CN101130508B - Process for synthesizing phenyl urethane in atmospheric condition - Google Patents
Process for synthesizing phenyl urethane in atmospheric condition Download PDFInfo
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- CN101130508B CN101130508B CN2006101124933A CN200610112493A CN101130508B CN 101130508 B CN101130508 B CN 101130508B CN 2006101124933 A CN2006101124933 A CN 2006101124933A CN 200610112493 A CN200610112493 A CN 200610112493A CN 101130508 B CN101130508 B CN 101130508B
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- dialkyl carbonate
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Abstract
The invention discloses a synthesizing method of carbanilate under normal pressure condition, which comprises the following steps: adopting N, N'-diphenylurea and alkyl dicarbonate as raw material; selecting low-toxicity and high-activity catalyst to heat and reflux under normal pressure to produce carbanilate. The invention makes the reacting condition more mild and reacting course simpler, whichreduces the cost for industrialized manufacturing effectively.
Description
Technical field
The invention belongs to a kind of method of synthesizing phenyl carbamate, specifically with N, the method for N '-diphenyl urea and dialkyl carbonate synthesizing phenyl carbamate.
Background technology
Isocyanic ester is the important organic synthesis intermediate of a class, and it can be widely used in macromolecular materials such as urethane, coating, dyestuff and agricultural chemicals.In traditional isocyanic ester compound probability, above product adopts phosgenation synthetic mostly, and along with the reinforcement day by day of environmental requirement, exploitation non-phosgene synthesis method is to become the crucial problem of chemical field.Wherein with phenyl urethan as reaction intermediate, the synthesis technique of the preparing isocyanate by pyrolyzing by phenyl urethan attracts tremendous attention.
The non-phosgene synthesis technique of phenyl urethan mainly comprises oxidative carbonylation method, reduction of nitrobenzene carbonyl process, carbonic ether method and the diphenyl urea method of aniline.US4629804 has announced with oil of mirbane, methyl alcohol and carbon monoxide are raw material, with ruthenium compound or carbonyl phosphine compound is catalyzer, the about 7MPa of the pressure of carbon monoxide, 160 ℃ of temperature of reaction, the nitrobenzene reduction carbonyl process of synthesizing Amino-methye-formate, US4876379 has announced with aniline, methyl alcohol and carbon monoxide are raw material, with air, oxygen or other compound are oxygenant, muriate with palladium or iron is a catalyzer, pressure 8.6MPa, 160 ℃ of temperature of reaction, the aniline oxidative carbonylation method of synthesizing Amino-methye-formate, but above-mentioned two kinds of synthetic methods need to carry out under High Temperature High Pressure, and reaction conditions is relatively harsher, the operating process more complicated, and have explosive danger.EP0752414 has announced that with methylcarbonate and aniline be raw material, with the zn cpds is catalyzer, 160 ℃ of temperature of reaction, the carbonic ether method of pressurization synthesizing Amino-methye-formate, EP0709363 has announced that with diphenyl urea and methyl alcohol be raw material, do not use catalyzer, 160 ℃ of temperature of reaction, the diphenyl urea method of pressurization synthesizing Amino-methye-formate, carbonic ether method and diphenyl urea method all with the green chemical methylcarbonate of nontoxic pollution-free or diphenyl urea as the carbonylation raw material, operating process is simple, and transformation efficiency and selectivity are all higher, but temperature of reaction is higher, and under the condition of pressurization, and have micromolecular by-product carbinol of equivalent or aniline to generate in this reaction, the Atom economy of reaction is low, a large amount of methyl alcohol and aniline easily generate by product N-monomethylaniline, increase isolating difficulty, reduced usage ratio of equipment, increased production cost.
In order to overcome the above-mentioned shortcoming of carbonic ether method and diphenyl urea method, CN1715267A has announced that with methyl alcohol, diphenyl urea and methylcarbonate be reaction raw materials, 170 ℃ of temperature of reaction, the method of pressurization synthesizing phenyl carbamate under the effect of catalyzer, wherein methyl alcohol is solvent, being again reactant, at first is that the reaction of diphenyl urea and methyl alcohol generates phenyl urethan and aniline, and aniline generates phenyl urethan and methyl alcohol with dimethyl carbonate again.Although this method has finally been stopped the generation of by product aniline, but a large amount of methyl alcohol are as reactant, formed the ternary reaction system of a complexity, and a large amount of methyl alcohol have not only reduced usage ratio of equipment and isolating difficulty as the solvent cycle utilization, also increased industrial energy consumption, temperature of reaction is also higher, and carries out under the condition of pressurization, very is unfavorable for industrial production.
Obtaining after US3627813 is coupled carbonic ether method and diphenyl urea method is reaction raw materials with carbonic ether and diphenyl urea only, with the chlorobenzene is solvent, synthesizing phenyl carbamate in the presence of the organic amine catalyzer, productive rate can reach 79%, although this reaction can be carried out under the non-pressurized condition, operating process is simple, and do not have other reactants and participate in, also not having other by products generates, improved the Atom economy of reaction widely, but because the use of solvent chlorobenzene has not only reduced usage ratio of equipment, also increased separation costs, and because the use of noxious solvent chlorobenzene extremely is unfavorable for environmental protection.
People such as Sunil P.Gupte (Chem.Commun., 2001, be reaction raw materials 2620-2601) with carbonic ether and diphenyl urea, do not use other solvents, 150 ℃ of temperature of reaction are solid catalyst with a kind of silica gel, but the productive rate that obtains phenyl urethan only is 18%.People (J.Mol.Catal.A:Chem.223 (2004) 85-92) such as Anand B.Shivarkar are reaction raw materials with carbonic ether and diphenyl urea, do not use other solvents, 150 ℃ of temperature of reaction, with the Dibutyltin oxide is homogeneous catalyst, under reaction pressure 3.4MPa, the productive rate that obtains phenyl urethan is 77%, but this is reflected at the reaction down of high pressure, high temperature, very is unfavorable for industrial production.
Summary of the invention
The objective of the invention is to overcome the many disadvantages of prior art in the preparation phenyl urethan, thereby the method for not using other solvents, reaction process is simple, energy consumption is low, cost is low non-phosgene synthesizing phenyl carbamate under a kind of normal pressure, the mild conditions, in reaction process is provided.
The objective of the invention is to realize by the following technical solutions:
The method of synthesizing phenyl carbamate provided by the invention is under condition of normal pressure, does not use other solvents, adds high activated catalyst, and under mild conditions, with N, N '-diphenyl urea and dialkyl carbonate are raw material, and reaction obtains phenyl urethan.In this reaction process, the N of a part, the dialkyl carbonate reaction of a N '-diphenyl urea and an one's share of expenses for a joint undertaking generates two molecule phenyl urethans, does not have other by-products and generates, and has improved N greatly, the utilization ratio of the functional group in N '-diphenyl urea and the dialkyl carbonate.
Preparation method of the present invention comprises the steps:
Under condition of normal pressure; N, N '-diphenyl urea, dialkyl carbonate and catalyzer join in the reactor; it (is the boiling point of methylcarbonate that blanketing with inert gas is heated to backflow; about 90 ℃), under reflux state, react and carried out 1～8 hour, wherein; N; the mol ratio of N '-diphenyl urea and dialkyl carbonate is 1:1～20, catalyzer and N, and N '-phenylbenzene weight percent is 1:10～100.
Aforesaid N, N '-diphenyl urea and dialkyl carbonate optimum mole ratio are 1:5～20.
Aforesaid dialkyl carbonate is methylcarbonate or diethyl carbonate.
Aforesaid phenyl urethan is methyl phenyl carbamate and N-phenylurethane.
Aforesaid rare gas element is meant helium, neon, argon gas, nitrogen or carbonic acid gas.
Aforesaid catalyzer is a basic metal, the oxide compound of alkaline-earth metal, alcoholate, acetate or oxyhydroxide, or in the oxide compound of other elements one or more.Catalyzer can be formed by liquid-phase precipitation, metal-salt decomposition or alkali decomposition.
Aforesaid basic metal, alkali earth metal are Li, Na, K, Cs, Mg and Ca.
The oxide compound of aforesaid other elements is Al
2O
3, SiO
2, SnO and ZnO.
In sum, compared with prior art, the present invention has following advantage:
(1) be reflected under the condition of normal pressure and carry out, reaction conditions is gentle more, and easy handling is low for equipment requirements, very is beneficial to industrial production.
(2) the not only active and selectivity height of catalyzer, and low toxicity, cheap and easy to get
(3) do not use other solvents in the reaction process, simplified separating technology.
Embodiment
Embodiment 1
Under condition of normal pressure, N, 0.1 mole of N '-diphenyl urea, 2 moles of methylcarbonates, NaOCH
3Catalyzer 20 grams join in the reactor, and blanketing with inert gas is heated to backflow, reacts under reflux state and carries out 4 hours; reduce to room temperature after the reaction,, analyze with high performance liquid chromatography to the reaction solution sampling; the yield of methyl phenyl carbamate is 88%, and selectivity is 99%.
Embodiment 2
Under condition of normal pressure, N, N '-diphenyl urea 0.2,1 mole of methylcarbonate, Al
2O
3Catalyzer 1.5 grams and CsOH catalyzer 1.5 grams join in the reactor; blanketing with inert gas is heated to backflow; under reflux state, react and carried out 2 hours; reduce to room temperature after the reaction; reaction solution is taken a sample; analyze with high performance liquid chromatography, the yield of methyl phenyl carbamate is 86%, and selectivity is 98%.
Embodiment 3
Under condition of normal pressure, N, N '-diphenyl urea 0.2,2 moles of methylcarbonates, CaO catalyzer 6 gram and KOCH
3Catalyzer 6 grams join in the reactor, and blanketing with inert gas is heated to backflow, reacts under reflux state and carries out 8 hours; reduce to room temperature after the reaction,, analyze with high performance liquid chromatography to the reaction solution sampling; the yield of methyl phenyl carbamate is 89%, and selectivity is 99%.
Embodiment 4
Under condition of normal pressure, N, N '-diphenyl urea 0.2,2 moles of methylcarbonates, SiO
2Catalyzer 3 gram and Al
2O
3Catalyzer 3 grams join in the reactor, and blanketing with inert gas is heated to backflow, reacts under reflux state and carries out 8 hours; reduce to room temperature after the reaction,, analyze with high performance liquid chromatography to the reaction solution sampling; the yield of methyl phenyl carbamate is 85%, and selectivity is 99%.
Embodiment 5
Under condition of normal pressure, N, N '-diphenyl urea 0.2,2 moles of methylcarbonates, KOCH
2CH
3Catalyzer 6 grams join in the reactor, and blanketing with inert gas is heated to backflow; under reflux state, react and carried out 8 hours, reduce to room temperature after the reaction, reaction solution is taken a sample; analyze with high performance liquid chromatography, the yield of N-phenylurethane is 83%, and selectivity is 97%.
Claims (6)
1. the method for a synthesizing phenyl urethane in atmospheric condition is characterized in that the preparation method comprises the steps:
Under condition of normal pressure, N, N '-diphenyl urea, dialkyl carbonate and catalyzer join in the reactor, and blanketing with inert gas is heated to backflow, under reflux state, react and carried out 1～8 hour, wherein, N, the mol ratio of N '-diphenyl urea and dialkyl carbonate is 1: 1～20, catalyzer and N, N '-diphenyl urea weight percent is 1: 10～50;
Described catalyzer is an alkali metal, the oxide compound of alkali earth metal, alcoholate, acetate, oxyhydroxide or nitrate, or Al
2O
3, SiO
2, among SnO and the ZnO one or more;
Described rare gas element is meant helium, neon, argon gas, nitrogen or carbonic acid gas.
2. the method for claim 1, it is characterized in that: described dialkyl carbonate is meant the dialkyl carbonate of the straight or branched of C1～C18.
3. method as claimed in claim 2 is characterized in that: described dialkyl carbonate is methylcarbonate or diethyl carbonate.
4. the method for claim 1, it is characterized in that: described phenyl urethan is meant the carbaniloyl alkyl ester of the straight or branched alkyl of C1～C18.
5. method as claimed in claim 4 is characterized in that: described phenyl urethan is methyl phenyl carbamate or N-phenylurethane.
6. the method for claim 1, it is characterized in that: described alkali metal, alkali earth metal are Li, Na, K, Cs, Mg and Ca.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101124933A CN101130508B (en) | 2006-08-22 | 2006-08-22 | Process for synthesizing phenyl urethane in atmospheric condition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101124933A CN101130508B (en) | 2006-08-22 | 2006-08-22 | Process for synthesizing phenyl urethane in atmospheric condition |
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| Publication Number | Publication Date |
|---|---|
| CN101130508A CN101130508A (en) | 2008-02-27 |
| CN101130508B true CN101130508B (en) | 2011-05-04 |
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|---|---|---|---|
| CN2006101124933A Expired - Fee Related CN101130508B (en) | 2006-08-22 | 2006-08-22 | Process for synthesizing phenyl urethane in atmospheric condition |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190602B (en) * | 2010-03-10 | 2013-07-03 | 中国石油天然气股份有限公司 | Method and equipment for preparing phenyl carbamate through continuous reaction |
| CN102397786A (en) * | 2011-12-02 | 2012-04-04 | 中国科学院山西煤炭化学研究所 | Catalyst for reactive synthesis of carbamate by urea and organic carbonic ester as well as preparation method and application thereof |
| CN103524381A (en) * | 2013-10-14 | 2014-01-22 | 中国科学院山西煤炭化学研究所 | Synthesis of N-methylmethyl carbamate |
| CN106810466B (en) * | 2016-12-30 | 2019-05-10 | 陕西煤业化工技术开发中心有限责任公司 | A method of by aniline and the direct synthesizing Amino-methye methyl formate of urea |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1519131A (en) * | 1976-04-14 | 1978-07-26 | Anic Spa | Productions of aromatic urethanes |
| EP0391473A1 (en) * | 1989-04-07 | 1990-10-10 | ENICHEM SYNTHESIS S.p.A. | Process for producing carbamates |
| CN1546464A (en) * | 2003-12-11 | 2004-11-17 | 中国科学院山西煤炭化学研究所 | Method for synthesizing carbanilate by the reaction of aniline, urea and alcohol |
| CN1715267A (en) * | 2004-06-14 | 2006-01-04 | 中国科学院成都有机化学有限公司 | New process for preparing carbaniloyl ester |
-
2006
- 2006-08-22 CN CN2006101124933A patent/CN101130508B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1519131A (en) * | 1976-04-14 | 1978-07-26 | Anic Spa | Productions of aromatic urethanes |
| EP0391473A1 (en) * | 1989-04-07 | 1990-10-10 | ENICHEM SYNTHESIS S.p.A. | Process for producing carbamates |
| CN1546464A (en) * | 2003-12-11 | 2004-11-17 | 中国科学院山西煤炭化学研究所 | Method for synthesizing carbanilate by the reaction of aniline, urea and alcohol |
| CN1715267A (en) * | 2004-06-14 | 2006-01-04 | 中国科学院成都有机化学有限公司 | New process for preparing carbaniloyl ester |
Non-Patent Citations (2)
| Title |
|---|
| Anand B. Shivarkar,et al.Carbamate synthesis via transfunctionalization of substituted.《Journal of Molecular Catalysis A: Chemical》.2004,第223卷85-92. * |
| Sunil P. Gupte,et al.amate synthesis by solid-base catalyzed reaction of disubstituted.《Chemcomm Communication》.2001,2620-2621. * |
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