CN1131207C - Process for preparing carbamide derivative by catalytic oxidation and oxonation of amine - Google Patents

Abstract

The present invention relates to a method for effectively and cleanly preparing dibasic carbamide by catalytic oxidation carbonylation of organic amine compounds. The present invention uses a gold catalyst carried by resin high polymers. Under the conditions with primary response pressure of 4.0 to MPa to 6.0MPa, reaction temperature of 100 DEG C to 200 DEG C and reaction time of 1h to 10 h, mixed gas of carbon monoxide and oxygen is used as an oxidation carbonylation agent so as to prepare the corresponding dibasic carbamide through the catalytic oxidation carbonylation of organic amine. The catalyst has the main characteristics of high efficiency, simple components, low gold content and easy separation from a reaction system, recovery and repeated use. Other solvents do not need to be added in the reaction process, wherein the one-way yield ratio of the dibasic carbamide is from 48% to 85%, and the product purity is higher than or equal to 99%. The present invention belongs to the technology of clean catalytic reaction and has good industrial application prospect.

Description

The method of preparing carbamide derivative by catalytic oxidation and oxonation of amine

The present invention relates to a kind of catalytic oxidation and carbonylation of amine and produce the method for urea derivatives.

Urea derivatives is important organic reaction intermediate and a pharmaceutical intermediate of a class, and it all has purposes very widely in agricultural chemicals, medical and health and other organic synthesis.The production method of current 2-substituted carbamide mainly is to use aminated compounds and isocyanic ester or phosgene reaction to realize.Use any method all can relate to the phosgene of severe toxicity, and have a large amount of corrosive gases hydrogenchloride to emit in the reaction, so the researchist makes great efforts to seek one and considers more suitably route from economy and environmental.And the method direct reaction that uses oxidative carbonylation or reduction carbonylation is produced the method for symmetric or unsymmetrical urea and is just being met this requirement, so each chemical enterprise and scientific research structure all concentrate on research and use the synthetic urea derivatives of carbonyl process.People generally use in this course 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, 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, Hayashi etc. (USP 5902889) use primary amine and cyclic carbonate to be reflected under the katalysis of sodium alkoxide and produce urea derivatives, but the cyclic carbonate price is relatively costly.Deng You congruence (Chinese patent publication number: CN1272959A) use vitriol to modify the zirconium dioxide carried palladium catalyst and realized that aminated compounds catalyzed oxidation carbonylation produces 2-substituted carbamide and obtained quite high catalytic activity.But the price of palladium is lasting surging in recent years, causes the cost of palladium catalyst to raise significantly, and meanwhile, the price of gold is then stable with a slight decline.Therefore, the alternative traditional palladium catalyst of exploitation Au catalyst not only has great scientific meaning but also good prospects for application is arranged.

The object of the present invention is to provide a kind of more environmental friendliness, the method for preparing carbamide derivative by catalytic oxidation and oxonation of amine efficiently.

The present invention realizes by following measure:

Use resin superpolymer supported aurum catalyst among the present invention.Wherein, gold is immobilized on the resin Polymer Surface with metal or golden oxide nano particles form, and the content that supports gold accounts for the 0.1%-5% of resin superpolymer weight.The resin superpolymer can be weakly acidic cation-exchange resin, weak base anion-exchange resin, storng-acid cation exchange resin, strongly basic anion exchange resin.Sodium, potassium are promotor, and the content of sodium, potassium accounts for the 1%-25% of resin superpolymer weight.Account at resene superpolymer supported aurum catalyst under the condition of 1%-20% of reactant, initial reaction pressure is 4.0-6.0MPa, and temperature of reaction is 100-200 ℃.Reaction times is 1-10 hour, uses carbon monoxide and oxygen mixture to be the oxidative carbonylation agent, efficiently the corresponding dibasic urea of the various aminated compounds systems of catalyzed oxidation carbonylation.The volume ratio of oxygen and carbon monoxide is 1: 10-1: 4.

The principal feature of this catalyzer be have efficient, form simultaneously simply relatively, separate with reaction system easily, characteristics such as recovery and repeated use.The typical building-up process that relates to catalyzer among the present invention is: under the normal temperature, takes by weighing 20-100 gram weakly acidic cation-exchange resin, adds 2-100 gram sodium hydroxide, and the 200-1000 ml water, magneton stirred 6 hours.With this sedimentation and filtration, with distilled water wash 3 times, 100 ℃ of dryings 3 hours.Adding an amount of quality percentage composition then is the aqueous solution of chloraurate of 0.36-1.8%, slowly stirs after 10 hours 60 ℃ of vacuum-dryings 3 hours, the solid resin supported aurum catalyst.

The canonical process of catalyzed oxidation oxonation involved in the present invention is: add above-mentioned pelleted catalyst 1-10 gram in the high-pressure reactor of 1 liter, add organic amine 10-100 gram (milliliter), the carbon monoxide of introducing the purity oxygen of 0.1-2.5MPa and 3.5-5.0Mpa respectively is to stagnation pressure 2.0-6.0Mpa, after reactor is heated to 100 ℃-200 ℃, stirring reaction 1-10 hour.Behind the reaction cool to room temperature, product is directly separated out with crystalline form, filters, and gained filtrate directly applies to reaction (purity is greater than 98%) next time.Product is with an amount of washing with acetone, and 60 ℃ of dryings are weighed, once through yield 50%-80%, GC/MS purity assay＞99%.

The present invention with the substantive distinguishing features that the method for the synthetic 2-substituted carbamide of carbon monoxide oxonation amine compounds of existing bibliographical information is compared is:

1. catalytic efficiency height, its corresponding transformation frequency can reach 500-2500 (molar reactive thing/mole gold/hour).

2. the catalyzer composition is simple relatively, and the loading of gold is relatively low.

3. compare with catalyst systems such as Pd, Rh, the price of Au catalyst system is relatively low.

4. reaction system is fairly simple, does not need to add in addition other promotor.

5. owing to adopted solid-carried catalyst, after finishing, reaction easily separates with reaction system.Simultaneously, make reaction become possibility with the continuous flow modes operation.

6. reaction does not need to add other solvent again.

7. reaction back condensation can directly obtain product, and product is separated out with crystallized form, and separate easily is purified.

8. catalyzer can be reused.

Implementation example 1-4:

Taking by weighing commercial disignation is resin 60 grams of D201 * 4, adds sodium hydroxide 30 grams, stirs 6 hours under the room temperature, adding 60ml quality percentage composition is 1.8% aqueous solution of chloraurate after the air at room temperature drying, slowly stir after 10 hours, 80 ℃ of dryings are 3 hours in the air, must react required catalyzer a.

With 60ml quality percentage composition is that 0.9% aqueous solution of chloraurate replaces 1.8% aqueous solution of chloraurate, catalyzer b.

With 60ml quality percentage composition is that 0.45% aqueous solution of chloraurate replaces 1.8% aqueous solution of chloraurate, catalyzer c.

Replace D201 * 4 type resins with D311SC, same step, the aqueous solution of chloraurate of adding 60ml1.8% gets catalyzer d.Concrete each catalyzer essential property sees Table one.

Table one, resin supported aurum catalyst essential property

Example	Catalyzer	Specific surface m 2/g 1	Pore radius 1	Au(wt％) 2
					1	a	1.59	46.4	1.02
2	b	1.78	53.7	0.50
					3	c	1.72	52.2	0.21
4	d	1.65	50.7	0.98

The 1:BET test result; 2: the atomic emission spectrum test result.Implementation example 5:

Add catalyzer a2 gram in churned mechanically 1 liter autoclave is housed, adds 30 milliliters of aniline, the carbon monoxide of introducing the pure oxygen of 1.0MPa and 4.0MPa respectively is heated to 170 ℃ with reactor, stirring reaction 3 hours to stagnation pressure 5.0MPa.Reactor cooling is to room temperature, and direct filtration is used washing with acetone, 60 ℃ of dryings 3 hours, weigh a yield, use the GC/MS purity assay.

Table two, catalyzer a catalysis aniline oxidative carbonylation system diphenyl urea result

Example	Transformation efficiency %	Selectivity %	A yield %	Purity %
					5	89	99	85	＞99

Implementation example 6-8:

Step is with implementation example 1, but replaces a catalyzer with b, and this catalyzer is reused 3 secondary response results as shown in Table 3.

Table three, catalyzer b catalysis aniline oxidative carbonylation system diphenyl urea result

Example	Transformation efficiency %	Selectivity %	A yield %	Purity %
					6	75	99	71	＞99
7	74	98	69	＞99
					8	77	99	70	＞99

Implementation example 9:

Step is with implementation example 1, but replaces catalyzer a with catalyzer c, but reacts 8 hours, and the result as shown in Table 4.

Table four, catalyzer c catalysis aniline oxidative carbonylation system diphenyl urea result

Example	Transformation efficiency %	Selectivity %	A yield %	Purity %
					9	69	95	58	＞99

Implementation example 10:

Step still replaces aniline and reaction to carry out 4 hours with P-nethoxyaniline with implementation example 1, the results are shown in Table five.

Table five, catalyzer a catalysis P-nethoxyaniline oxidative carbonylation system di-p-methoxy phenylurea result

Example	Transformation efficiency %	Selectivity %	A yield %	Purity %
					10	94	99	80	＞99

Implementation example 11:

Step is with implementation example 1, but replaces aniline with hexahydroaniline, reacts 3 hours, the results are shown in Table six.

Table six, catalyzer a catalysis hexahydroaniline oxidative carbonylation system dicyclohexylurea (DCU) result

Example	Transformation efficiency %	Selectivity %	A yield %	Purity %
					11	54	99	48	＞99

Implementation example 12:

Step is with implementation example 1, but replaces catalyzer a with catalyzer d, reacts 5 hours, the results are shown in Table seven.

Table seven, catalyzer d catalysis aniline oxidative carbonylation system diphenyl urea result

Example	Transformation efficiency %	Selectivity %	A yield %	Purity %
					12	83	97	76	＞96

Claims (4)

1. the method for a catalyzed oxidation carbonylation system 2-substituted carbamide, it is characterized in that the Au catalyst that uses the resene superpolymer to support, at initial reaction pressure is 4.0-6.0Mpa, temperature of reaction is 100-200 ℃, reaction times is 1-10 hour, use carbon monoxide and oxygen mixture to be the oxidative carbonylation agent, the corresponding 2-substituted carbamide of catalyzed oxidation carbonylation organic amine system.

2. method according to claim 1 is characterized in that the loading of gold is the 0.1%-5% of resene superpolymer weight; The content of promotor sodium or potassium is the 1%-25% of resene superpolymer weight.

3. method according to claim 1, the consumption that it is characterized in that the Au catalyst that the resene superpolymer supports is the 1-20% of reactant weight.

4. as method as described in claims 1, the volume ratio that it is characterized in that oxygen and carbon monoxide is 1: 10-1: 4.