CN110041218B - Preparation method of oxamide - Google Patents
Preparation method of oxamide Download PDFInfo
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- CN110041218B CN110041218B CN201810034258.1A CN201810034258A CN110041218B CN 110041218 B CN110041218 B CN 110041218B CN 201810034258 A CN201810034258 A CN 201810034258A CN 110041218 B CN110041218 B CN 110041218B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
Abstract
The invention provides a preparation method of oxamide, which comprises the following steps: with CO, O2And an amine compound is used as a raw material, under the action of a catalyst 1, the intermediate oxamide derivative is prepared by oxidation and carbonylation, and then under the action of a catalyst 2, the oxamide derivative is aminolyzed to prepare the oxamide. The invention uses a brand-new method to co-produce the oxamide and the oxamide derivatives, and solves the problems of toxic raw materials for synthesizing the oxalamide, low catalyst efficiency and the like in the prior art for synthesizing the oxamide by the ammonolysis of the oxalate. In addition, the substrate for synthesizing the oxamide derivative by the process has good applicability, and can be used in the fields of medicines, pesticides, synthetic ligands, food additives and the like.
Description
Technical Field
The invention belongs to the technical field of oxamide synthesis, and particularly relates to a preparation method of oxamide.
Background
Oxamides, also known as oxalic acid diamide, oxalyldiamide (CAS No. 471-46-5), are widely used in the field of agricultural fertilizers as a compound with a very high nitrogen content. The oxamide has the characteristics of no toxicity, easy storage, low solubility and the like, so that the oxamide has better performance than other fertilizers. For example, oxamide gradually decomposes and releases ammonia and carbon dioxide during biodegradation, and is harmless to the environment; the use of the oxamide can improve the utilization rate of the fertilizer, reduce the fertilization times and reduce the harm to water resources; the use of oxamide as a fertilizer can reduce the cost of fertilizers, manpower and time in the agricultural production process, which is proved in the existing agricultural practice (see references: Shenzhong, Zxu Mei, modern agricultural science and technology of resource and environment science 2015, 6, 220; Po Dongshi, Wang Lijun, Zhang Tan, Feng Wen Gui, Zhang Deli, China cotton, 2014, 41(12), 17-19).
Currently, there are four main methods for synthesizing oxamides:
hydrocyanic acid oxidation hydrolysis method: hydrocyanic acid (HCN) is used as a raw material, and is firstly oxidized to generate cyanogen ((CN)2), and then oxamide is obtained by hydrolysis (see: US 3989753). The method has the defects of high toxicity of cyanide, high production cost and the like, and has no relevant industrial report.
Ammonium oxalate or urea oxalate pyrolysis method: ammonium oxalate or urea oxalate is used as a raw material, and oxamide is obtained through high-temperature pyrolysis. The method has the advantages of high production cost and low practical value, so that related researches are few.
And (3) carrying out oxalic ester ammonolysis on CO: CO is used as a raw material, firstly, the CO and nitrite are coupled to synthesize oxalate, and then the oxalate and ammonia gas or urea are subjected to ammonolysis reaction in fatty alcohol to generate oxamide and fatty alcohol (see: CN102267921A, CN201510559739.0, US6348626 and US 5393319). Although a great deal of research has been carried out in recent years on the synthesis process (see: Chinese patent CN 103288666A describes a method for synthesizing oxamide by continuous gas phase transesterification in a fluidized bed reactor; Chinese patents CN201110143358.6 and CN201310197093.7 describe continuous processes for synthesizing oxamide; Chinese patent CN 201611071466.6 describes a catalyst for the process and a preparation method thereof; and U.S. patent US5393319 and Chinese patent CN 103242188A study on the problem of particle formation in the process), the method also has many problems in industrial actual production, such as poor performance and recycling of the catalyst in the preparation of oxalate, difficult separation of products and the like.
CO and N2The direct synthesis method comprises the following steps: CO and N2 are used as raw materials, and oxamide is directly synthesized under the action of a hafnium complex (see references: Donald J. Knobuch, Emil Lobkovsky, Paul J. Chirik, Naturechemistry, 2010, 2, 30-35). The method is still in a research stage at present, and the technology is immature.
In addition, the method for synthesizing the oxamide derivative by oxidative carbonylation of CO and amine can only be realized in a homogeneous palladium complex catalyst system (see: WO 2010/130696 AI; CN 201080021316.9 and reference I.Pri-Bar, H.Alper, Can.J.chem., 1990, 68, 1544-1547), and still has the problems of catalyst recycling, product separation and the like, and is not reported in relevant industrialization.
Disclosure of Invention
In order to solve the above-mentioned drawbacks, the present invention provides a novel method for synthesizing oxamide, which comprisesThe method enriches the prior oxamide synthesis technology, fills the defects of the prior art, and provides a brand-new method for synthesizing oxamide by aminolysis of oxamide derivatives. The method adopts a step method to prepare the oxamide, firstly prepares the oxamide derivative by the oxidative carbonylation of CO and amine in the presence of a heterogeneous bimetallic catalyst, and then synthesizes the oxamide by the ammonolysis of the oxamide derivative under the action of the catalyst. In the method, the amine compound can be recycled, and the reaction is actually carried out by CO and O2And NH3The indirect synthesis of oxamide has high atom economic benefit. In addition, the synthesis process of the invention is a heterogeneous catalytic reaction process, the catalyst preparation process is simple, the cyclic regeneration is easy, the reaction product is easy to separate, and the industrial production is expected to be realized.
In order to achieve the above object, the present invention provides a novel method for preparing oxamide, comprising the steps of: with CO, O2And an amine compound is taken as a raw material, under the action of a catalyst 1, an intermediate oxamide derivative is prepared by oxidation and carbonylation, and then under the action of a catalyst 2, the oxamide derivative is aminolyzed to prepare oxamide, wherein the synthetic route is as follows:
wherein, in the synthetic route, said R1Comprising one of hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compounds with or without heteroatoms, R2Including one of hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compounds with or without heteroatoms.
Preferably, the preparation method is carried out in a reaction solvent comprising one or more of dimethylsulfoxide, N-dimethylformamide, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, toluene, xylene, mesitylene, or dioxane.
Preferably, the volume fraction of CO is 80%, and the CO and O are2The total amount of the amine compound is 1 to 100 equivalents.
Preferably, the oxamide derivative and NH3The molar ratio of (A) to (B) is 1: 1-1: 10.
Preferably, the catalyst 1 is a solid supported catalyst, and the catalyst 1 comprises an active component comprising one or more of a transition metal, a main group metal, a metalloid, or a metal oxide.
Preferably, the carrier of the catalyst 1 comprises one of alumina, titania, silica, activated carbon, graphene oxide or molecular sieve.
Preferably, the catalyst 2 is a solid supported catalyst, and the catalyst 2 includes an active component including one or more of a transition metal or a transition metal oxide.
Preferably, the catalyst 2 further comprises a catalytic promoter, and the catalytic promoter is one or more of an oxide, a solid acid base or an ionic liquid.
Preferably, the carrier of the catalyst 2 comprises one of alumina, titania, silica, activated carbon or molecular sieve.
Preferably, the reaction temperature for preparing the oxamide derivative is 50-80 ℃, and the reaction temperature for preparing the oxamide by aminolysis of the oxamide derivative is 100-160 ℃.
As a preference, NH in the process3Can be derived from ammonia gas, urea, ammonium salt, etc., and preferably ammonia gas and urea.
As a preference, O in the process2Can be derived from oxygen, air, etc., preferably air.
When preparing the oxamide derivative, firstly adding a reaction solvent and a catalyst 1 into a reaction kettle, and then sequentially introducing CO and O according to the proportion2Stirring the mixture for reaction,finally, separating the mixture obtained by the reaction to obtain the oxamide derivative; when preparing the oxamide, the oxamide derivative, the reaction solvent and the catalyst 2 are added into a reaction kettle according to the proportion, and then N is introduced2And (3) replacing air in the kettle, continuously introducing the air to a certain pressure, stirring for reaction, and finally separating a mixture obtained by the reaction to obtain the oxamide.
As a preference, CO and O are used in the preparation of oxamide derivatives2The total pressure of (A) is 0.1-5.5 MPa, the volume fraction of CO is 80%, and CO and O2The dosage of the amine compound is 1-100 equivalent of the amine compound; preparation of oxamide N2At a pressure of 0.1 to 3MPa, an oxamide derivative and NH3The molar ratio of (A) to (B) is 1: 1-1: 10.
The invention calculates the single-pass yield range of the oxamide derivative by taking the amine compound as a standard to be 60-99 percent, and the single-pass yield of the oxamide is 52-96 percent.
The invention has the beneficial effects that:
1. the invention discloses a novel method for preparing oxamide, which takes CO as a raw material and an oxamide derivative as an intermediate product to indirectly produce oxamide and enriches the synthesis methods of oxamide and the derivatives thereof. The method has excellent substrate practicability, and is well compatible with amine compounds substituted by various chemical functional groups (such as alkyl, aryl, alkenyl, halogen, ester group, ether group, hydroxyl, amino, allylamine, acyl, amide, trifluoromethyl and the like).
2. The obtained oxamide derivative is co-produced, the problems that the existing oxamide derivative is complex in synthesis process, inapplicable to aromatic substrates and the like are solved, and the oxamide derivative can be further applied to the fields of medicines, pesticides, synthetic ligands, food additives and the like.
3. In the whole process, the amine compound can be recycled, and other byproducts are not generated; the synthesis process is a heterogeneous catalytic reaction process, and the preparation process of the catalyst is simple; the target yield is moderate to excellent, and effective guarantee is provided for large-scale and economical supply of oxamide.
Detailed Description
The following examples are provided to aid in the further understanding of the invention, but are not intended to limit the invention thereto.
When preparing the oxamide derivative, firstly adding a reaction solvent and a catalyst 1 into a reaction kettle, and then sequentially introducing CO and O2Stirring for reaction, and finally separating a mixture obtained by the reaction to obtain an oxamide derivative; when preparing the oxamide, firstly adding the oxamide derivative, the reaction solvent and the catalyst 2 into a reaction kettle, and then introducing N2And (3) replacing air in the kettle, continuously introducing the air to a certain pressure, stirring for reaction, and finally separating a mixture obtained by the reaction to obtain the oxamide.
Preparation of catalyst
The preparation method of the catalyst takes the preparation process of the catalyst 1-6 as an example, 1-3 is the preparation process of the catalyst 1, and 4-12 is the preparation process of the catalyst 2, and the preparation method is embodied as follows:
example 1: catalyst 1-1
2.13g of copper nitrate pentahydrate and 3.22g of anhydrous palladium chloride were weighed into a round bottom flask, and 20 wt% NH was added4The OH solution was completely dissolved, 15g of pseudo-boehmite was added, and the mixture was stirred at room temperature for 2 hours. And then, carrying out suction filtration, washing the product to be neutral by using distilled water, drying the product for 12h at 120 ℃, roasting the product for 3h at 450 ℃ in a muffle furnace, and grinding and sieving the product (80-100 meshes) to obtain the active catalyst 1-1 provided by the invention.
Example 2: catalysts 1-2
Weighing 2.13g of copper nitrate pentahydrate, 3.22g of anhydrous palladium chloride and 15g of pseudo-boehmite, adding into a round-bottom flask, adding 20mL of distilled water, stirring, dispersing, precipitating by using 10 wt% of NaOH solution as a precipitator, precipitating until the pH value is about 10, heating to 80 ℃, and aging for 4 hours. And (3) cooling, carrying out suction filtration, washing with distilled water to neutrality, drying at 120 ℃ for 12h, roasting at 450 ℃ in a muffle furnace for 3h, grinding and sieving (80-100 meshes) to obtain the active catalyst 1-2 provided by the invention.
Example 3: catalysts 1 to 3
Weighing 2.13g of copper nitrate pentahydrate, 3.22g of anhydrous palladium chloride and 15g of pseudo-boehmite, adding into a round-bottom flask, adding 20mL of distilled water, stirring, dispersing, precipitating by using 50 wt% of urea solution as a precipitator, precipitating until the pH value is about 10, heating to 105 ℃, and aging for 4 hours. And (3) cooling, carrying out suction filtration, washing with distilled water to neutrality, drying at 120 ℃ for 12h, roasting at 450 ℃ in a muffle furnace for 3h, grinding and sieving (80-100 meshes) to obtain the active catalyst 1-3 provided by the invention.
Example 4: catalyst 2-1
Weighing 15.69g of copper nitrate pentahydrate and 55.00g of silicon dioxide, adding into a round-bottom flask, adding 85mL of distilled water, stirring for dissolving and dispersing, precipitating by using 50 wt% of urea solution as a precipitator, raising the temperature to 105 ℃, and aging for 4 hours. Cooling, vacuum filtering, washing with distilled water to neutrality, oven drying at 120 deg.C for 12 hr, roasting at 450 deg.C in muffle furnace for 3 hr, grinding, and sieving (80-100 mesh). The sieved roasted samples were incubated at 400 ℃ and 1% (H)2+N2) Reducing and activating for 3h in the atmosphere to obtain the active catalyst 2-1 provided by the invention.
Example 5: catalyst 2-2
Weighing 15.69g of copper nitrate pentahydrate, 3.95g of zinc nitrate hexahydrate and 55g of silicon dioxide, adding into a round-bottom flask, adding 85mL of deionized water, taking 50 wt% urea solution as a precipitator for precipitation, precipitating until the pH value is about 10, heating to 105 ℃, and aging for 4 h. Cooling, vacuum filtering, washing with distilled water to neutrality, oven drying at 120 deg.C for 12 hr, roasting at 450 deg.C in muffle furnace for 3 hr, grinding, and sieving (80-100 mesh). The sieved roasted samples were incubated at 400 ℃ and 1% (H)2+N2) Reducing and activating for 3h in the atmosphere to obtain the active catalyst 2-2 provided by the invention.
Example 6: catalysts 2 to 3
Weighing 15.69g of copper nitrate pentahydrate, 4.96g of silver nitrate and 55g of silicon dioxide, adding into a round-bottom flask, adding 85mL of deionized water, taking 50 wt% urea solution as a precipitator for precipitation, precipitating until the pH value is about 10, heating to 105 ℃, and aging for 4 h. Cooling, vacuum filtering, washing with distilled water to neutrality, oven drying at 120 deg.C for 12 hr, roasting at 450 deg.C in muffle furnace for 3 hr, grinding, and sieving (80-100 mesh). The sieved roasted samples were incubated at 400 ℃ and 1% (H)2+N2) Reducing and activating for 3h in the atmosphere to obtain the active catalyst 2-3 provided by the invention.
Example 7: catalysts 2 to 4
15.69g of copper nitrate pentahydrate, 4.96g of silver nitrate and 55g of graphite were weighedAlkene, adding into a round-bottom flask, adding 85mL of deionized water, taking 50 wt% urea solution as a precipitator for precipitation, precipitating until the pH value is about 10, heating to 105 ℃, and aging for 4 hours. Cooling, vacuum filtering, washing with distilled water to neutrality, oven drying at 120 deg.C for 12 hr, roasting at 450 deg.C in muffle furnace for 3 hr, grinding, and sieving (80-100 mesh). The sieved roasted samples were incubated at 400 ℃ and 1% (H)2+N2) Reducing and activating for 3h in the atmosphere to obtain the active catalyst 2-4 provided by the invention.
Example 8: catalysts 2 to 5
Weighing 15.69g of copper nitrate pentahydrate and 24.96g of aluminum nitrate, adding the copper nitrate pentahydrate and the aluminum nitrate into a round-bottom flask, adding 1% of polyethylene glycol solution, dropwise adding 35% ammonia water under vigorous stirring until the pH value is about 10, putting the mixture into an ice water bath for aging for 4 hours, then performing suction filtration, washing the mixture to be neutral by using distilled water, drying the mixture for 12 hours at 120 ℃, and grinding and sieving the mixture (80-100 meshes). And obtaining the active catalyst 2-5 after sieving.
Example 9: catalysts 2 to 6
Weighing 15.69g of copper nitrate pentahydrate, 4.96g of silver nitrate and 24.96g of aluminum nitrate, adding the mixture into a round-bottom flask, adding a 5% polyethylene glycol solution, dropwise adding 35% ammonia water under vigorous stirring until the pH value of the precipitate is about 10, putting the precipitate into an ice water bath, aging for 4 hours, then carrying out suction filtration, washing the precipitate with distilled water to be neutral, drying the precipitate at 120 ℃ for 12 hours, and grinding and sieving the precipitate (80-100 meshes). And obtaining the 2-6 active catalyst after sieving.
Example 10: catalysts 2 to 7
Adding 10g of silica gel into 40mL of mixed solvent (the volume ratio of ethanol to water is 1: 1), adding 10mL of gamma- (methacryloyloxy) propyl trimethoxy silane, reacting at the constant temperature of 50 ℃ for 24h, extracting the filtered product with ethanol for 2h, separating, and vacuum-drying for 24 h. Then, the dried silica gel powder was placed in a four-necked flask, 5mL of styrene and 25mL of toluene were added, and the mixture was stirred at 80 ℃ for 5 hours and dried to obtain a bonded silica gel. And (3) placing the bonded silica gel into a conical flask, adding 20mL of 98% concentrated sulfuric acid, adding 5.23g of anhydrous copper sulfate, sulfonating for 2h at 180 ℃, filtering by using a sand core funnel, washing by using distilled water to be neutral, and drying to obtain the active catalyst 2-7 provided by the invention.
Example 11: catalysts 2 to 8
Weighing 15.69g of copper nitrate pentahydrate, 4.96g of silver nitrate and 24.96g of aluminum nitrate, adding the copper nitrate pentahydrate, the silver nitrate pentahydrate and the aluminum nitrate into a round-bottom flask, adding 5% of 1-hexadecyl-2, 3-dimethylimidazole hexafluorophosphate (CAS No. 640282-17-3) solution, dropwise adding 35% ammonia water under vigorous stirring until the pH value is about 10 after precipitation, putting the mixture into an ice water bath, aging for 4 hours, then performing suction filtration, washing the mixture with distilled water to be neutral, drying for 12 hours at 120 ℃, and grinding and sieving (80-100 meshes) to obtain the active catalyst 2-8 provided by the invention.
Example 12: catalysts 2 to 9
Weighing 15.69g of copper nitrate pentahydrate, 4.96g of silver nitrate and 24.96g of aluminum nitrate, adding the copper nitrate pentahydrate, adding a 5% N-hexylpyridinebis (trifluoromethanesulfonyl) imide salt (CAS number 460983-97-5) solution into a round-bottomed flask, dropwise adding 35% ammonia water under vigorous stirring until the pH value is about 10 after precipitation, putting the flask into an ice-water bath, aging for 4 hours, then performing suction filtration, washing the flask with distilled water to be neutral, drying the flask at 120 ℃ for 12 hours, and grinding and sieving the flask (80-100 meshes) to obtain the active catalyst 2-9 provided by the invention.
Step two, preparation of oxamide derivative
The preparation method of the oxamide derivative can be further exemplified by the preparation processes of 13-17, and is embodied as follows:
example 13:
1.00g of morpholine, 5mL of anhydrous tetrahydrofuran and 20mg of catalyst 1 were weighed out accurately and charged in a stirred autoclave. 4MPa CO and 1MPa air are charged into the high-pressure reaction kettle, the reaction temperature is set to be 60 ℃, and the continuous reaction is carried out for 10 hours at the stirring speed of 700 rpm. And (3) after the temperature in the reaction kettle is reduced to room temperature, opening an emptying valve, reducing the pressure in the reaction kettle to the atmospheric pressure, taking out the mixture in the reaction kettle, and recrystallizing to obtain a solid-phase product, namely 1.20g of the oxalyl morpholine, wherein the single-pass yield of the oxalyl morpholine is 92.3 percent by taking the morpholine as a standard, and the results are shown in Table 1.
Example 14:
the same embodiment as in example 13, except that 2MPa CO, 0.2MPaair and 2mL of anhydrous tetrahydrofuran were added. The results of the analysis of the product are shown in Table 1.
Example 15:
the same as in example 13, except that anhydrous tetrahydrofuran was added in an amount of 3mL, the reaction temperature was room temperature, and the reaction time was 20 hours. The results of the analysis of the product are shown in Table 1.
Example 16:
the same as in example 13, except that the substrate was 1.00g of piperidine and anhydrous tetrahydrofuran was added in an amount of 2 mL. The results of the analysis of the product are shown in Table 1.
Example 17:
the same as in example 13, except that the substrate was 1.00g of aniline and anhydrous tetrahydrofuran was added in an amount of 2 mL. The results of the analysis of the product are shown in Table 1.
Step III preparation of oxamide
The preparation method of oxamide can be further exemplified by the preparation processes of 18-24, and is embodied as follows:
example 18:
1.00g of oxalyl morpholine, 12g of urea, 5mL of anhydrous tetrahydrofuran and 50mg of catalyst 4 were weighed out and charged in a stirred autoclave respectively. Introduction of N2The autoclave was purged of air and then pressurized to 0.5MPa, set at 70 ℃ and stirred continuously at 700rpm for 1 hour. The reaction temperature was set at 160 ℃ and the reaction was continued for 15h at a stirring speed of 700 rpm. And (3) after the temperature in the reaction kettle is reduced to room temperature, opening an emptying valve, reducing the pressure in the kettle to the atmospheric pressure, taking out the mixture in the kettle, filtering to obtain a solid-phase product, cleaning and drying to obtain 0.31g of white oxamide powder, wherein the single-pass yield of oxamide is 80.3% by taking oxalyl morpholine as a standard, and the results are shown in Table 2.
Example 19:
the same as in example 18, except that the reaction pressure was 0.5MPa and anhydrous tetrahydrofuran was added in an amount of 10 mL. The results of the analysis of the product are shown in Table 2.
Example 20:
the same as in example 18, except that the amount of the catalyst used was 20mg, the reaction pressure was 1MPa, and the amount of anhydrous tetrahydrofuran added was 10 mL. The results of the analysis of the product are shown in Table 2.
Example 21:
the same as in example 18, except that the reaction pressure was 0.5MPa and the reaction temperature was 140 ℃. The results of the analysis of the product are shown in Table 2.
Example 22:
the same as in example 18, except that the substrate added was oxalanilide 1.00g, the reaction pressure was 3MPa, and the solvent used was anhydrous methanol 5 mL. The results of the analysis of the product are shown in Table 2.
Example 23:
the same as in example 18, except that 1.00g of oxalanilide was added as the substrate, the reaction pressure was 3MPa, and 100mg of catalyst 4 was used. The results of the analysis of the product are shown in Table 2.
Example 24:
the same as in example 18, except that 1.00g of oxalanilide was added as the substrate, the reaction pressure was 3MPa, and the catalyst used in the reaction was catalyst 10 in an amount of 100 mg. The results of the analysis of the product are shown in Table 2.
| Substrate | Oxamide derivatives | Single pass yield (%) | |
| Example 13 | Morpholine 1.00g | 1.27g | 92.3％ |
| Example 14 | Morpholine 1.00g | 1.19g | 91.5％ |
| Example 15 | Morpholine 1.00g | 1.26g | 95.9％ |
| Example 16 | Piperidine 1.00g | 0.25g | 64.8％ |
| Example 17 | Aniline 1.00g | 0.20g | 54.5％ |
TABLE 1
| Substrate | Oxamides | Single pass yield of oxamide (%) | |
| Example 18 | Oxalyl morpholine 1.00g | 0.31g | 80.3％ |
| Example 19 | Oxalyl morpholine 1.00g | 0.36g | 93.3％ |
| Example 20 | Oxalyl morpholine 1.00g | 0.37g | 95.9％ |
| Example 21 | Oxalyl morpholine 1.00g | 0.25g | 64.8％ |
| Example 22 | Oxalanilide 1.00g | 0.20g | 54.5％ |
| Example 23 | Oxalanilide 1.00g | 0.33g | 90.0％ |
| Example 24 | Oxalanilide 1.00g | 0.35g | 95.4％ |
TABLE 2
It should be noted that the above-mentioned preferred embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. The preparation method of the oxamide is characterized by comprising the following steps of: with CO, O2Morpholine, piperidine or aniline as raw materials, under the action of a catalyst 1, oxidizing and carbonylating to prepare an intermediate oxamide derivative, and then under the action of a catalyst 2, aminolyzing the oxamide derivative to prepare oxamide;
the catalyst 1 is a solid supported catalyst, the catalyst 1 comprises an active component, the active component in the catalyst 1 comprises one or more of transition metal, main group metal, metalloid or metal oxide, and the carrier of the catalyst 1 comprises one of alumina, titanium oxide, silicon oxide, activated carbon, graphene oxide or molecular sieve;
the catalyst 2 is a solid supported catalyst, the catalyst 2 comprises an active component, the active component in the catalyst 2 comprises one or more of transition metal or transition metal oxide, the catalyst 2 further comprises a catalytic assistant, the catalytic assistant is one or more of oxide, solid acid-base or ionic liquid, and the carrier of the catalyst 2 comprises one of alumina, titanium oxide, silicon oxide, activated carbon or molecular sieve.
2. A process for the preparation of oxamide as claimed in claim 1, characterised in that: the preparation method is carried out in a reaction solvent, and the reaction solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, toluene, xylene, mesitylene or dioxane.
3. Grass according to claim 1A process for the preparation of amides, characterized in that: the volume fraction of CO is 80%, and the CO and O2The total amount of the compound is 1 to 100 equivalents of morpholine, piperidine or aniline.
4. A process for the preparation of oxamide as claimed in claim 1, characterised in that: the molar ratio of the oxamide derivative to NH3 is 1: 1-1: 10.
5. a process for the preparation of oxamide as claimed in claim 1, characterised in that: CO and O in the preparation of intermediate oxamide derivatives2The total pressure of (A) is 0.1 to 5.5 MPa.
6. A process for the preparation of oxamide as claimed in claim 1, characterised in that: the reaction temperature for preparing the intermediate oxamide derivative is 50-80 ℃, and the reaction temperature for preparing the oxamide by aminolysis of the oxamide derivative is 100-160 ℃.
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