CN1277959A - Method for preparing urea derivatives by catalytic oxidation and carbonylation of amine - Google Patents
Method for preparing urea derivatives by catalytic oxidation and carbonylation of amine Download PDFInfo
- Publication number
- CN1277959A CN1277959A CN 00104412 CN00104412A CN1277959A CN 1277959 A CN1277959 A CN 1277959A CN 00104412 CN00104412 CN 00104412 CN 00104412 A CN00104412 A CN 00104412A CN 1277959 A CN1277959 A CN 1277959A
- Authority
- CN
- China
- Prior art keywords
- reaction
- carbonylation
- amine
- urea derivatives
- sulfuric acid
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method of preparing carbamide derivative by amine compound catalytic oxidation and oxonation reactions. Ziroconium dioxide carried palladium is used as catalyst, the mixture of carbon monoxide and oxygen under 3.5-4.5MPa pressure and reaction temp. of 120-160 deg.C as oxidation and oxonation catalyst to catalytic oxidize and oxonize different organic amines to prepare correspodent carbamide derivative. The total yield of symmetrical carbamide derivative can be up to 90-99%, and its purity can be equal to or higher than 99.0%.
Description
The present invention relates to a kind of clean catalytic oxidization oxonation amine and produce the method for urea derivatives.
Urea derivatives is organic reaction intermediate and the pharmaceutical intermediate that a class has extensive use.Traditional production method is to use aminated compounds and isocyanic ester or phosgene reaction to realize.In these reactions, all relate to the phosgene that uses severe toxicity inevitably, and have a large amount of corrosive gases hydrogenchloride to emit in the reaction.Use the method for catalyzed oxidation carbonylation or reduction carbonylation itrogenous organic substance, direct reaction is produced corresponding symmetric or asymmetric urea, is one and considers all very favorable route from environment and economic aspect.In research work in the past, what generally use is that the macromole of precious metals such as palladium, ruthenium, rhodium contains the nitrogen complex homogeneous catalysis system or with sulphur, the selenium catalyzer as main active component.The former catalyst preparation process relative complex also need be added other promotor, with the reaction system separation difficulty and easily run off; Latter's activity is lower and very big toxicity is arranged, even Determination of Trace Selenium remnants also can cause serious pollution to product.Recently, produce urea derivatives under the katalysis that Hayashi etc. (USP 5902889) claims to use primary amine and cyclic carbonate to be reflected at sodium alkoxide.But the cyclic carbonate price is relatively costly, is unfavorable for industrial application.
The object of the present invention is to provide a kind of environmental friendliness, the method for preparing carbamide derivative by catalytic oxidation and oxonation of amine efficiently.
The present invention realizes by following measure:
Use sulfuric acid to modify the palladium catalyst that zirconium dioxide supports among the present invention.Catalyzer involved in the present invention is compared with traditional oxidative carbonylation catalyst system, and maximum difference is that to have adopted the zirconium white of sulphating be the relative simple catalyst system that carrier and palladium constitute, and has catalyzed oxidation and carbonylation function simultaneously.The macromole that does not need the preparation process relative complex contain nitrogen complex-palladium homogeneous catalysis system and reaction medium separate with catalyst system easy in, can under gentle relatively reaction conditions, obtain urea derivatives with high yield.
The method of preparing urea derivatives by catalytic oxidation and carbonylation of amine involved in the present invention, it is characterized in that reaction substrate selects fat or aromatic series organic amine for use, the zirconium dioxide loaded palladium of modifying with sulfuric acid is as catalyzer, in reaction pressure is 3.5-4.5MPa, under 120 ℃-160 ℃ of the temperature of reaction, use the mixed gas of carbon monoxide and oxygen to be the oxidative carbonylation agent, the corresponding urea derivatives of organic amine system that the catalyzed oxidation carbonylation is different.Wherein, the consumption of the zirconium dioxide carried palladium catalyst that sulfuric acid is modified is the 2-3.5% of fat or aromatic series organic amine weight, zirconia carrier is handled through the 0.5-1.0 mol sulfuric acid, and the weight percentage of sulfate radical is 1-5%, and the weight percentage of activity of such catalysts component palladium is 3-10%.
The present invention is the oxidative carbonylation agent with pure oxygen and carbon monoxide.The pressure ratio of oxygen and carbon monoxide is 1: 9-3, and reaction pressure is 3.5-4.5MPa, and temperature of reaction is 120-160 ℃, and the reaction times is 0.5-2 hour.
The present invention is a solvent with second cyanogen or aniline, and the weight ratio of reaction substrate and quantity of solvent is 1: 7.5-15.The weight ratio of catalyst levels and reaction substrate is 2-3.5%.
The typical building-up process of related catalyzer is among the present invention: under the normal temperature, add the 0.18g Palladous chloride in 12ml 0.62M zirconium oxychloride aqueous solution, the strong aqua that drips 25-28% under stirring gets the precipitation of hydroxide of zirconium and palladium to PH=8.With this sedimentation and filtration, with distilled water wash number time.Then, precipitation is placed 120 ℃ dry 10 hours of baking oven.After the cooling, soaked 5 minutes with the sulfuric acid of 15ml 1M, the supernatant liquid that inclines, after the gained catalyst precursor drying, 600 ℃ of roastings are 2 hours in muffle furnace, about 0.92 gram of solid granulates catalyzer.
The canonical process of catalyzed oxidation oxonation involved in the present invention is: add granularity and be about 350 milligrams of the above-mentioned catalyzer of 120 purposes in 1 liter high-pressure reactor, add reaction substrate 10-20 gram, add 150 milliliters of solvent second cyanogen or aniline.Introduce the pure oxygen of 0.5-1.0MPa and carbon monoxide to the stagnation pressure of 3.0-3.5MPa respectively and reach 3.5-4.5MPa, reactor is heated to 130-160 ℃, stirring reaction 0.25-2 hour.Reactor cooling is to room temperature, and sampling is carried out qualitative, quantitative and purity check with U.S. HP6890/5973GC-MS combined instrument.Higher conversion and optionally under the situation will directly be separated out the crystallization of product urea, after separating after filtration, pure product (GC-MS affirmation).Weigh, get direct yield.Residual filtrate is separated through evaporation can further obtain purpose product urea, adds direct yield, can get total recovery.Wherein, symmetrical urea derivatives total yield of products can reach 90-99%, purity 〉=99.0%.
The present invention with the substantive distinguishing features that existing synthetic urea derivatives method is compared is:
1. have efficiently simultaneously, catalyzer is simple relatively, does not need promotor, and the consumption of palladium is relatively low.
2. owing to adopted supported catalyzer, reaction finishes after the simple filtration catalyzer just can separate with reaction system.
3. synthesize the synthetic of corresponding symmetry or unsymmetrical urea derivative applicable to fat or aromatic amine, be particularly suitable for the synthetic corresponding symmetrical urea of fatty amine.
Embodiment 1-3:
Stir 1 liter and press and to add granularity in the reactor and be about 350 milligrams of 120 purpose catalyzer in that magneton is housed, add reaction substrate n-Butyl Amine 99 15 grams (embodiment 1), or hexahydroaniline 17 grams (embodiment 2), or positive amino dodecane 10 grams (embodiment 3), add 150 milliliters in solvent second cyanogen.Introduce the pure oxygen of 0.5MPa and carbon monoxide to the stagnation pressure of 35MPa respectively and reach 4.0MPa, reactor is heated to 140 ℃, stirring reaction 1 hour.Reactor assembly is cooled to room temperature, will separate out the crystallization of product urea, separate after filtration, after washing and the drying, pure product (GC-MS affirmation).Weigh, get direct yield.At this moment, with the reaction substrate difference, still be dissolved with the products of different amounts in the filtration raffinate.The residual filtrate sampling is done further qualitative and quantitative analysis with U.S.'s HP6890/5973GC-MS combined instrument.Residual filtrate can further obtain purpose product urea through separating, and adds above-mentioned direct yield, gets total recovery.
The zirconia catalyst system that table 1 palladium-sulfuric acid is modified is to the once direct % of the bearing reaction reactant transformation efficiency selectivity dialkyl ureas total recovery example % % of the corresponding urea of catalytic carbonylation system of amine
Yield % example 1 n-Butyl Amine 99 SRI 434-37 100 98 79 90 examples 2 hexahydroaniline dicyclohexylurea (DCU) 100 96 93 95 examples 3 positive amino dodecane two positive amino dodecane base ureas 100 100 99 99
Embodiment 4:
In above-mentioned same reactor, add reaction substrate normal hexyl Amine 20 grams, adding be solvent be again 150 milliliters of the aniline of one of reactant.Other operating process in reaction conditions all with embodiment 1-3.Reaction result sees Table 2.
The zirconia catalyst system that table 2 palladium-sulfuric acid is modified is to the result of the catalytic carbonylation system unsymmetrical urea of different amine
Reaction-ure conversion-age/% 1-hexyl, 3-phenylurea selectivity/% total recovery/% aniline+normal hexyl Amine 99 88 67
Claims (6)
1. the method for a preparing urea derivatives by catalytic oxidation and carbonylation of amine, it is characterized in that reaction substrate selects fat or aromatic series organic amine for use, the zirconium dioxide loaded palladium of modifying with sulfuric acid is as catalyzer, in reaction pressure is 3.5-4.5MPa, under 120 ℃-160 ℃ of the temperature of reaction, use the mixed gas of carbon monoxide and oxygen to be the oxidative carbonylation agent, the corresponding urea derivatives of organic amine system that the catalyzed oxidation carbonylation is different.
2. the method for claim 1 is characterized in that the consumption of the zirconium dioxide carried palladium catalyst that sulfuric acid is modified is the 2-3.5% of fat or aromatic series organic amine weight.
3. the method for claim 1, the volume ratio that it is characterized in that oxygen and CO (carbon monoxide converter) gas is 1: 3-9.
4. the method for claim 1 is characterized in that reaction solvent is second cyanogen or aniline, and the weight ratio of fat or aromatic series organic amine and quantity of solvent is 1: 7.5-15.
5. the method for claim 1 is characterized in that zirconia carrier through the processing of 0.5-1.0 mol sulfuric acid, and wherein the weight percentage of sulfate radical is 1-5%.
6. the method for claim 1, the weight percentage that it is characterized in that activity of such catalysts component palladium is 3-10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00104412A CN1113860C (en) | 2000-06-21 | 2000-06-21 | Method for preparing urea derivatives by catalytic oxidation and carbonylation of amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00104412A CN1113860C (en) | 2000-06-21 | 2000-06-21 | Method for preparing urea derivatives by catalytic oxidation and carbonylation of amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1277959A true CN1277959A (en) | 2000-12-27 |
| CN1113860C CN1113860C (en) | 2003-07-09 |
Family
ID=4577301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00104412A Expired - Fee Related CN1113860C (en) | 2000-06-21 | 2000-06-21 | Method for preparing urea derivatives by catalytic oxidation and carbonylation of amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1113860C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417478A (en) * | 2017-06-05 | 2017-12-01 | 南京师范大学 | A kind of method of catalysis oxidation carbonyl compound into asymmetric 2-substituted carbamide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5902889A (en) * | 1997-09-18 | 1999-05-11 | The Goodyear Tire & Rubber Company | Process for hydrogenation of carbon-carbon double bonds of a water-soluble olefinically unsaturated carboxylic acid salt |
-
2000
- 2000-06-21 CN CN00104412A patent/CN1113860C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417478A (en) * | 2017-06-05 | 2017-12-01 | 南京师范大学 | A kind of method of catalysis oxidation carbonyl compound into asymmetric 2-substituted carbamide |
| CN107417478B (en) * | 2017-06-05 | 2020-05-05 | 南京师范大学 | Method for synthesizing asymmetric disubstituted urea by catalytic oxidation carbonylation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1113860C (en) | 2003-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104710325B (en) | The method of Supported Manganese oxygen compound catalysis alkohol and amine one-step synthesis imines | |
| CN101695657A (en) | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin | |
| Shi et al. | Silica Gel Confined Ionic Liquid+ Metal Complexes for Oxygen‐Free Carbonylation of Amines and Nitrobenzene to Ureas | |
| CN109317168B (en) | Synthetic method of selenium-doped zirconia catalyst | |
| CN100434175C (en) | Catalyst and its use for synthesizing 4-nitro-3-methyl benzoic acid | |
| CN1113860C (en) | Method for preparing urea derivatives by catalytic oxidation and carbonylation of amine | |
| JPH05124803A (en) | Production of hydrogen peroxide | |
| CN1209347C (en) | Production of twice substituted urea by amine reacted with carbon dioxide | |
| US4503249A (en) | Hydrogenation catalysts | |
| CN111437875A (en) | Cerium-iron molecular sieve based catalyst with wide temperature range and preparation method thereof | |
| CN114433127B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic acid by maleic anhydride hydrogenation | |
| CN107597173B (en) | Catalyst for synthesizing benzenediol by phenol hydroxylation and preparation method thereof | |
| CN101781223A (en) | Method for catalytically synthesizing aminated compounds by using carbon-silicon solid acid as catalysts | |
| CN1978426A (en) | Method for preparing disubstituted urea by carbon dioxide and amide reaction | |
| CN109824634A (en) | A kind of method that furfural direct oxidation esterification prepares methylfuroate | |
| CN101602014B (en) | Load type carbon nano-fiber catalyst and application thereof | |
| US4394298A (en) | Hydrogenation catalyst | |
| CN112724017B (en) | Method for synthesizing asymmetric organic carbonate at room temperature | |
| CN100553767C (en) | The catalyst of gas phase oxidation of toluene and method for making thereof and purposes | |
| CN1131207C (en) | Process for preparing carbamide derivative by catalytic oxidation and oxonation of amine | |
| CN1087012C (en) | Clean catalytic oxidization process for synthesizing adipic acid | |
| CN101759602B (en) | Method for synthesizing cyclohexyl carbamate | |
| CN108187747B (en) | Multifunctional integrated catalyst, synthesis method and application | |
| CN110124682A (en) | A kind of synthetic method of Ce-Co modification manganese oxide | |
| CN1903823A (en) | Method of large scale synthesizing glutaric acid by environment friendly catalyzing and oxidizing cyclopentene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |