol recrystallization, get elaboration.α is separated out in the bath of ethanol mother liquor, and the beta-unsaturated acid elaboration is used ethyl alcohol recrystallization, gets elaboration.Twice elaboration merged, and low temperature is dry down, gets α, the beta-unsaturated acid finished product.
Employed solvent can be a glacial acetic acid in aforesaid method, and the contact substance of use can be the mixing solutions of the vitriol oil and glacial acetic acid.
With the synthetic 3-methoxyl group of aforesaid method-4-hydroxyl-TRANSCINNAMIC ACID, be with 3-methoxyl group-4-hydroxyl-phenyl aldehyde and acid by 1: 1-3.5 mixes, add an amount of solvent, the mixing solutions that drips small amount of acid and this solvent is made contact substance, other reaction conditions and operate same as above.Get 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID finished product at last, average yield is 72.4%, and the highest yield can reach 80.6%.
Employed in the method acid, solvent and contact substance are respectively the mixing solutionss of propanedioic acid (or diethyl malonate), glacial acetic acid, the vitriol oil and glacial acetic acid.
The present invention compared with prior art has following advantage:
1, simple, easy and simple to handle, safe, the suitable mass production in batch of entire synthesis process equipment,
2, use raw material to be easy to get, the side reaction thing is few, and yield improves 28.5% than former synthesis method, and cost reduces by 50～60%.
3, improved synthesis method has been got rid of the great pyridine of stink, piperidines, thereby has reduced the pollution to environment.
The present invention is further described below with reference to embodiment:
Embodiment 1: add raw material 3-methoxyl group-4-hydroxyl-phenyl aldehyde and propanedioic acid (mol ratio is 1: 3.5) and mix in the exsiccant round-bottomed flask, add glacial acetic acid, drip the mixing solutions of a small amount of contact substance-vitriol oil and glacial acetic acid, round-bottomed flask is placed 40 ℃ of stirred in water bath reactions 3.5 hours, in reactant impouring frozen water, suction filtration gets 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID crude product, with ethyl alcohol recrystallization, get elaboration.The bath of ethanol mother liquor, suction filtration gets its crude product, uses ethyl alcohol recrystallization, gets its elaboration, merges elaboration twice, dry below 60 ℃, gets 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID finished product, and yield is 80.6%.
Embodiment 2: the raw material 3-methoxyl group-4-hydroxyl-phenyl aldehyde of adding and propanedioic acid (mol ratio 1: 1) mix, temperature of reaction is about 70 ℃, and the stirring reaction time is 0.5 hour, and other is operated with embodiment 1, get 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID finished product, yield is 49.6%.
Embodiment 3: adding raw material p-nitro-benzene formaldehyde and propanedioic acid (mol ratio 1: 2) temperature of reaction is about 50 °, and the stirring reaction time is 2 hours, and other is operated with embodiment 1, must be to nitro TRANSCINNAMIC ACID finished product, and yield is 58%.
Claims (4)
1, α, the synthetic method of beta-unsaturated acid is characterized in that: a kind of aldehyde and a kind of acid 1: 1 in molar ratio～3.5 are mixed, add an amount of solvent, the mixed solution that drips small amount of acid and this solvent is made contact substance, reaction mixture is heated at 40～70 ℃ stirring reaction 0.5～3.5 hour, in reactant impouring frozen water, suction filtration gets α, and beta-unsaturated acid finished product crude product gets its elaboration with ethyl alcohol recrystallization, obtain α after the drying, the beta-unsaturated acid finished product.
2, α according to claim 1, the synthetic method of beta-unsaturated acid is characterized in that: said solvent, contact substance are respectively the mixing solutions of glacial acetic acid, the vitriol oil and glacial acetic acid.
3, the synthetic method of 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID, it is characterized in that, 3-methoxyl group-4-hydroxyl-phenyl aldehyde and acid 1: 1 in molar ratio～3.5 are mixed, add an amount of solvent, the mixed solution that drips small amount of acid and this solvent is made contact substance, reaction mixture is heated at 40～70 ℃, stirring reaction 0.5～3.5 hour, in reactant impouring frozen water, suction filtration, get 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID crude product, get its elaboration, obtain 3-methoxyl group-4-hydroxyl-TRANSCINNAMIC ACID finished product after the drying with ethyl alcohol recrystallization.
4, the synthetic method of 3-methoxyl group according to claim 2-4-hydroxyl-TRANSCINNAMIC ACID, it is characterized in that: said acid, solvent, contact substance are respectively the mixing solutions of propanedioic acid, glacial acetic acid, the vitriol oil and glacial acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90106186 CN1027756C (en) | 1990-11-28 | 1990-11-28 | Alpha,beta-undersaturated acid synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90106186 CN1027756C (en) | 1990-11-28 | 1990-11-28 | Alpha,beta-undersaturated acid synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1050869A true CN1050869A (en) | 1991-04-24 |
| CN1027756C CN1027756C (en) | 1995-03-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90106186 Expired - Lifetime CN1027756C (en) | 1990-11-28 | 1990-11-28 | Alpha,beta-undersaturated acid synthetic method |
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| CN (1) | CN1027756C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100353936C (en) * | 2003-08-07 | 2007-12-12 | 丽珠集团利民制药厂 | Ferulaic acid sodium transfusion and prescription and preparation thereof |
| CN103396368A (en) * | 2013-07-29 | 2013-11-20 | 中国人民解放军第四军医大学 | Application of free radical of nitroxide to treatment of ischemia reperfusion injury |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3132098A1 (en) | 2022-01-25 | 2023-07-28 | Rhodia Operations | Process for the preparation of p-hydroxycinnamic acid |
-
1990
- 1990-11-28 CN CN 90106186 patent/CN1027756C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100353936C (en) * | 2003-08-07 | 2007-12-12 | 丽珠集团利民制药厂 | Ferulaic acid sodium transfusion and prescription and preparation thereof |
| CN103396368A (en) * | 2013-07-29 | 2013-11-20 | 中国人民解放军第四军医大学 | Application of free radical of nitroxide to treatment of ischemia reperfusion injury |
| CN103396368B (en) * | 2013-07-29 | 2016-01-13 | 中国人民解放军第四军医大学 | The application of nitroxyl free radical in treatment ischemical reperfusion injury |
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| Publication number | Publication date |
|---|---|
| CN1027756C (en) | 1995-03-01 |
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Expiration termination date: 20101128 Granted publication date: 19950301 |