CN1271728A - Process for synthesizing allantoin - Google Patents
Process for synthesizing allantoin Download PDFInfo
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- CN1271728A CN1271728A CN 99115350 CN99115350A CN1271728A CN 1271728 A CN1271728 A CN 1271728A CN 99115350 CN99115350 CN 99115350 CN 99115350 A CN99115350 A CN 99115350A CN 1271728 A CN1271728 A CN 1271728A
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Abstract
A process for synthesizing allantoin uses acetaldehyde as raw material and includes such steps as using nitric acid to control oxidation to obtain oxidized solution containing glyoxylic acid, adding precipitant, gradually neutralizing to deposit out oxalate and glyoxylate, treating glyoxylate with strong acid or medium-strong acid, adding urea and condensation reaction to obtain the product. Its advantages include short reaction time, high output rate and cyclic use of mother liquor.
Description
Wallantoin is a kind of important fine chemical product, conveniently has a wide range of applications at medicine, light industry, agricultural, daily-use chemical industry, biotechnology etc.The wallantoin synthetic method has a lot, and industrial production generally adopts oxalic acid electrolytic process or oxalic dialdehyde nitric acid oxidation method.Oxalic acid electrolytic process raw material is easy to get, low price, but facility investment is big, technical process is complicated, energy consumption is high.The technical process of oxalic dialdehyde method is simple, but prices of raw and semifnished materials costliness, the production cost height.
It is raw material that Poland Patent Pol 124455 proposes with acetaldehyde, nitric acid, urea, the synthetic allantoin for the treatment of different things alike.Its working method is with the rare nitric acid oxidation of acetaldehyde solution, add then urea condensation react wallantoin, yield about 22% (in acetaldehyde).This method raw material is easy to get inexpensive, but the reaction times oversize (only condensation reaction just reached more than 24 hours), and yield is lower, about 22% (in acetaldehyde) only, reaction mother liquor composition complexity and recycle difficulty.
The objective of the invention is to overcome above the deficiencies in the prior art and provide a kind of reaction times short, yield is high, the wallantoin synthesis technique of mother liquor reusable edible.
Technical scheme of the present invention is: drop into all or part of acetaldehyde solution earlier, add reaction initiator and a small amount of salpeter solution more respectively, after reaction causes, drop into remaining salpeter solution or drop into remaining salpeter solution and remaining acetaldehyde solution simultaneously, control reaction temperature is carried out oxidizing reaction, and the degree of oxidation of controlled oxidation reaction, in time stopped reaction adds precipitation agent, reaction solution is neutralized gradually, separate out oxalate precipitation earlier, treat that oxalate is separated out fully after, remove by filter oxalate, continuing to be neutralized to glyoxylate again separates out fully, filter, washing obtains glyoxylate, adds inorganic acid or middle strong acid, and oxoethanoic acid dissociates, if any precipitation, remove by filter, add urea again, heat up and obtain wallantoin through condensation reaction.
Reaction can be to reaction solution bubbling air or oxygen after causing.
The degree of oxidation of controlled oxidation reaction in oxidation reaction process, promptly the oxalic dialdehyde in the controlled oxidation reaction solution, the mole number of oxoethanoic acid, oxalic acid satisfies
Used precipitation agent can be the water soluble of calcium, barium, lead, copper or compound or its composition of acid.
Acetaldehyde and nitric acid proportioning (mole) they are 1: 0.5-2.5, and glyoxylate and inorganic acid or middle strong acid proportioning (equivalent) they are 1: 1-2, oxoethanoic acid and urea proportioning (mole) they are 1: 2.5-6,
Acetaldehyde solution and salpeter solution are that the oxidation liquid behind the employing extraction oxoethanoic acid is formulated.
The present invention is owing to become oxoethanoic acid with oxidation of acetaldehyde, and extract, utilize the reaction of oxoethanoic acid and urea condensation to form wallantoin then, compared with prior art the reaction times shortens (condensation reaction only needs about 3 hours) greatly, the yield height, can reach 26-29% (in acetaldehyde), oxidation mother liquor behind the extraction oxoethanoic acid (major ingredient is nitrate, acetic acid, a small amount of oxalic dialdehyde) and condensation reaction mother liquor (major ingredient is urea, inorganic salt, a small amount of residual acid, wallantoin) composition are simple, reusable edible, reduce discharge of wastewater, and can reclaim useful matter wherein.
Embodiment 1: with the acetaldehyde solution of 10g 40% (weight), 0.8g Sodium Nitrite, the salpeter solution of 10g 35% (weight) drops in the reaction flask, the initiated oxidation reaction of 40 ℃ of left and right sides of controlled temperature takes place, then, drip the acetaldehyde solution of 90g 40% (weight) and the salpeter solution of 175g 35% (weight) simultaneously, control rate of addition and temperature of cooling water, temperature of reaction is controlled at about 40 ℃, after adding material, be raised to and react 2.5 hours about 55 ℃ to oxidizing reaction end, the degree of oxidation of oxidizing reaction
Add the 50g Calcium Chloride Powder Anhydrous, with the sodium hydroxide neutralization, treat that calcium oxalate precipitation fully after, remove by filter, continue to be neutralized to oxoethanoic acid calcium and separate out fully with sodium hydroxide, filter, wash the oxoethanoic acid calcium deposit.The oxoethanoic acid calcium deposit is added stirring and dissolving in the 90ml 6.5N hydrochloric acid, add 78g urea, rise to 70 ℃ of condensation reactions about 3 hours, cooling, crystallization is filtered, and washing obtains the wallantoin white solid, with the water recrystallization, get the wallantoin white crystals, the wallantoin yield is 26.5% (in acetaldehyde).
Embodiment 2: synthesis technique is with embodiment 1, and different is, drops into the 124g barium chloride and makes precipitation agent, and the wallantoin yield is 27.9% (in acetaldehyde).
Embodiment 3: synthesis technique is with embodiment 1, and different is, after nitric acid has all been thrown, slowly blasts air to reaction solution, finishes until oxidizing reaction.The degree of oxidation of oxidizing reaction was 0.57 (mol ratio) when oxidizing reaction finished.The wallantoin yield is 27.6% (in acetaldehyde).
Embodiment 4: synthesis technique is with embodiment 1, and different is that acetaldehyde solution and salpeter solution are that the oxidation liquid behind the employing extraction oxoethanoic acid is formulated.The degree of oxidation of oxidizing reaction was 0.60 (mol ratio) when oxidizing reaction finished.The wallantoin yield can reach 29.8% (in acetaldehyde).
Claims (9)
1, a kind of synthesis technique of wallantoin, it is characterized in that dropping into earlier all or part of acetaldehyde solution, add reaction initiator and a small amount of salpeter solution more respectively, after reaction causes, drop into remaining salpeter solution or drop into remaining salpeter solution and remaining acetaldehyde solution simultaneously, control reaction temperature is carried out oxidizing reaction, and the degree of oxidation of controlled oxidation reaction, timely stopped reaction, add precipitation agent, reaction solution is neutralized gradually, separate out oxalate precipitation earlier, after treating that oxalate is separated out fully, remove by filter oxalate, continue to be neutralized to glyoxylate again and separate out fully, filter, washing obtains glyoxylate, add inorganic acid or middle strong acid, the oxoethanoic acid that dissociates if any precipitation, removes by filter, add urea again, heat up and obtain wallantoin through condensation reaction.
2, the synthesis technique of wallantoin as claimed in claim 1 is characterized in that
A, acetaldehyde and nitric acid proportioning (mole) they are 1: 0.5-2.5,
B, glyoxylate and inorganic acid or middle strong acid proportioning (equivalent) they are 1: 1-2,
C, oxoethanoic acid and urea proportioning (mole) they are 1: 2.5-6,
D, oxidizing reaction temperature are controlled at 30-80 ℃, and setting-up point is controlled at 50-85 ℃.
3, the synthesis technique of wallantoin as claimed in claim 1 or 2, the degree of oxidation that it is characterized in that oxidizing reaction be in the oxidation liquid oxalic dialdehyde, the mole number of oxoethanoic acid, oxalic acid satisfies
4, the synthesis technique of wallantoin as claimed in claim 1 or 2 is characterized in that precipitation agent is the water soluble of calcium, barium, lead, copper or compound or its composition of acid.
5, the synthesis technique of wallantoin as claimed in claim 3 is characterized in that precipitation agent is the water soluble of calcium, barium, lead, copper or compound or its composition of acid.
6, as the synthesis technique of claim 1 or 2 or 5 described wallantoins, it is characterized in that oxidizing reaction causes after, can be to reaction solution bubbling air or oxygen.
7, the synthesis technique of wallantoin as claimed in claim 3, it is characterized in that oxidizing reaction causes after, can be to reaction solution bubbling air or oxygen.
8, the synthesis technique of wallantoin as claimed in claim 4, it is characterized in that oxidizing reaction causes after, can be to reaction solution bubbling air or oxygen.
9, a kind of synthesis technique of wallantoin is characterized in that acetaldehyde solution and salpeter solution are that the oxidation liquid that adopt to extract behind the oxoethanoic acid is formulated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99115350 CN1271728A (en) | 1999-04-27 | 1999-04-27 | Process for synthesizing allantoin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99115350 CN1271728A (en) | 1999-04-27 | 1999-04-27 | Process for synthesizing allantoin |
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| CN1271728A true CN1271728A (en) | 2000-11-01 |
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| CN 99115350 Pending CN1271728A (en) | 1999-04-27 | 1999-04-27 | Process for synthesizing allantoin |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786409A (en) * | 2012-07-26 | 2012-11-21 | 湖北省宏源药业有限公司 | Refining method for glyoxalic acid |
| CN102898376A (en) * | 2012-10-08 | 2013-01-30 | 北京桑普生物化学技术有限公司 | Allantoin synthesis method |
| CN103145621A (en) * | 2013-03-01 | 2013-06-12 | 凤台县精华助剂有限公司 | Allantoin preparation method |
| CN103724272A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN103724273A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN104829029A (en) * | 2015-05-05 | 2015-08-12 | 湖北省宏源药业科技股份有限公司 | Treatment method of industrial wastewater from synthesis of allantoin |
| CN107805222A (en) * | 2017-11-23 | 2018-03-16 | 天津市职业大学 | A kind of method of comprehensive utilization of allantoin synthesis mother liquid |
-
1999
- 1999-04-27 CN CN 99115350 patent/CN1271728A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786409A (en) * | 2012-07-26 | 2012-11-21 | 湖北省宏源药业有限公司 | Refining method for glyoxalic acid |
| CN102898376A (en) * | 2012-10-08 | 2013-01-30 | 北京桑普生物化学技术有限公司 | Allantoin synthesis method |
| CN102898376B (en) * | 2012-10-08 | 2014-07-09 | 北京桑普生物化学技术有限公司 | Allantoin synthesis method |
| CN103145621A (en) * | 2013-03-01 | 2013-06-12 | 凤台县精华助剂有限公司 | Allantoin preparation method |
| CN103724272A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN103724273A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN104829029A (en) * | 2015-05-05 | 2015-08-12 | 湖北省宏源药业科技股份有限公司 | Treatment method of industrial wastewater from synthesis of allantoin |
| CN104829029B (en) * | 2015-05-05 | 2016-09-07 | 湖北省宏源药业科技股份有限公司 | A kind of processing method of the industrial wastewater of synthetic allantoin |
| CN107805222A (en) * | 2017-11-23 | 2018-03-16 | 天津市职业大学 | A kind of method of comprehensive utilization of allantoin synthesis mother liquid |
| CN107805222B (en) * | 2017-11-23 | 2020-07-17 | 天津市职业大学 | Comprehensive utilization method of allantoin synthetic mother liquor |
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