CN102134205A - Method for preparing carbamate - Google Patents
Method for preparing carbamate Download PDFInfo
- Publication number
- CN102134205A CN102134205A CN2010101004092A CN201010100409A CN102134205A CN 102134205 A CN102134205 A CN 102134205A CN 2010101004092 A CN2010101004092 A CN 2010101004092A CN 201010100409 A CN201010100409 A CN 201010100409A CN 102134205 A CN102134205 A CN 102134205A
- Authority
- CN
- China
- Prior art keywords
- carbamate
- acetate
- catalyzer
- amine
- methylcarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing carbamate. The method for preparing the carbamate comprises the following processes of: dissolving carbonic ester, amine and acetate catalyst into a proper solvent so that the molar ratio of the carbonic diester to the amine is 2 to 20 times stoichiometric ratio and the molar ratio of the catalyst to the amine is 1:5-1:100; and then reacting for 0.5 to 16 hours at the temperature of between 30 and 160 DEG C, and performing separation and purification to obtain the required carbamate. The method has the main advantages that: the catalyst has stable chemical performance and low price; and the product separation and purification processes are simple.
Description
Technical field
The present invention relates to a kind of method for preparing carbamate.
Background technology
Amino formate compounds has purposes widely, can be used as the intermediate of agricultural chemicals, medicine, synthetic resins modification and organic synthesis etc.As organic synthesis intermediate, can be used for synthesizing isocyanate, nontoxic polyurethane, cyanamid dimerization derivative, dialkyl carbonate and polyvinylamine etc., carbamate can with reactions such as unsaturated hydrocarbons, aldehyde ketone, polyvalent alcohol and aromatic ring, generate the derivative of various uses, also can be used for heterogeneous ring compounds such as synthetic pyrroles, triazolone and quinoline imidazolone, have good application prospects.
Traditional synthetic method mainly is to be raw material with hypertoxic phosgene, separates through alcoholysis and ammonia and obtains carbamate.In recent years, along with the development of society, various countries more and more pay attention to environment, and new synthetic method is sought all in active research by many countries, with production and the application that replaces phosgene gradually.Although the carbamate of commercially producing has at present mainly adopted based on the reaction between organic alcohol and the isocyanic ester, yet this not environmental protection of route, because industrial production isocyanic ester, need high energy input, and still adopting the phosgene of severe toxicity is raw material, and by-product hydrochloric acid has strong corrodibility again, therefore, in essence, remain a kind of phosgenation route.The non-phosgene synthetic route of some synthesizing organic carbonic ethers is developed, and mainly comprises: 1) nitroreduction carbonyl process: under Pd, Ru or Rh catalyst action, generate carbamate by nitro-compound, pure and mild reaction of carbon monoxide.This method reaction conditions gentleness, by product is few, but poor selectivity, and the utilization ratio of CO has only 1/3 in the reaction process, has CO and CO
2Separation problem.Because the production cost height need be under high pressure carried out in the existence of gas phase CO; 2) amino oxidation carbonyl process: under the Pd catalyst action, prepare carbamate through dioxygen oxidation by amine, carbon monoxide and methyl alcohol.This reaction preference and transformation efficiency are all than higher.Technology is simple, but product is difficult to assurance, and side reaction is many; 3) alcoholysis of urea: with urea, amine and alcohol is initial reactant, through the effect of catalyzer, at first generates the alkyl biuret, and then under catalyst action, the alcoholysis reaction of urea takes place, and generates carbamate.Although with respect to other non-phosgene, the raw material that this method adopts more cleans, and its severe reaction conditions needs to carry out under High Temperature High Pressure.4) methylcarbonate amine-decomposing method: under the effect of catalyzer, generate carbamate by amine and dimethyl carbonate.This route reaction mild condition, the main raw material methylcarbonate that is adopted (being called for short DMC) has the low and active advantages of higher of toxicity, is described as " green chemical ".Byproduct of reaction is a methyl alcohol, can be reclaimed, and is used further to Synthesis of dimethyl carbonate, can accomplish " zero release " of chemical process like this, realize atom economy, be the production technique of environmentally friendly type, can adapt to the requirement of sustainable development, therefore, have very large development potentiality.
The key that the methylcarbonate amine-decomposing method prepares the carbamate route is catalyzer.Custom catalysts comprises alkaline catalysts, Lewis acid catalyst and composition catalyst etc. in this route.Wherein alkaline catalysts has the alcoholate of basic metal (Li, Na, K) or alkaline-earth metal (Mg, Ca), zinc subcarbonate and ventilation breather etc.; The Lewis acid catalyst has organic acid or inorganic acid salt and the loading type thereof etc. of Ti, Zr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb, Bi, Cd; Composition catalyst is formula M O
y(OCONR)
zCompound, wherein, M is zinc, copper; X value 1～4; Y value 0～1; Z value 1～6; R is C
1～C
12Straight or branched alkane, or C
5～C
7Cycloalkyl or aryl.Romano etc. (GB 2091730) are catalyzer with the alcoholate of basic metal (Li, Na, K) or alkaline-earth metal (Mg, Ca), and with methylcarbonate and amine reaction synthesis of carbamates, when amine was aniline, transformation efficiency reached as high as 87%.And Bosettl etc. (US 5698731) are when being catalyzer with zinc subcarbonate and ventilation breather, and the transformation efficiency of aniline reaches as high as 87%, and the yield of phenyl urethan is 97.5%.Richard (WO9855450) is a catalyzer with the organic acid of Ti, Zr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb, Bi, Cd or inorganic acid salt etc., can make tolylene diamine, 4, the transformation efficiency of 4 '-ditan diamines etc. is higher than 98%, and selectivity is higher than 90%.
As can be seen, prepare in the carbamate route at above-mentioned existing methylcarbonate amine-decomposing method, related catalyzer mainly is divided into two big classes, that is: the salt of transition metal or IIIA-VA family metal and the alcoholate of basic metal or alkaline-earth metal, and these catalyzer all exist certain deficiency.First kind catalyzer is after reaction finishes and separates from reaction system, having a certain amount of metal ion remains in the product carbamate, and these metal ions all are active constituents of custom catalysts, therefore, are easy to depositing or use and bring disadvantageous effect carbamate.The second class catalyzer then costs an arm and a leg, meets water decomposition, operation condition harshness.Therefore, necessary exploitation is used to prepare the new catalyst of carbamate.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing carbamate.
The present invention prepares the method for carbamate, it is characterized in that, and with acetate catalyzer, by containing the reaction of amino compound and carbonic diester, prepare carbamate.
The present invention prepares the method for carbamate, and it is further characterized in that, involved catalyzer is a kind of in sodium-acetate, Potassium ethanoate, calcium acetate, magnesium acetate and the Burow Solution; Involved reactant is to contain amino compound and carbonic diester, wherein, containing amino compound is aromatics or the fatty compounds that contains at least one amino group, for example, hexanediamine, isophorone diamine, the dicyclohexyl methyl hydride diamines, n-Butyl Amine 99, normal hexyl Amine, n-octyl amine, n-Decylamine, dibutylamine, hexahydroaniline, benzylamine, methylbenzylamine, carbonic diester is a dialkyl carbonate, diaryl carbonate or carbonate alkyl aryl ester, for example, methylcarbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, carbonic acid aminomethyl phenyl ester; Depend on that used reactant is monoamine or diamines, preparation-obtained carbamate can be single-amido acid ester or diurethanes.
The present invention prepares the method for carbamate, and being specially adapted to the sodium-acetate is catalyzer, and by 1,6-hexanediamine and dimethyl carbonate prepare 1,6-hexa-methylene diamino manthanoate.
The present invention prepares the method for carbamate, its concrete processing step is: carbonic diester, amine and catalyzer are dissolved in the appropriate solvent, make that the mol ratio of carbonic diester and amine is 2～20 times of stoichiometric ratio, the mol ratio of catalyzer and amine is 1: 5～1: 100, under 30-160 ℃ of temperature, reacted 0.5-16 hour then, behind separation and purifying, promptly obtain needed carbamate.
The present invention prepares the method for carbamate, and its outstanding advantage is: 1) stable chemical performance of catalyzer is good, price is inexpensive; 2) reaction and product separation purifying technique are simple; 3) the yield height of carbamate is a catalyzer with the sodium-acetate, by hexamethylene-diamine and dimethyl carbonate, and under optimized conditions, 1, the yield of 6-hexa-methylene diamino manthanoate can reach 98 above %.
Embodiment
Embodiment 1 blank assay
In 250 milliliters there-necked flask, add hexanediamine 11.6 grams successively, methylcarbonate 70ml under agitation is warming up to 80 ℃, reacts after 8 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, reaction conversion ratio 10%, selectivity 90%, productive rate 9%.
The contrast of embodiment 2 sodium acetate catalysts and blank assay
In 250 milliliters there-necked flask, add hexanediamine 11.6 grams successively, methylcarbonate 70ml, sodium-acetate 0.8 gram under agitation is warming up to 80 ℃, reacts after 8 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, reaction conversion ratio 96%, selectivity 90%, productive rate 86.4%.
Embodiment 3 sodium acetate catalysts, methanol solvate
In 250 milliliters there-necked flask, add hexanediamine 11.6 grams successively, methylcarbonate 70ml, methyl alcohol 20ml, sodium-acetate 1.6 grams under agitation are warming up to 70 ℃, react after 6 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, purity＞99%, yield＞98%.
Embodiment 4 sodium acetate catalysts, methanol solvate
In 250 milliliters there-necked flask, add hexanediamine 5.8 grams successively, methylcarbonate 40ml, methyl alcohol 20ml, sodium-acetate 1.0 grams under agitation are warming up to 65 ℃, react after 8 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, purity＞99%, yield＞98%.
Embodiment 5 sodium acetate catalysts, methanol solvate
In 250 milliliters there-necked flask, add hexanediamine 5.8 grams successively, methylcarbonate 40ml, methyl alcohol 30ml, sodium-acetate 1.2 grams under agitation are warming up to 75 ℃, react after 8 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, purity＞99%, yield＞98%.
Embodiment 6 sodium acetate catalysts, methanol solvate
In 250 milliliters there-necked flask, add hexanediamine 11.6 grams successively, methylcarbonate 18ml, methyl alcohol 50ml, sodium-acetate 1.6 grams under agitation are warming up to 75 ℃, react after 10 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, reaction conversion ratio 100%, selectivity 96%, productive rate 96%.
Embodiment 7 sodium acetate catalysts, acetonitrile solvent
In 250 milliliters there-necked flask, add hexanediamine 11.6 grams successively, methylcarbonate 18ml, acetonitrile 50ml, sodium-acetate 1.6 grams under agitation are warming up to 75 ℃, react after 10 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, reaction conversion ratio 97%, selectivity 80%, productive rate 77.6%.
Embodiment 8 sodium acetate catalysts, methyl alcohol and methylcarbonate mixed solvent
In 250 milliliters there-necked flask, add hexanediamine 11.6 grams successively, methylcarbonate 43ml, methyl alcohol 25ml, sodium-acetate 1.6 grams under agitation are warming up to 75 ℃, react after 10 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, reaction conversion ratio 100%, selectivity 98%, productive rate 98%.
Embodiment 9 Burow Solution catalyzer
In 250 milliliters there-necked flask, add hexanediamine 11.6 grams successively, methylcarbonate 70ml, Burow Solution 2 grams under agitation are warming up to 80 ℃, react after 8 hours, and unnecessary methylcarbonate and methyl alcohol are extracted in decompression out, obtain white powder.Add 200ml distilled water then, be heated to 100 ℃, be cooled to room temperature again, separate out hexa-methylene diamino dioctyl phthalate methyl esters white crystal, reaction conversion ratio 79%, selectivity 81%, productive rate 64%.
Claims (3)
1. a method for preparing carbamate is characterized in that, is catalyzer with acetate, by containing the reaction of amino compound and carbonic diester, prepares carbamate.
2. according to the described method for preparing carbamate of claim 1, it is characterized in that, is catalyzer with a kind of in sodium-acetate, Potassium ethanoate, calcium acetate, magnesium acetate and the Burow Solution, by aliphatic amide and dimethyl carbonate, prepares carbamate.
3. according to the described method for preparing carbamate of claim 1, it is characterized in that, is catalyzer with the sodium-acetate, and by 1,6-hexanediamine and dimethyl carbonate prepare 1,6-hexa-methylene diamino manthanoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101004092A CN102134205A (en) | 2010-01-25 | 2010-01-25 | Method for preparing carbamate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101004092A CN102134205A (en) | 2010-01-25 | 2010-01-25 | Method for preparing carbamate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102134205A true CN102134205A (en) | 2011-07-27 |
Family
ID=44294158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101004092A Pending CN102134205A (en) | 2010-01-25 | 2010-01-25 | Method for preparing carbamate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102134205A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349110A (en) * | 2015-07-17 | 2017-01-25 | 大东树脂化学股份有限公司 | Two-stage method and one-pot synthesis method for preparing aliphatic diisocyanate |
| CN111971119A (en) * | 2018-03-28 | 2020-11-20 | 科思创知识产权两合公司 | Heterogeneous catalyst for carbamate synthesis |
| CN112707815A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for coupling production of diphenyl carbonate and methyl phenylcarbamate |
| CN114605308A (en) * | 2022-03-18 | 2022-06-10 | 阜新孚隆宝医药科技有限公司 | Preparation method of azabicyclo medical intermediate of paroxetine and intermediate |
| CN115073324A (en) * | 2022-07-05 | 2022-09-20 | 中国科学院过程工程研究所 | Method for preparing pentanedicarbamate by homogeneous catalysis |
| CN115894300A (en) * | 2021-09-22 | 2023-04-04 | 中国科学院过程工程研究所 | Method for purifying 1,6-hexamethylene dicarbamate |
-
2010
- 2010-01-25 CN CN2010101004092A patent/CN102134205A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349110A (en) * | 2015-07-17 | 2017-01-25 | 大东树脂化学股份有限公司 | Two-stage method and one-pot synthesis method for preparing aliphatic diisocyanate |
| CN111971119A (en) * | 2018-03-28 | 2020-11-20 | 科思创知识产权两合公司 | Heterogeneous catalyst for carbamate synthesis |
| CN111971119B (en) * | 2018-03-28 | 2023-12-08 | 科思创知识产权两合公司 | Heterogeneous catalyst for carbamate synthesis |
| CN112707815A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for coupling production of diphenyl carbonate and methyl phenylcarbamate |
| CN115894300A (en) * | 2021-09-22 | 2023-04-04 | 中国科学院过程工程研究所 | Method for purifying 1,6-hexamethylene dicarbamate |
| CN114605308A (en) * | 2022-03-18 | 2022-06-10 | 阜新孚隆宝医药科技有限公司 | Preparation method of azabicyclo medical intermediate of paroxetine and intermediate |
| CN114605308B (en) * | 2022-03-18 | 2023-12-19 | 阜新孚隆宝医药科技有限公司 | Preparation method of azabicyclo medicine intermediate of Pa Luo Weide and intermediate |
| CN115073324A (en) * | 2022-07-05 | 2022-09-20 | 中国科学院过程工程研究所 | Method for preparing pentanedicarbamate by homogeneous catalysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102134205A (en) | Method for preparing carbamate | |
| US10421705B2 (en) | Carboxylic acid ester production method | |
| JP5804472B2 (en) | Ester production method | |
| CA2591754A1 (en) | Process for producing aromatic carbonate | |
| CN109721545B (en) | Preparation method of azoxystrobin intermediate | |
| CN101054351B (en) | Method for cleanly synthesizing phenylamido formate | |
| CN101245001A (en) | Process for synthesizing carbonochloridic acid 9-fluorene methyl ester | |
| CN102060837B (en) | Preparation method of cyclic carbonic ester | |
| CN101130508B (en) | Process for synthesizing phenyl urethane in atmospheric condition | |
| KR101038271B1 (en) | Method for Preparing Aliphatic Dicarbamates | |
| CN101468959A (en) | Method for synthesizing hexamethylene carbamate | |
| KR101307559B1 (en) | Synthesis of glycerol carbonate using high active catalysts | |
| CN1715267A (en) | New process for preparing carbaniloyl ester | |
| CN100417444C (en) | Catalyst for coupling reaction of annular carbonic acid esters and organic dibasic acid ester | |
| CN100358902C (en) | Synthesis of binuclear metal complex compound and its catalyzed copolymerization and cycloaddition reaction of carbon dioxide and epoxide | |
| CN103182325B (en) | Catalyst, its preparation method and use its prepare the method for aromatic carbonate from dialkyl carbonate | |
| CN102513087A (en) | Catalyst for synthesizing phenyl carbamate from diphenyl urea, preparation method and application | |
| CN101759600A (en) | Method for synthesizing alkyl carbamate by NH3, CO2 and micromolecular fatty alcohol | |
| CN103113263B (en) | Method for recycling aniline in phenyl carbamate preparation process by urea coupling method | |
| JP5434919B2 (en) | Method for producing carbamate compound | |
| CN101698670B (en) | Method for preparing phenyl iso-propenyloxysilane | |
| CN100369671C (en) | Method for preparing N-substituted carbamate using cyclohexane zine butyrate | |
| CN110818595A (en) | Preparation method for preparing carbamate | |
| JPH07330708A (en) | Production of carbamate | |
| CN116102466B (en) | Preparation method of 1, 3-dipropylurea compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110727 |