CN106397271A - Method for synthesis of N-substituted dicarbamate with urea as carbonyl source - Google Patents
Method for synthesis of N-substituted dicarbamate with urea as carbonyl source Download PDFInfo
- Publication number
- CN106397271A CN106397271A CN201610771198.2A CN201610771198A CN106397271A CN 106397271 A CN106397271 A CN 106397271A CN 201610771198 A CN201610771198 A CN 201610771198A CN 106397271 A CN106397271 A CN 106397271A
- Authority
- CN
- China
- Prior art keywords
- polyureas
- catalyst
- alcohol
- carbamide
- nitrogen
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesis of N-substituted dicarbamate with urea as a carbonyl source; the method comprises the steps of taking a non precious metal composite oxide as a catalyst, taking polyurea, urea and alcohol as raw materials, and carrying out a reaction at the temperature of 180-220 DEG C for 10-22 hours to obtain N-substituted dicarbamate; an active component of the catalyst is a complex of two non precious metal oxides of zinc, copper, titanium and niobium. The method has the advantages of high conversion rate, high yield, high catalyst activity and good stability, and can be reused.
Description
Technical field
The present invention relates to degrading with carbamide for the polyureas in carbonyl source under a kind of catalyst action in non-noble metal composite oxide
The method that synthetic nitrogen replaces diurethane.
Background technology
Carbamate is the important fine chemicals of a class, can be used as organic synthesis intermediate, with unsaturated hydrocarbons, aldehyde
The functional group reactionses such as ketone, polyhydric alcohol and aromatic ring, generate the derivant of various uses, such as isocyanates, polyurethane, dialkyl carbonate
Ester, melamine derivative and various heterocyclic compound.Meanwhile, such compound also is used as pesticide, medicine and synthesis
Resin modified intermediate, such as antimicrobial drug, anticarcinogen, Insecticides (tech) ＆ Herbicides (tech) etc..Additionally, in polypeptide and combinatorial chemistry field, amino
Formic acid esters are also a kind of effective amino protecting groups and functional group's linking agent.Therefore, with carbamate application
Constantly expand, the clean and effective synthesis of such compound gets the attention.
The traditional synthetic method of carbamate is mainly with hypertoxic phosgene as raw material, obtains through alcoholysis and amine solution.Existing
Non-phosgene synthetic method be mainly with CO, dialkyl carbonate, CO2With alkyl carbamate etc. for carbonylation agent conjunction
Become route.Using CO as the process of non-phosgene carbonylation agent, be Pd that is expensive with active component and being easy to run off, Pt, Ru,
The coordination compound of the noble metals such as Rh, Ir is catalyst, and separation and recovery of catalyst is difficult and reusability is poor, and CO utilization rate is only
1/3, and have that CO toxicity is big and the CO of by-product2The problems such as separate difficult.Reaction needs to carry out under high-temperature and high-pressure conditions, deposits
Mix the danger that blast occurs in CO at high temperature under high pressure with oxygen, limit CO application in this process.Dialkyl carbonate
Ester is a kind of green chemical that developed recently gets up, and wherein N- is synthesized with dimethyl carbonate for carbonylation agent and amine and takes
Research for carbamate is more.This process condition is gentle, raw material environmental friendliness, and the methanol of by-product can recycle in
Synthesis of dimethyl carbonate, is a kind of chemical process of green relatively.But dimethyl carbonate large usage quantity in course of reaction, and and
Methanol easily forms common waste, is not readily separated.And at present, the price of dimethyl carbonate also costly, seriously hinders
Its large-scale industrialization promotion and application.CO2It is used for synthesizing N- substituted-amino formic acid as the important and cheap carbonyl source of a class
Ester is CO2The study hotspot in recycling field.With CO2Synthesize the process of N- substituted carbamate for carbonylation agent, can
It is prevented effectively from the use of hypertoxic phosgene and CO, meets the theme of current Green Chemistry, also for CO2Recycling provide one
Plant effective approach.But because of CO2, it is more difficult to activate, the yield of the method target product is relatively low for the chemical inertness of itself.Therefore, open
Sending out catalyst that is efficient, easily reclaiming is CO2Urgent problem during recycling.Alkyl carbamate is permissible
By carbamide and small molecular alcohol degraded synthesis, compare dimethyl carbonate preparation process simply, price is relatively low, does not exist and first
Alcohol forms the problem of azeotropic mixture, thus causing to separate difficulty；Ratio CO small toxicity, using comparatively safe；Compare CO2Reactivity is high,
It is the efficient carbonylation agent of a class developed in recent years, be widely used in the synthesis of N- substituted carbamate.But
Should during catalyst easy in inactivation, the serious, reusability of running off poor.In consideration of it, being badly in need of developing a kind of efficient solid catalysis
Agent is to meet industrial demand.
In sum, the new carbonylation agent of research and development and catalysis activity is high, long service life and segregative non-
Homogeneous catalyst is the key in carbamate preparation process.
Content of the invention
It is an object of the invention to provide a kind of method that diurethane is replaced for carbonyl source synthetic nitrogen with carbamide.
The present invention is with diamine compounds and CO2Reacting the polyureas preparing is raw material, with carbamide cheap and easy to get is
Carbonylation agent, with non-noble metal composite oxide as catalyst, the synthetic nitrogen for polyureas degraded high conversion, high yield takes
For diurethane.Wherein polyureas conversion ratio is up to 96%, and product nitrogen replaces diurethane yield and is up to 92%, and
And almost do not have alkylating carbamate to generate.
A kind of method with carbamide for carbonyl source synthetic nitrogen replacement diurethane is it is characterised in that be combined with base metal
Oxide is catalyst, with polyureas, carbamide, alcohol as raw material, obtains final product within 10～22 hours nitrogen in 180～220 DEG C of reactions and replaces diamino
Carbamate；The active component of described catalyst is the complex of 2 kinds of non-noble metal oxides in zinc, copper, titanium and niobium.
In the complex of described 2 kinds of non-noble metal oxides, the mol ratio of 2 kinds of metallic elements is 0.5～2.
The precursor of described catalyst is nitrate, carbonate or oxide, the sintering temperature in its preparation process is 300～
1000 ℃.
The consumption of described catalyst is 7～13 wt% of polyureas consumption.
Described polyureas is butanediamine polyureas, hexamethylene diamine polyureas, 4,4- dicyclohexyl methyl hydride diamidogen polyureas, isophorone diamine
Polyureas or m-xylene diamine polyureas.
Described alcohol is methanol, ethanol, butanol, n-amyl alcohol, Hexalin or benzyl alcohol.
The mol ratio of described polyureas, carbamide and alcohol is 1:1.5:10～40.
The implementation process of the present invention is：Add catalyst, polyureas, carbamide and alcohol in autoclave, it is warming up to 180～
220 DEG C, react 10～22 h.Reaction terminates, and after the cooling of question response liquid, reclaims catalyst, gained by sedimentation or filtration separation
Catalyst is after ethanol or the simple cleaning-drying of acetone, you can reuse.After reaction, product is through gas chromatogram（GC）, makings connection
With（GC-MS）Carry out qualitative and quantitative analysis.
Advantage compared with traditional carbamate production method for the present invention：
1st, the present invention is with polyureas, carbamide and alcohol as raw material, cheap is easy to get.Wherein polyureas and carbamide all can be by CO2Synthesis, because
This this process can realize CO indirectly2, diamidogen and alcohol one-step synthesis carbamate, its by-product only has water, environmental friendliness, atom
Utilization rate is high, meets the requirement of green chemistry.
2nd, catalyst activity of the present invention is high, not easy in inactivation.The consumption of catalyst is 7～13 wt% of polyureas consumption, reaction
Carry out at 180～220 DEG C, react 10～22 h, you can the synthesis of effective catalytic amino formic acid esters, yield> 78%.
3rd, catalyst stability of the present invention is good, easily regenerates, reusable.It is multiple that catalyst of the present invention belongs to base metal
Close oxide catalyst, solve the problems, such as that homogeneous catalyst is separated with product difficulty, is not easily recycled recycling, both reduced operation
Expense, improves product quality again.
Specific embodiment
For a better understanding of the present invention, it is illustrated further with reference to embodiment, but these embodiments should not be managed
Solve as any limitation of the invention.
1）The preparation coprecipitation of copper zinc composite oxide catalyst
Copper nitrate, zinc nitrate are presoma, and the sodium carbonate precipitant of 1.5 mol/L is titrated to pH=9-11, and precipitate is in 70 DEG C
Aging 12 hours, gained precipitation was repeatedly washed to neutrality through distilled water, 80 DEG C of dryings 12 hours, and 300～700 DEG C of roastings obtain
Pulverulent solids, are labeled as xCuO-yZnO-Z, the wherein span for 0.5～2, y for the span of x is 0.5～2, Z generation
Table sintering temperature.
Embodiment 1
114 g butanediamine polyureas, 90 g technical grade carbamide, 8.2 g above-mentioned CuO-ZnO-500 catalyst, 1750 mL ethanol, plus
Enter 5L stainless steel cauldron, closed reactor, after nitrogen purging, be warming up to 200 DEG C of reaction 20 h, period is purged with nitrogen, control
Nitrogen flow rate 20 L/h processed, after the cooling of question response liquid, catalyst is recovered by filtration, and products therefrom adds internal standard substance biphenyl, warp
Inner mark method ration is analyzed, and the selectivity that the conversion ratio of gained polyureas replaces bisurethane for 93%, N- is 98%.
Embodiment 2
142g hexamethylene diamine polyureas, 90 g technical grade carbamide, 8.2 g above-mentioned CuO-ZnO-500 catalyst, 1750 mL ethanol, plus
Enter 5L stainless steel cauldron, closed reactor, after nitrogen purging, be warming up to 200 DEG C of reaction 20 h, after the cooling of question response liquid, phase
Between with nitrogen purging, control nitrogen flow rate 20 L/h, catalyst is recovered by filtration, products therefrom adds internal standard substance biphenyl, warp
Inner mark method ration is analyzed, and the selectivity that the conversion ratio of gained polyureas replaces bisurethane for 92%, N- is 96%.
Embodiment 3
236 g 4,4- dicyclohexyl methyl hydride diamidogen polyureas, 90 g technical grade carbamide, 8.2 g above-mentioned CuO-ZnO-500 catalyst,
1750 mL ethanol, add 5L stainless steel cauldron, closed reactor, after nitrogen purging, are warming up to 200 DEG C of reaction 22 h, phase
Between with nitrogen purging, control nitrogen flow rate 20 L/h, question response liquid cooling after, catalyst is recovered by filtration, and products therefrom adds
Enter internal standard substance biphenyl, through inner mark method ration analysis, the conversion ratio 88% of gained polyureas, N- replaces the selection of bisurethane
Property 97%.
Embodiment 4
206 g isophorone diamine polyureas, 90 g technical grade carbamide, 8.2 g above-mentioned CuO-ZnO-500 catalyst, 1750 mL second
Alcohol, adds 5L stainless steel cauldron, closed reactor, after nitrogen purging, is warming up to 200 DEG C of reaction 22 h, period is blown with nitrogen
Sweep, control nitrogen flow rate 20 L/h, after the cooling of question response liquid, catalyst is recovered by filtration, and products therefrom adds internal standard Internet of Things
Benzene, through inner mark method ration analysis, the conversion ratio of gained polyureas is the selectivity 96% that 83%, N- replaces bisurethane.
Embodiment 5
162g m-xylene diamine polyureas, 90 g technical grade carbamide, 8.2 g above-mentioned CuO-ZnO-500 catalyst, 1750 mL ethanol,
Add 5L stainless steel cauldron, closed reactor, after nitrogen purging, be warming up to 200 DEG C of reaction 22 h, period is purged with nitrogen,
Control nitrogen flow rate 20 L/h, after the cooling of question response liquid, catalyst is recovered by filtration, and products therefrom adds internal standard substance biphenyl,
Through inner mark method ration analysis, the conversion ratio of gained polyureas is the selectivity 98% that 83%, N- replaces bisurethane.
Embodiment 6
142g hexamethylene diamine polyureas, 90 g technical grade carbamide, the above-mentioned CuO-ZnO-500 catalyst using after five times of 8.2 g,
1750 mL ethanol, add 5L stainless steel cauldron, closed reactor, after nitrogen purging, are warming up to 200 DEG C of reaction 22 h, phase
Between with nitrogen purging, nitrogen flow rate 20 L/h, question response liquid cooling after, catalyst is recovered by filtration, products therefrom add in
Mark Internet of Things benzene, through inner mark method ration analysis, the conversion ratio of gained polyureas is the selectivity that 94%, N- replaces bisurethane
For 95%.
2）The preparation of niobium titanium compound oxide catalyst
Potassium carbonate, titanium dioxide and niobium pentaoxide are fully ground as after certain mixed in molar ratio, under nitrogen protection will
It is placed in 1000 DEG C of tubular type kiln roastings 12 hours, is cooled to after room temperature fully washing, 80 DEG C of dryings 2 hours.Take a certain amount of
The nitric acid of 65-68% is processed, gained sample with aminopropyl trimethoxysilane neutralize a week, finally scrubbed, 80 DEG C do
Dry 2 hours standby after 400-600 DEG C of roasting.Obtain pulverulent solids, be labeled as TixNbyO-Z, wherein x, y represents titanium niobium
Mol ratio, its span is 0.5～2；Z represents sintering temperature, and its value is 400,500,600.
Embodiment 7
114 g butanediamine polyureas, 90 g technical grade carbamide, the above-mentioned Ti of 8.2 g1Nb1O-400 catalyst, 1167 mL ethanol, plus
Enter 5L stainless steel cauldron, closed reactor, after nitrogen purging, be warming up to 200 DEG C of reaction 14 h, period is purged with nitrogen, control
Nitrogen flow rate 20 L/h processed, after the cooling of question response liquid, catalyst is recovered by filtration, and products therefrom adds internal standard substance biphenyl, warp
Inner mark method ration is analyzed, and the conversion ratio of gained polyureas is the selectivity 99% that 96%, N- replaces bisurethane.
Embodiment 8
142g hexamethylene diamine polyureas, 90 g technical grade carbamide, the above-mentioned Ti of 8.2 g1Nb1O-400 catalyst, 1167mL ethanol, add
5L stainless steel cauldron, closed reactor, after nitrogen purging, it is warming up to 200 DEG C of reaction 14 h, after the cooling of question response liquid, period
With nitrogen purging, control nitrogen flow rate 20 L/h, catalyst is recovered by filtration, products therefrom adds internal standard substance biphenyl, through interior
Standard quantitative analysis, the conversion ratio 94% of gained polyureas, N- replaces the selectivity 97% of bisurethane.
Embodiment 9
236 g 4,4- dicyclohexyl methyl hydride diamidogen polyureas, 90 g technical grade carbamide, the above-mentioned Ti of 8.2 g1Nb1O-400 catalyst,
1167 mL ethanol, add 5L stainless steel cauldron, closed reactor, after nitrogen purging, are warming up to 200 DEG C of reaction 16 h, phase
Between with nitrogen purging, control nitrogen flow rate 20 L/h, question response liquid cooling after, catalyst is recovered by filtration, and products therefrom adds
Enter internal standard substance biphenyl, through inner mark method ration analysis, the conversion ratio 86% of gained polyureas, N- replaces the selection of bisurethane
Property 96%.
Embodiment 10
206 g isophorone diamine polyureas, 90 g technical grade carbamide, the above-mentioned Ti of 8.2 g1Nb1O-400 catalyst, 1167 mL second
Alcohol, adds 5L stainless steel cauldron, closed reactor, after nitrogen purging, is warming up to 200 DEG C of reaction 16 h, period is blown with nitrogen
Sweep, control nitrogen flow rate 20 L/h, after the cooling of question response liquid, catalyst is recovered by filtration, and products therefrom adds internal standard Internet of Things
Benzene, through inner mark method ration analysis, the selectivity that the conversion ratio of gained polyureas replaces bisurethane for 82%, N- is 96%.
Embodiment 11
142g hexamethylene diamine polyureas, 90 g technical grade carbamide, the above-mentioned Ti using after 3 times of 8.2 g1Nb1O-400 catalyst, 1167
ML ethanol, adds 5L stainless steel cauldron, closed reactor, after nitrogen purging, is warming up to 200 DEG C of reaction 16 h, period nitrogen
Air-blowing is swept, nitrogen flow rate 20 L/h, and after the cooling of question response liquid, catalyst is recovered by filtration, and products therefrom adds internal standard Internet of Things
Benzene, through inner mark method ration analysis, the selectivity that the conversion ratio of gained polyureas replaces bisurethane for 92%, N- is 95%.
Embodiment 12
After terminating as the course of reaction in embodiment 1, the recycling step of subsequent product is：After the cooling of question response liquid, catalyst leads to
It is recovered by filtration, 20～50 DEG C of rotary evaporations reclaim unnecessary ethanol, 70～90 DEG C of decompression steamings take diethyl carbonate（diethyl
Carbonate, DEC）, it is urethanes that extracting waste solid is steamed in 100～120 DEG C of decompressions（Ethyl carbamate, EC）,
The white solid that residue obtains is 1,6- hexamethylene diamine base butyl formate（Dibutyl hexamethylenedicarbamate,
BHDC）, its purity can reach 99%.
Analytical test strip part
After reaction, products therefrom adds internal standard substance biphenyl, through inner mark method ration analysis, using Agilent Technologies
7890A gas chromatography system quantitative analyses.Chromatographic condition is：The capillary of chromatographic column 30 m × 0.25 mm × 0.33 μm
Pipe, hydrogen flameionization（FID）Detector.Qualitative analyses utilize Agilent Technologies 7890B-5977A GC-MS
Complete, chromatographic condition is：The capillary tube of chromatographic column 30 m × 0.25 mm × 0.25 μm, EI ion source, long-acting high-energy
Electron multiplier detector.
Claims (7)
1. a kind of the method for diurethane is replaced it is characterised in that with base metal composite oxygen for carbonyl source synthetic nitrogen with carbamide
Compound is catalyst, with polyureas, carbamide, alcohol as raw material, obtains final product within 10～22 hours nitrogen in 180～220 DEG C of reactions and replaces diaminourea
Formic acid esters；The active component of described catalyst is the complex of 2 kinds of non-noble metal oxides in zinc, copper, titanium and niobium.
2. the method for claim 1 is it is characterised in that 2 kinds of metals in the complex of described 2 kinds of non-noble metal oxides
The mol ratio of element is 0.5～2.
3. the method for claim 1 is it is characterised in that the precursor of described catalyst is nitrate, carbonate or oxidation
Thing, the sintering temperature in its preparation process is 300～1000 DEG C.
4. the method for claim 1 is it is characterised in that the mol ratio of described polyureas, carbamide and alcohol is 1:1.5:10～
40.
5. the method for claim 1 is it is characterised in that the consumption of described catalyst is 7～13 wt% of polyureas consumption.
6. the method as described in claim 1,4 or 5 it is characterised in that described polyureas be butanediamine polyureas, hexamethylene diamine polyureas, 4,
4- dicyclohexyl methyl hydride diamidogen polyureas, isophorone diamine polyureas or m-xylene diamine polyureas.
7. the method as described in claim 1 or 4 is it is characterised in that described alcohol is methanol, ethanol, butanol, n-amyl alcohol, Hexalin
Or benzyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610771198.2A CN106397271A (en) | 2016-08-31 | 2016-08-31 | Method for synthesis of N-substituted dicarbamate with urea as carbonyl source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610771198.2A CN106397271A (en) | 2016-08-31 | 2016-08-31 | Method for synthesis of N-substituted dicarbamate with urea as carbonyl source |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106397271A true CN106397271A (en) | 2017-02-15 |
Family
ID=58004089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610771198.2A Pending CN106397271A (en) | 2016-08-31 | 2016-08-31 | Method for synthesis of N-substituted dicarbamate with urea as carbonyl source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397271A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734626A (en) * | 2019-01-03 | 2019-05-10 | 中国科学院兰州化学物理研究所 | A kind of thermal cracking isocyanates forms the depolymerization method of polymer in the process |
| CN114315649A (en) * | 2022-03-15 | 2022-04-12 | 中国科学院过程工程研究所 | Method for purifying ethyl xylylene dicarbamate by melt crystallization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0437258A1 (en) * | 1990-01-12 | 1991-07-17 | Nkk Corporation | Method of manufacturing aromatic urethane |
| CN1365969A (en) * | 2001-01-16 | 2002-08-28 | 西北大学 | Process for preparing aminoformate |
| CN103980161A (en) * | 2014-05-15 | 2014-08-13 | 上海沣勃新材料科技有限公司 | Method for synthesizing aliphatic/cycloaliphatic dicarbamate by one-pot reaction process |
| CN104761454A (en) * | 2014-01-07 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Method for direct synthesis of diethyl carbonate and simultaneously by-production of ethyl carbamate through urea alcoholysis |
-
2016
- 2016-08-31 CN CN201610771198.2A patent/CN106397271A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0437258A1 (en) * | 1990-01-12 | 1991-07-17 | Nkk Corporation | Method of manufacturing aromatic urethane |
| CN1365969A (en) * | 2001-01-16 | 2002-08-28 | 西北大学 | Process for preparing aminoformate |
| CN104761454A (en) * | 2014-01-07 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Method for direct synthesis of diethyl carbonate and simultaneously by-production of ethyl carbamate through urea alcoholysis |
| CN103980161A (en) * | 2014-05-15 | 2014-08-13 | 上海沣勃新材料科技有限公司 | Method for synthesizing aliphatic/cycloaliphatic dicarbamate by one-pot reaction process |
Non-Patent Citations (3)
| Title |
|---|
| QINGHE LI等: "Catalytic degradation of polyurea: synthesis of N-substituted carbamates with CuO–ZnO as the catalyst", 《GREEN CHEMISTRY》 * |
| 尚建鹏等: "MgO-ZnO复合氧化物催化聚脲与碳酸二烷基酯原子经济反应合成N-取代的氨基甲酸酯", 《中国化学会第28届学术年会第1分会场摘要集》 * |
| 王娜等: "尿素羰基化作用研究进展", 《化学通报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734626A (en) * | 2019-01-03 | 2019-05-10 | 中国科学院兰州化学物理研究所 | A kind of thermal cracking isocyanates forms the depolymerization method of polymer in the process |
| CN109734626B (en) * | 2019-01-03 | 2021-06-22 | 中国科学院兰州化学物理研究所 | Depolymerization method for forming polymer in isocyanate preparation process by thermal cracking |
| CN114315649A (en) * | 2022-03-15 | 2022-04-12 | 中国科学院过程工程研究所 | Method for purifying ethyl xylylene dicarbamate by melt crystallization |
| CN114315649B (en) * | 2022-03-15 | 2022-05-24 | 中国科学院过程工程研究所 | Method for purifying ethyl xylylene dicarbamate by melt crystallization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jayarathne et al. | Selective iron-catalyzed N-formylation of amines using dihydrogen and carbon dioxide | |
| Cenini et al. | Ruthenium carbonyl catalyzed reductive carbonylation of aromatic nitro compounds. A selective route to carbamates | |
| CN111187148B (en) | Method for simultaneously preparing o-hydroxy phenetole and 1, 3-benzodioxole-2-one | |
| JP6049757B2 (en) | Process for the production of secondary amines in the liquid phase | |
| CN109438215A (en) | A kind of method of carbonylation synthesis phenylacetic acid | |
| SG190750A1 (en) | Method for producing and purifying 3-aminopropanol | |
| CN104355955B (en) | Method for synthetizing carbamate | |
| CN104829493A (en) | Synthetic method for romatic carbamic acid ester | |
| CN105237434A (en) | Method for producing cyclohexanone oxime | |
| CN106397271A (en) | Method for synthesis of N-substituted dicarbamate with urea as carbonyl source | |
| CN103172538A (en) | Method for synthesis of carbamate under mild conditions | |
| KR101540636B1 (en) | Process for preparing N,N'-substituted urea derivatives using cerium dioxide catalyst | |
| WO2013178693A1 (en) | Method for producing a mono-n-alkyl piperazine | |
| JPH0730059B2 (en) | Method for producing N-methylpiperazine | |
| CN109734626B (en) | Depolymerization method for forming polymer in isocyanate preparation process by thermal cracking | |
| CN101468957A (en) | Method for synthesizing diamino formic ether | |
| CN114436897A (en) | Preparation method and preparation device of p-trifluoromethoxyphenyl isocyanate | |
| CN106946668A (en) | A kind of method that phenol hydrogenation prepares cyclohexanone | |
| CN111574380A (en) | Method for preparing 4,4 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by reduction coupling method | |
| CN114591185B (en) | Method for selectively preparing alkamine from ethylene glycol and nitroarene | |
| CN101468960A (en) | Process for preparing phenyl urethane | |
| CN114478320A (en) | Production method and production device of phenyl isocyanate | |
| CN104292113A (en) | Preparation method of 3-chloro-4-fluoroaniline | |
| Alinezhad et al. | Reductive amination of aldehydes and ketones in a heterogeneous system in THF and under solvent-free conditions using sodium borohydride-silica phosphoric acid | |
| Cao et al. | Oxidative Carbonylation of Amines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170215 |