CN101468959A - Method for synthesizing hexamethylene carbamate - Google Patents
Method for synthesizing hexamethylene carbamate Download PDFInfo
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- CN101468959A CN101468959A CN 200710308600 CN200710308600A CN101468959A CN 101468959 A CN101468959 A CN 101468959A CN 200710308600 CN200710308600 CN 200710308600 CN 200710308600 A CN200710308600 A CN 200710308600A CN 101468959 A CN101468959 A CN 101468959A
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Abstract
The invention discloses a method for synthesizing cyclohexyl carbamate, which is to select dialkyl carbonate and N,N'-dicyclohexylurea as reactants, control the reaction temperature to be between 100 and 250 DEG C and the reaction pressure to be between 0.5 and 2.0 MPa, and synthesize the cyclohexyl carbamate under the action of a catalyst. The method mainly has the characteristics of mild reaction conditions, cheap and easily obtained catalyst, easy reclaiming, good reusability, economic atomic reaction, high purity of products obtained by separation, small number of byproducts, and high industrial application value.
Description
Technical field
The present invention relates to a kind of synthetic method of cyclohexyl carbamate, specifically catalyzed carbon acid dialkyl ester and N, N '-dicyclohexylurea (DCU) method for synthesizing cyclohexyl carbamate.
Background technology
Isocyanic ester is the important organic synthesis intermediate of a class, is urethane synthetic main raw material, can be widely used in macromolecular materials such as urethane, coating, dyestuff and agricultural chemicals.According to statistics, domestic and international demand to various isocyanic ester is significantly increasing.In traditional isocyanic ester compound probability, most products adopt phosgenation synthetic.Shortcomings such as this synthesis technique exists that route is long, cost is high, raw material is hypertoxic, by-product hydrochloric acid etching apparatus, product residual chlorine are difficult to remove, environmental pollution is serious.Along with the enhancing of environmental consciousness, phosgenation is produced isocyanic ester and is eliminated gradually.The non-phosgene route has become the focus of domestic and international research institution and chemical enterprise concern, is raw material with the carbamate wherein, and the synthesis technique for preparing isocyanic ester by thermo-cracking gets most of the attention.
Carbamate is the raw material of the multiple fine chemicals of preparation, can be used as the intermediate of agricultural chemicals, medicine and organic synthesis.The research of synthesizing carbamic acid ester without phosgene mainly concentrates on the following aspects: the reduction carbonylation of the oxidative carbonylation of aminated compounds, nitro compound, the ammonia of dialkyl carbonate are separated and the alcoholysis of 2-substituted carbamide.Preceding two kinds of reactions are the carbonyl source with CO, and precious metal chemical complex is a catalyzer, under High Temperature High Pressure, carry out, and severe reaction conditions, thus limited their progress and process of industrialization.For back two kinds of reactions, though reaction conditions gentleness, operating process are simple, their are by-product alkohol and amine respectively, has reduced reaction raw materials official energy
The effective rate of utilization of group, Atom economy is relatively poor.
Except that above synthetic route, utilizing dicyclohexylurea (DCU) and dialkyl carbonate synthesizing cyclohexyl carbamate (1) also is a promising non-phosgene route.From reaction (1) as can be seen, the functional group of urea and carbonic ether all is utilized in the reaction raw materials, and Atom economy reaches 100%.
Material carbon acid dialkyl ester and dicyclohexylurea (DCU) can be passed through CO
2Between be bonded into.Because CO
2Unreactiveness, directly utilize CO
2Infeasible substantially as carbonylating agent.But utilize the CO after the activation
2With ammonia or amine urea synthesis or urea, urea or urea alcoholysis obtain active very high carbonylating agent alkyl carbamate or dialkyl carbonate, have very high industrial application value.Therefore, this reaction can promote CO
2Effective utilization, reduce of the influence of its greenhouse to environment, meet the requirement of current Green Chemistry.
In U.S.Pat.No.3190905, use N, N '-dialkyl ureas and dialkyl carbonate are higher than under 200 ℃ in temperature, generate the process of corresponding isocyanic ester and alcohol.Shortcoming: at high temperature, single step reaction N, N '-dialkyl ureas and dialkyl carbonate synthesize corresponding isocyanic ester, cause yield lower.In U.S.Pat.No.3627813, be under 60-200 ℃ in temperature of reaction, under the triethylamine effect, by methylcarbonate and N, N '-diphenyl urea synthesizing Amino-methye-formate, the yield of target product are 71%.In U.S.Pat.No.4381404, be 180 ℃ in temperature of reaction, by diethyl carbonate and N, N '-diphenyl urea synthesizing Amino-methye ethyl formate, target product yield is higher.In U.S.Pat.No.4567287, be under 135 ℃ in temperature of reaction, be under the catalyzer with the aluminium foil, by diethyl carbonate and N, N '-diphenyl urea synthesizing Amino-methye ethyl formate, the yield of target product is 98.2%.At Chem.Commun. such as Sunil P.Gupte, 2001, among the 2620-2621, use carbonic ether and N, N '-2-substituted carbamide is synthetic corresponding carbamate under basic catalyst.Be catalyzer wherein with the Mg-Al hydrotalcite, under 150 ℃ by diphenyl carbonate and N, the reaction of N '-diphenyl urea synthesizing Amino-methye phenyl formate, the yield of target product is 95%.At Green Chem. such as Junjie Gao, 2007,9, among the 572-576, under 90 ℃, with NaOCH
3For catalyzer by methylcarbonate and N, N '-diphenyl urea synthesizing Amino-methye-formate, the yield of its target product are 74.3%.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of cyclohexyl carbamate.
A kind of synthetic method of cyclohexyl carbamate is characterized in that reactant selects dialkyl carbonate and N for use, N '-dicyclohexylurea (DCU), control reaction temperature 100-250 ℃, reaction pressure 0.5-2.0MPa, synthesizing cyclohexyl carbamate under the effect of catalyzer; Wherein catalyzer is selected from NaOCH
3, MgO, Cs
2CO
3, MgCO
3, (BiO)
2CO
3Or KOH.
The structural formula of the dialkyl carbonate described in the present invention is
Wherein R is
—CH
3 —C
2H
5 —C
4H
9 —C
6H
5
Described cyclohexyl carbamate, can carry out continuously, semicontinuously carry out, carry out in batches.For the raw material of described reaction and/or the adding order of catalyzer, there is no particular limitation, can determine the best mode of the adding order of raw material and/or catalyzer orientative experiment (concrete enforcement in the reaction).
If described temperature of reaction is too low, can cause the significantly reduction of speed of reaction; If temperature of reaction is too high, the risk that causes productive rate and/or selectivity to reduce because of disadvantageous side reaction will significantly increase.
Described for catalyst consumption, there is no special qualification, as long as impel reaction to reach enough yields.Preferably, catalyzer and N, the weight ratio of N '-dicyclohexylurea (DCU) is no more than 1:1, particularly preferably, and catalyzer and N, the weight ratio of N '-dicyclohexylurea (DCU) is 0.01:1-0.2:1.
Described for N, the mol ratio of N '-dicyclohexylurea (DCU) and dialkyl carbonate is 1:1～1:40.
The advantage of cyclohexyl carbamate synthetic method of the present invention:
1. reaction conditions is relatively gentleer;
2. operating process is simple;
3. reaction is an atom economy;
4. indirect utilization CO
2
5. catalyzer can be reused;
6. do not need other solubilizing agent;
7. reaction preference and yield height are a kind of satisfy industrialization demand and stronger novel methods of practicality.
Embodiment
The quantitative analysis of described purpose product cyclohexyl carbamate can utilize Agilent 1790 GC to finish, and these Agilent 1790 GC have the kapillary (fid detector) of 30m * 0.25mm * 0.33 μ m.The cyclohexyl carbamate utilizes external standard method quantitative.The qualitative analysis of the byproduct that other of described reaction are possible can utilize HP 6890/5973 GC-MS to finish, and this HP 6890/5973 GC-MS has the capillary column of 30m * 0.25mm * 0.33 μ m and has the chem workstation of NIST spectra database.
Embodiment 1
In the autoclave of 0.5 liter, add methylcarbonate (DMC) 32.4 grams, N, N '-dicyclohexylurea (DCU) (DCU) 4.4 grams, catalyst n aOCH
30.2 gram is 180 ℃ in temperature, pressure is that 1.5MPa and rotating speed are under 500 rev/mins of conditions, keeps temperature, pressure and 5 hours afterreactions of tachyphylaxis to finish.When treating the temperature cool to room temperature, open that reactor sampling obtains a limpid liquid and solid sample 1 is arranged at the bottom, sample 1 is dissolved in the hot ethanol of 60 ℃ of 100ml and carries out stratographic analysis.With hot ethanol solution, under 80 ℃ of 60mmHg, distill ethanol and DMC.Elevated temperature to 140 ℃ then, vacuum tightness remains unchanged, and distillation obtains the cyclohexyl Urethylane.Remain unreacted DCU, catalyzer and minor by-products, use cold alcohol extraction to reclaim DCU and recycle.Catalyzer is separated the extraction of use distilled water, distillation recovery catalyzer with minor by-products.Stratographic analysis cyclohexyl Urethylane yield as a result is 86%, the transformation efficiency of DCU is 90%, the selectivity 96% of cyclohexyl Urethylane, the selectivity 1.0% of by product cyclohexyl isocyanate, the selectivity 2% of hexahydroaniline, the selectivity of N-methylcyclohexylamine are 1.0%.
Embodiment 2
In the autoclave of 2 liters, add methylcarbonate (DMC) 650 grams, N, N '-dicyclohexylurea (DCU) (DCU) 88 grams, catalyzer MgO4 gram, in temperature is 180 ℃, and pressure is that 1.5MPa and rotating speed are under 500 rev/mins of conditions, keeps temperature, pressure and 5 hours afterreactions of tachyphylaxis to finish.When treating the temperature cool to room temperature, open that reactor sampling obtains a limpid liquid and solid sample 1 is arranged at the bottom, sample 1 is dissolved in filtering recovering catalyst in 100ml60 ℃ the hot ethanol, carry out stratographic analysis then.With hot ethanol solution, under 80 ℃ of 60mmHg, distill ethanol and DMC.Elevated temperature to 140 ℃ then, vacuum tightness remains unchanged, and distillation obtains the cyclohexyl Urethylane.Remain unreacted DCU and minor by-products, use cold alcohol extraction to reclaim DCU and recycle.Stratographic analysis cyclohexyl Urethylane yield as a result is 84%, the transformation efficiency of DCU is 89%, the selectivity 94% of cyclohexyl Urethylane, the selectivity 2.0% of by product cyclohexyl isocyanate, the selectivity 3% of hexahydroaniline, the selectivity of N-methylcyclohexylamine are 1.0%.
Embodiment 3
In the autoclave of 0.5 liter, add diethyl carbonate (DEC) 46 grams, N, N '-dicyclohexylurea (DCU) (DCU) 4.4 grams, catalyzer Cs
2CO
30.2 gram is 180 ℃ in temperature, pressure is that 1.0MPa and rotating speed are under 500 rev/mins of conditions, keeps temperature, pressure and 5 hours afterreactions of tachyphylaxis to finish.When treating the temperature cool to room temperature, open that reactor sampling obtains a limpid liquid and solid sample 1 is arranged at the bottom, sample 1 is dissolved in the hot ethanol of 60 ℃ of 100ml and carries out stratographic analysis.With hot ethanol solution, under 90 ℃ of 60mmHg, distill ethanol and DEC.Elevated temperature to 135 ℃ then, vacuum tightness remains unchanged, and distillation obtains the cyclohexyl urethanum.Remain unreacted DCU, catalyzer and minor by-products, use cold alcohol extraction to reclaim DCU and recycle.Catalyzer is separated the extraction of use distilled water, distillation recovery catalyzer with minor by-products.Stratographic analysis cyclohexyl urethanum yield as a result is 88%, the transformation efficiency of DCU is 92%, the selectivity 96% of cyclohexyl urethanum, the selectivity 1.5% of by product cyclohexyl isocyanate, the selectivity 1.5% of hexahydroaniline, the selectivity of N-ethyl cyclohexylamine are 1.0%.
Embodiment 4
In the autoclave of 2 liters, add diethyl carbonate (DEC) 920 grams, N, N '-dicyclohexylurea (DCU) (DCU) 88 grams, catalyzer MgCO
35 grams are 180 ℃ in temperature, and pressure is that 1.0MPa and rotating speed are under 500 rev/mins of conditions, keep temperature, pressure and 5 hours afterreactions of tachyphylaxis to finish.When treating the temperature cool to room temperature, open that reactor sampling obtains a limpid liquid and solid sample 1 is arranged at the bottom, sample 1 is dissolved in the hot ethanol of 60 ℃ of 100ml and carries out stratographic analysis.With hot ethanol solution, under 90 ℃ of 60mmHg, distill ethanol and DEC.Elevated temperature to 135 ℃ then, vacuum tightness remains unchanged, and distillation obtains the cyclohexyl urethanum.Remain unreacted DCU, catalyzer and minor by-products, use cold alcohol extraction to reclaim DCU and recycle.Catalyzer is separated the extraction of use distilled water, distillation recovery catalyzer with minor by-products.Stratographic analysis cyclohexyl urethanum yield as a result is 86%, the transformation efficiency of DCU is 90%, the selectivity 96% of cyclohexyl urethanum, the selectivity 1.5% of by product cyclohexyl isocyanate, the selectivity 1.5% of hexahydroaniline, the selectivity of N-ethyl cyclohexylamine are 1.0%.
Embodiment 5
In the autoclave of 0.5 liter, add dibutyl carbonate (DBC) 62 grams, N, N '-dicyclohexylurea (DCU) (DCU) 4.4 grams, catalyzer (BiO)
2CO
30.2 gram is 180 ℃ in temperature, pressure is that 0.8MPa and rotating speed are under 500 rev/mins of conditions, keeps temperature, pressure and 5 hours afterreactions of tachyphylaxis to finish.When treating the temperature cool to room temperature, open that reactor sampling obtains a limpid liquid and solid sample 1 is arranged at the bottom, sample 1 is dissolved in 100ml60 ℃ the hot ethanol and carries out stratographic analysis.With hot ethanol solution, under 100 ℃ of 60mmHg, distill ethanol and DBC.Elevated temperature to 145 ℃ then, vacuum tightness remains unchanged, and distillation obtains the cyclohexyl butyl carbamate.Remain unreacted DCU, catalyzer and minor by-products, use cold alcohol extraction to reclaim DCU and recycle.Catalyzer is separated the extraction of use distilled water, distillation recovery catalyzer with minor by-products.Stratographic analysis cyclohexyl butyl carbamate yield as a result is 89%, the transformation efficiency of DCU is 93%, the selectivity 96% of hexamethylene amino based butyl formate, the selectivity 2.0% of by product cyclohexyl isocyanate, the selectivity 1.0% of hexahydroaniline, the selectivity of N-butyl hexahydroaniline is 1.0%.
Embodiment 6
In the autoclave of 2 liters, add dibutyl carbonate (DBC) 1200 grams, N, N '-dicyclohexylurea (DCU) (DCU) 88 grams, catalyzer KOH5 gram, in temperature is 180 ℃, and pressure is that 0.8MPa and rotating speed are under 500 rev/mins of conditions, keeps temperature, pressure and 5 hours afterreactions of tachyphylaxis to finish.When treating the temperature cool to room temperature, open that reactor sampling obtains a limpid liquid and solid sample 1 is arranged at the bottom, sample 1 is dissolved in 100ml60 ℃ the hot ethanol and carries out stratographic analysis.With hot ethanol solution, under 100 ℃ of 60mmHg, distill ethanol and DBC.Elevated temperature to 145 ℃ then, vacuum tightness remains unchanged, and distillation obtains the cyclohexyl butyl carbamate.Remain unreacted DCU, catalyzer and minor by-products, use cold alcohol extraction to reclaim DCU and recycle.Catalyzer is separated the extraction of use distilled water, distillation recovery catalyzer with minor by-products.Stratographic analysis cyclohexyl butyl carbamate yield as a result is 88%, the transformation efficiency of DCU is 92%, the selectivity 96% of cyclohexyl butyl carbamate, the selectivity 2.0% of by product cyclohexyl isocyanate, the selectivity 1.0% of hexahydroaniline, the selectivity of N-butyl hexahydroaniline is 1.0%.
Claims (3)
1, a kind of synthetic method of cyclohexyl carbamate, it is characterized in that reactant selects dialkyl carbonate and N for use, N '-dicyclohexylurea (DCU), control reaction temperature 100-250 ℃, reaction pressure 0.5-2.0MPa, synthesizing cyclohexyl carbamate under the effect of catalyzer; Wherein catalyzer is selected from NaOCH
3, MgO, Cs
2CO
3, MgCO
3, (BiO)
2CO
3Or KOH.
2, the method for claim 1 is characterized in that the structural formula of dialkyl carbonate is
Wherein R is-CH
3-C
2H
5-C
4H
9-C
6H
5
3, the method for claim 1 is characterized in that N, and the mol ratio of N '-dicyclohexylurea (DCU) and dialkyl carbonate is 1:1～1:40.
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| CN 200710308600 CN101468959A (en) | 2007-12-28 | 2007-12-28 | Method for synthesizing hexamethylene carbamate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483224A (en) * | 2013-10-14 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | Substituted urea alcoholysis method for synthesizing carbamate compounds |
| CN106478459A (en) * | 2016-08-29 | 2017-03-08 | 吴琦琪 | A kind of method that cyclohexyl carbamate is prepared in catalysis |
| CN108732290A (en) * | 2018-05-22 | 2018-11-02 | 威海迪素制药有限公司 | A kind of detection method of Glipizide genotoxicity impurity |
| CN112479931A (en) * | 2020-12-09 | 2021-03-12 | 安徽广信农化股份有限公司 | Synthesis process of cyclohexyl |
| 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 |
-
2007
- 2007-12-28 CN CN 200710308600 patent/CN101468959A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483224A (en) * | 2013-10-14 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | Substituted urea alcoholysis method for synthesizing carbamate compounds |
| CN106478459A (en) * | 2016-08-29 | 2017-03-08 | 吴琦琪 | A kind of method that cyclohexyl carbamate is prepared in catalysis |
| CN108732290A (en) * | 2018-05-22 | 2018-11-02 | 威海迪素制药有限公司 | A kind of detection method of Glipizide genotoxicity impurity |
| CN112479931A (en) * | 2020-12-09 | 2021-03-12 | 安徽广信农化股份有限公司 | Synthesis process of cyclohexyl |
| 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 |
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Open date: 20090701 |