CN101928237A - Process for preparing N,N'-dicyclohexyl carbodiimide by regeneration method - Google Patents
Process for preparing N,N'-dicyclohexyl carbodiimide by regeneration method Download PDFInfo
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- CN101928237A CN101928237A CN2010102245965A CN201010224596A CN101928237A CN 101928237 A CN101928237 A CN 101928237A CN 2010102245965 A CN2010102245965 A CN 2010102245965A CN 201010224596 A CN201010224596 A CN 201010224596A CN 101928237 A CN101928237 A CN 101928237A
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Abstract
The invention discloses a process for preparing N,N'-dicyclohexyl carbodiimide by a regeneration method, which comprises the following steps of: removing impurities from N,N'-dicyclohexyl urea (DCU) serving as a raw material through alkaline wash, and performing regeneration by using an oxidizing agent; and reacting under stirring of an organic solvent at the temperature of between 40 and 42 DEG C for 0.15 to 2 hours to regenerate the N,N'-dicyclohexyl carbodiimide (DCC), wherein the regeneration rate is up to between 60 and 78 percent, and the DCC content of the product reaches over 99.5 percent. The process has the advantages of readily available raw materials, convenient operation and low cost, and provides the beneficial condition for the circular production and use of the DCC and particular the application to industry of medicine, the synthesis of amide and polypeptide and the like.
Description
Technical field
The present invention relates to a kind of N, the production technique of N '-dicyclohexylcarbodiimide belongs to the organic compound synthesis technical field.
Background technology
N, N '-dicyclohexylcarbodiimide is called for short DCC, is organic synthesis and medical process industry dehydrating agent commonly used, and it can make two molecules that can not react originally, and dehydration forms chemical bond.Be mainly used in the production of products such as Amikacin Sulphate and glutathione in China.
N, the molecular formula of N '-dicyclohexylcarbodiimide is C
13H
22N
2, structural formula is:
The preparation method of DCC can be divided into thiocarbamide method and N, N '-dicyclohexylurea (DCU) (DCU) method.The thiocarbamide method has two kinds of synthetic methods, at first all is to form corresponding thiourea derivative by 2 molecule hexahydroaniline with 1 molecule dithiocarbonic anhydride, adopts different reaction reagent depriving hydrogen sulphides then respectively, is translated into DCC.First method is to adopt red precipitate to make reaction reagent; Second method adopts clorox to make reaction reagent.The former has used the compound of mercury can be influential to environment, therefore an appropriate experimental chamber prepares on a small quantity, and the raw material sources that the latter uses are convenient, and production cost is low, be the common method of industrial production DCC, Chinese patent CN100434416C has carried out detailed report to this method.
N, N '-dicyclohexylurea (DCU) method also is to be starting raw material with the hexahydroaniline, through forming N, N '-dicyclohexylurea (DCU) intermediate product, and then form DCC through dehydration reaction.N wherein, N '-dicyclohexylurea (DCU) can be made by hexahydroaniline and phosgene direct reaction, also can be made by hexahydroaniline, urea and primary isoamyl alcohol back flow reaction.In addition, DCC also can generate N in actual application, N '-dicyclohexylurea (DCU) (DCU), if not in addition recycling can cause the waste and the environmental pollution of raw material.
Summary of the invention
The object of the present invention is to provide a kind of method of reproduction to prepare N, the production technique of N '-dicyclohexylcarbodiimide, this kind technology regains DCC with the DCU that the back produces by regeneration with DCC, can realize the cycle applications of former material like this, can solve the emission problem of industrial waste again.
The technical scheme that the present invention takes is:
A kind of method of reproduction prepares N, and the production technique of N '-dicyclohexylcarbodiimide comprises the steps:
(1) pre-treatment: with N, N '-dicyclohexylurea (DCU) (DCU) raw material is put into alkaline aqueous solution and is embathed, the water-soluble impurity that may exist in the flush away raw material, and the raw material centrifuge dehydration after will embathing is put into drying plant and is carried out drying;
(2) regenerative response: with dried N, N '-dicyclohexylurea (DCU) (DCU) adds in the organic solvent and mixes, dropping oxidizing agent was at 40 ℃ of-42 ℃ of following stirring reaction 0.15-2 hours in this mixture, then reacted product is added drop-wise to and carries out alkali cleaning in the alkaline aqueous solution, will wash after product at last and move to standing demix in the separating funnel;
(3) condensing crystal: with the concentrated DCC product that promptly obtains of the organic phase after the layering.
N, N '-dicyclohexylurea (DCU) (DCU) raw material can be by chemosynthesis preparation pure product, also can be the by product that pharmacy, synthetic industry use DCC to generate as dehydrating agent.
Above-mentioned organic solvent is methylene dichloride, tetrahydrofuran (THF), acetonitrile, N, one or more in the dinethylformamide.
Above-mentioned oxygenant is one or more in phosphorus oxychloride, toluene sulfonyl chloride, benzene sulfonyl chloride, the Vanadium Pentoxide in FLAKES.
Above-mentioned alkaline aqueous solution is the aqueous solution of sodium hydroxide or yellow soda ash or sodium bicarbonate, and concentration range is 5-35% (wt%), and the consumption in the step (1) is mol ratios such as solute and DCU, and the consumption in the step (2) is mol ratios such as solute and oxygenant.
Dried N in the above-mentioned steps (2), the usage ratio of N '-dicyclohexylurea (DCU) and organic solvent and oxygenant is as follows: N, N '-dicyclohexylurea (DCU) and organic solvent mass ratio are 1: 3～5; N, the mol ratio of N '-dicyclohexylurea (DCU) and oxygenant is 1: 1.05～1.2.
Do not have other organic compound to generate in the above-mentioned reaction except that main reaction product D CC, have only small amounts of inorganic salt to exist, the latter is easy to remove by washing.The content of product is more than 99.5% as can be known by gas chromatography determination, and the infrared spectra spectrum analysis of product has confirmed that also the structure of the chemical structure of product and DCC is identical substantially.
The invention has the beneficial effects as follows:
Can realize N with DCU, N '-dicyclohexylcarbodiimide (DCC) regeneration, regeneration rate is up to 60～78%, and product DCC content reaches more than 99.5%.Raw material obtains easily, easy to operate, cost is lower, for the cyclic production of DCC provides favourable condition with using particularly the application in industries such as medicine, acid amides and synthesizing of polypeptide.
Description of drawings
The N that Fig. 1 makes for embodiment 1, N '-dicyclohexylcarbodiimide gas chromatogram;
The N that Fig. 2 makes for embodiment 1, N '-dicyclohexylcarbodiimide infrared spectrogram.
Embodiment
The present invention will be described in detail below in conjunction with embodiment.
With 5.0kg N, N '-dicyclohexylurea (DCU) (DCU) raw material is put into alkaline aqueous solution and is embathed the water-soluble impurity that exists in the flush away raw material three times.Raw material centrifuge dehydration after will embathing is put into vacuum drying oven and be dried to constant weight under 60 ℃.Raw material after the constant weight is put to the polypropylene packing bag standby.
Take by weighing the dried DCU of 40.00g, take by weighing methylene dichloride 175.00 grams, both are joined respectively in the there-necked flask, take by weighing phosphorus oxychloride 35.50g and join in the dropping funnel of 250ml.Open whipping appts, drip phosphorus oxychloride to reaction system then, add the back and kept stirring reaction 2 hours, will note in the reaction process maintaining the temperature between 40 ℃ to 42 ℃; Reaction solution is poured in the dropping funnel, in there-necked flask, added 160g liquid industrial caustic soda (about 30%) then, add 275ml distilled water.Open and stir, dropwise reaction liquid adds the back and continues to stir 10 minutes, and temperature is controlled at below 40 degree.At last product is poured in the separating funnel of 1L into standing demix.The organic phase of lower floor is emitted, put it into that condensing crystal promptly obtains the DCC product in the Rotary Evaporators.Regeneration rate 75%, product DCC content 99.5%.
Embodiment 2
Take by weighing the dried DCU of 40.00g, take by weighing tetrahydrofuran (THF) 180.00 grams, both are joined respectively in the there-necked flask, take by weighing phosphorus oxychloride 35.50g and join in the dropping funnel of 250ml.Open whipping appts, drip phosphorus oxychloride to reaction system then, add the back and kept stirring reaction 2 hours, will note in the reaction process maintaining the temperature between 40 ℃ to 42 ℃; Reaction solution is poured in the dropping funnel, in there-necked flask, added 160g liquid industrial caustic soda (about 30%) then, add 275ml distilled water.Open and stir, dropwise reaction liquid adds the back and continues to stir 10 minutes, and temperature is controlled at below 40 degree.At last product is poured in the separating funnel of 1L into standing demix.The organic phase of lower floor is emitted, put it into that condensing crystal promptly obtains the DCC product in the Rotary Evaporators.Regeneration rate 60%, product DCC content 99.6%.
Embodiment 3
Take by weighing the dried DCU of 40.00g, take by weighing acetonitrile 150.00 grams, both are joined respectively in the there-necked flask, take by weighing phosphorus oxychloride 35.50g and join in the dropping funnel of 250ml.Open whipping appts, drip phosphorus oxychloride to reaction system then, add the back and kept stirring reaction 2 hours, will note in the reaction process maintaining the temperature between 40 ℃ to 42 ℃; Reaction solution is poured in the dropping funnel, in there-necked flask, added the 130g industrial sodium carbonate then, add 250ml distilled water.Open and stir, dropwise reaction liquid adds the back and continues to stir 10 minutes, and temperature is controlled at below 40 degree.At last product is poured in the separating funnel of 1L into standing demix.The organic phase of lower floor is emitted, put it into that condensing crystal promptly obtains the DCC product in the Rotary Evaporators.Regeneration rate 70%, product DCC content 99.8%.
Embodiment 4
Take by weighing the dried DCU of 40.00g, take by weighing tetrahydrofuran (THF) 175.00 grams, both are joined respectively in the there-necked flask, take by weighing toluene sulfonyl chloride 35.50g and join in the dropping funnel of 250ml.Open whipping appts, drip toluene sulfonyl chloride to reaction system then, add the back and kept stirring reaction 2 hours, will note in the reaction process maintaining the temperature between 40 ℃ to 42 ℃; Reaction solution is poured in the dropping funnel, in there-necked flask, added 160g liquid industrial caustic soda (about 30%) then, add 275ml distilled water.Open and stir, dropwise reaction liquid adds the back and continues to stir 10 minutes, and temperature is controlled at below 40 degree.At last product is poured in the separating funnel of 1L into standing demix.The organic phase of lower floor is emitted, put it into that condensing crystal promptly obtains the DCC product in the Rotary Evaporators.Regeneration rate 65%, product DCC content 99.6%.
Embodiment 5
Take by weighing the dried DCU of 40.00g, take by weighing N, dinethylformamide 145.00 grams join both respectively in the there-necked flask, take by weighing phosphorus oxychloride 35.50g and join in the dropping funnel of 250ml.Open whipping appts, drip phosphorus oxychloride to reaction system then, add the back and kept stirring reaction 2 hours, will note in the reaction process maintaining the temperature between 40 ℃ to 42 ℃; Reaction solution is poured in the dropping funnel, in there-necked flask, added the 100g industrial sodium carbonate then, add 225ml distilled water.Open and stir, dropwise reaction liquid adds the back and continues to stir 10 minutes, and temperature is controlled at below 40 degree.At last product is poured in the separating funnel of 1L into standing demix.The organic phase of lower floor is emitted, put it into that condensing crystal promptly obtains the DCC product in the Rotary Evaporators.Regeneration rate 78%, product DCC content 99.5%.
Embodiment 6
Take by weighing the dried DCU of 40.00g, take by weighing methylene dichloride 175.00 grams, both are joined respectively in the there-necked flask, take by weighing benzene sulfonyl chloride 35.50g and join in the dropping funnel of 250ml.Open whipping appts, drip benzene sulfonyl chloride to reaction system then, add the back and kept stirring reaction 2 hours, will note in the reaction process maintaining the temperature between 40 ℃ to 42 ℃; Reaction solution is poured in the dropping funnel, in there-necked flask, added 160g liquid industrial caustic soda (about 30%) then, add 275ml distilled water.Open and stir, dropwise reaction liquid adds the back and continues to stir 10 minutes, and temperature is controlled at below 40 degree.At last product is poured in the separating funnel of 1L into standing demix.The organic phase of lower floor is emitted, put it into that condensing crystal promptly obtains the DCC product in the Rotary Evaporators.Regeneration rate 72%, product DCC content 99.7%.
Claims (5)
1. a method of reproduction prepares N, and the production technique of N '-dicyclohexylcarbodiimide is characterized in that, comprises the steps:
(1) pre-treatment: with N, N '-dicyclohexylurea (DCU) raw material is put into alkaline aqueous solution and is embathed, and the raw material dehydration after will embathing is also dry;
(2) regenerative response: with dried N, N '-dicyclohexylurea (DCU) adds in the organic solvent and mixes, dropping oxidizing agent and in this mixture at 40 ℃ of-42 ℃ of following stirring reaction 0.15-2 hours, then reacted product is added drop-wise to and carries out alkali cleaning in the alkaline aqueous solution, will wash after product at last and move to standing demix in the separating funnel;
(3) condensing crystal: with the concentrated DCC product that promptly obtains of the organic phase after the layering.
2. prepare N according to the described method of reproduction of claim 1, the production technique of N '-dicyclohexylcarbodiimide is characterized in that, described organic solvent is methylene dichloride, tetrahydrofuran (THF), acetonitrile, N, one or more in the dinethylformamide.
3. prepare N according to the described method of reproduction of claim 1, the production technique of N '-dicyclohexylcarbodiimide is characterized in that, described oxygenant is one or more in phosphorus oxychloride, toluene sulfonyl chloride, benzene sulfonyl chloride, the Vanadium Pentoxide in FLAKES.
4. prepare N according to the described method of reproduction of claim 1, the production technique of N '-dicyclohexylcarbodiimide is characterized in that, described alkaline aqueous solution is the aqueous solution of sodium hydroxide or yellow soda ash or sodium bicarbonate, and concentration range is 5-35%.
5. prepare N according to the described method of reproduction of claim 1, the production technique of N '-dicyclohexylcarbodiimide, it is characterized in that, dried N in the step (2), the consumption of N '-dicyclohexylurea (DCU) and organic solvent and oxygenant is as follows: N, and N '-dicyclohexylurea (DCU) and organic solvent mass ratio are 1: 3～5; N, the mol ratio of N '-dicyclohexylurea (DCU) and oxygenant is 1: 1.05～1.2.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408355A (en) * | 2011-11-24 | 2012-04-11 | 浙江工业大学 | Method for synthesizing dicyclohexylcarbodiimide compound |
| CN102643215A (en) * | 2012-04-20 | 2012-08-22 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of carbodiimide |
| CN102775329A (en) * | 2012-08-02 | 2012-11-14 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of carbodiimide |
| CN102816087A (en) * | 2011-06-10 | 2012-12-12 | 上海朗亿功能材料有限公司 | Method for preparing hydrolysis stabilizer for adhesive |
| CN103922970A (en) * | 2014-04-10 | 2014-07-16 | 李娜 | Synthesis method of dicyclohexyl carbodiimide |
| CN104262200A (en) * | 2014-09-02 | 2015-01-07 | 山东巨业精细化工有限公司 | Production method for preparing N,N'-dicyclohexylcarbodiimide (DCC) by recycling wastewater |
| CN104529832A (en) * | 2014-11-18 | 2015-04-22 | 江苏泰仓农化有限公司 | Production technology of N-cyclohexylurea |
| CN105439870A (en) * | 2015-12-05 | 2016-03-30 | 山东汇海医药化工有限公司 | Method for recycling recycled N,N'-dicyclohexylurea |
| CN109081792A (en) * | 2018-07-23 | 2018-12-25 | 常州大学 | A kind of preparation method of pyribenzoxim by-product of dicyclohexylurea recovery |
| CN110903217A (en) * | 2019-12-11 | 2020-03-24 | 山东汇海医药化工有限公司 | Method for reducing waste residues of N, N' -dicyclohexylcarbodiimide product |
| CN110903218A (en) * | 2019-12-16 | 2020-03-24 | 山东金城柯瑞化学有限公司 | Preparation method of dicyclohexylcarbodiimide |
| CN112759534A (en) * | 2020-12-31 | 2021-05-07 | 山东金城柯瑞化学有限公司 | Method for producing N, N' -dicyclohexylcarbodiimide |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816087A (en) * | 2011-06-10 | 2012-12-12 | 上海朗亿功能材料有限公司 | Method for preparing hydrolysis stabilizer for adhesive |
| CN102408355A (en) * | 2011-11-24 | 2012-04-11 | 浙江工业大学 | Method for synthesizing dicyclohexylcarbodiimide compound |
| CN102643215A (en) * | 2012-04-20 | 2012-08-22 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of carbodiimide |
| CN102775329A (en) * | 2012-08-02 | 2012-11-14 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of carbodiimide |
| CN103922970A (en) * | 2014-04-10 | 2014-07-16 | 李娜 | Synthesis method of dicyclohexyl carbodiimide |
| CN104262200B (en) * | 2014-09-02 | 2016-06-29 | 山东巨业精细化工有限公司 | One recycles waste water and prepares N, N ' production method of-dicyclohexylcarbodiimide |
| CN104262200A (en) * | 2014-09-02 | 2015-01-07 | 山东巨业精细化工有限公司 | Production method for preparing N,N'-dicyclohexylcarbodiimide (DCC) by recycling wastewater |
| CN104529832A (en) * | 2014-11-18 | 2015-04-22 | 江苏泰仓农化有限公司 | Production technology of N-cyclohexylurea |
| CN105439870A (en) * | 2015-12-05 | 2016-03-30 | 山东汇海医药化工有限公司 | Method for recycling recycled N,N'-dicyclohexylurea |
| CN109081792A (en) * | 2018-07-23 | 2018-12-25 | 常州大学 | A kind of preparation method of pyribenzoxim by-product of dicyclohexylurea recovery |
| CN110903217A (en) * | 2019-12-11 | 2020-03-24 | 山东汇海医药化工有限公司 | Method for reducing waste residues of N, N' -dicyclohexylcarbodiimide product |
| CN110903218A (en) * | 2019-12-16 | 2020-03-24 | 山东金城柯瑞化学有限公司 | Preparation method of dicyclohexylcarbodiimide |
| CN112759534A (en) * | 2020-12-31 | 2021-05-07 | 山东金城柯瑞化学有限公司 | Method for producing N, N' -dicyclohexylcarbodiimide |
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Application publication date: 20101229 |