CN116178215A - Preparation method of 1, 3-dialkyl urea compound - Google Patents

Preparation method of 1, 3-dialkyl urea compound Download PDF

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CN116178215A
CN116178215A CN202211593407.0A CN202211593407A CN116178215A CN 116178215 A CN116178215 A CN 116178215A CN 202211593407 A CN202211593407 A CN 202211593407A CN 116178215 A CN116178215 A CN 116178215A
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dicyclohexylurea
compound
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陈阳
周明东
王景芸
熊南妮
庞威军
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Shenyang University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

A preparation method of a 1, 3-dicyclohexylurea compound, which relates to a preparation method of a compound, and the method comprises the following steps: introducing carbon dioxide for ventilation, adding n-propylamine compound, metal oxide and inorganic salt into an organic solvent, controlling the temperature to be 130-170 ℃ in the carbon dioxide (5 MPa) atmosphere, and reacting 12-48 h under the magnetic stirring condition; after the reaction is finished, the temperature is restored to room temperature after the reaction is finished, a catalyst is collected by filtration, then 100 mL deionized water is added into the filtrate, the mixture is stirred at room temperature for 30 minutes and then filtered, and a white solid target product 1, 3-dicyclohexylurea compound is obtained; the reaction substrate is an organic amine compound, and the structure of the reaction substrate is shown as a formula (I). Wherein R is C3-C6 alkyl or cycloalkyl; (I). The separation method is simple, the raw materials are cheap and easy to obtain, the byproduct is water, the cleanliness of the reaction is improved, and the pollution to the environment is reduced.

Description

Preparation method of 1, 3-dialkyl urea compound
Technical Field
The invention relates to a compound synthesis method, in particular to a preparation method of a 1, 3-dialkyl urea compound.
Background
CO 2 Is a rich, nontoxic, nonflammable and low-cost C1 source, and has gained wide attention in recent years. CO is processed by 2 The direct conversion into high value-added chemicals has great development potential. CO 2 Has strong double bond and stable chemical property, and the direct chemical conversion is generally difficult and has great challenges. With CO 2 The reduction to methanol and formic acid is preferred over the non-reduction to carbonate, carbamate and urea chemicals from the energy input point of view, where urea derivatives are an important class of carbonyl compounds useful as intermediates for synthesis of pharmaceutical or agrochemical products and as fuel additives.
The conventional synthesis method of urea derivatives is to prepare phosgene or derivatives thereof. However, the phosgene process has considerable disadvantages such as the toxicity of phosgene and the generation of a large amount of by-products during the conversion process. In addition to this, the process for synthesizing urea derivatives comprises oxidative carbonylation of amine with CO, reductive carbonylation of amine with CO, transamidation of urea with amine, reaction of carbonate with amine, and CO 2 Reaction with amines. In these methods, CO 2 The urea derivative generated by directly reacting with amine has very broad prospect, and the byproduct in the conversion process is water, which accords with the development concept of green chemistry. From an industrial, environmental and economic point of view, it is more desirable to use heterogeneous catalytic or heterogeneous catalytic systems.
Disclosure of Invention
The invention aims to provide a preparation method of dialkyl urea compounds, which takes carbon dioxide as a reaction raw material to synthesize the dialkyl urea compounds, provides a direction for reducing emission of greenhouse gases in chemical industry, and can separate out catalysts through filtration, and the separation method is simple. The defect of using high-toxicity phosgene in the existing synthesis method is avoided, the raw materials are cheap and easy to obtain, the byproduct is water, the reaction cleanliness is improved, and the environmental pollution is reduced.
The technical scheme adopted by the invention is as follows:
a process for the preparation of a 1, 3-dicyclohexylurea compound, comprising the steps of: introducing carbon dioxide for ventilation, adding n-propylamine compound, metal oxide and inorganic salt into an organic solvent, controlling the temperature to be 130-170 ℃ in the carbon dioxide (5 MPa) atmosphere, and reacting 12-48 h under the magnetic stirring condition; after the reaction is finished, the temperature is restored to room temperature after the reaction is finished, a catalyst is collected by filtration, then 100 mL deionized water is added into the filtrate, the mixture is stirred at room temperature for 30 minutes and then filtered, and a white solid target product 1, 3-dicyclohexylurea compound is obtained; the reaction substrate is an organic amine compound, and the structure of the reaction substrate is shown as a formula (I). Wherein R is C3-C6 alkyl or cycloalkyl;
Figure 423672DEST_PATH_IMAGE002
（Ⅰ）。
the organic solvent is acetonitrile (MeCN), tetrahydrofuran (THF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) polar solvent.
The preparation method of the 1, 3-dicyclohexylurea compound comprises the step of preparing the metal oxide, wherein the metal oxide is CeO 2 、ZnO 2 、ZrO 2 And MnO 2 One of them.
The preparation method of the 1, 3-dicyclohexylurea compound comprises the step of preparing NaOH, KOH, K as the inorganic salt 3 PO 4 And K 2 HPO 3 One of them.
The preparation method of the 1, 3-dicyclohexylurea compound comprises the step that the dosage of metal oxide is 0.1-1.0 equiv of reaction substrate organic amine.
The preparation method of the 1, 3-dicyclohexylurea compound comprises the step of adding 0.5-10 mol% of inorganic salt as a reaction substrate of organic amine.
The beneficial effects of the invention are as follows:
the invention synthesizes dialkyl urea compounds by taking carbon dioxide as a reaction raw material, and reduces emission and extracts for chemical utilization of greenhouse gases
The direction is provided. The catalyst can be separated by filtration, and the separation method is simple. The defect of using high-toxicity phosgene in the traditional synthesis method is avoided, the raw materials are cheap and easy to obtain, the byproduct is water, the reaction cleanliness is improved, and the environmental pollution is reduced. The synthesis method has the characteristics of simplicity and high efficiency.
The invention aims at energy conservation and high efficiency, takes the aim of green chemistry and takes the atomic economy as consideration, takes CO2 and organic amine compounds as raw materials, carries out the carbointercalation reaction under the action of a composite heterogeneous catalyst of metal oxide and inorganic salt, and converts CO2 into dialkyl urea products with high efficiency, thus having important research significance.
Drawings
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of 1, 3-dicyclohexylurea according to the invention.
Detailed Description
According to the invention, an organic amine compound (I) is used as a raw material, carbon dioxide is introduced for ventilation, then a composite heterogeneous catalyst and a solvent are sequentially added, and the reaction is carried out under a carbon dioxide atmosphere (5 MPa) and a certain temperature condition to obtain a dialkyl urea compound shown in a formula (II), wherein the reaction route is as follows:
Figure DEST_PATH_IMAGE003
wherein R in the formula (II) is C3-C6 alkyl or cycloalkyl.
The catalyst is a composite heterogeneous catalyst of metal oxide (MO 2) and inorganic salt, wherein M is Ce2+, zn2+, zr2+, mn2+, and the like; inorganic salts are NaOH, KOH, K PO4, K2HPO3, etc.
The metal oxide is one of cerium oxide, zinc oxide, zirconium oxide and manganese oxide, and the preferred metal oxide is cerium oxide.
The metal oxide is used in an amount of 0.1 to 1.0 equiv., and the metal oxide is preferably used in an amount of 0.3 to 0.5 equiv.
The inorganic salt is one of sodium hydroxide, potassium phosphate and potassium phosphite, and the preferable inorganic salt is potassium phosphate.
The inorganic salt is used in an amount of 0.5 mol% to 10 mol%, and the preferable inorganic salt is used in an amount of 1 mol% to 1.2 mol%.
The organic solvent is one of acetonitrile, tetrahydrofuran, N-methyl pyrrolidone and dimethyl sulfoxide, and the preferable organic solvent is N-methyl pyrrolidone.
The reaction temperature is 130 to 170℃and preferably 130 ℃.
The reaction time is 12 to 48 and h, preferably 24 h.
The invention will now be described in further detail by way of examples and specific examples of the synthesis of 1, 3-dicyclohexylurea, but the examples are not intended to be limiting.
The test procedures, which are not specifically described in the examples below, were carried out according to methods and conditions conventional in the art, and the materials used, unless otherwise specified, were commercially available.
Example 1
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
cerium oxide (861 mg,0.1 equiv.) potassium phosphate (106 mg,1 mol%), cyclohexylamine (50 mmol) and dried N-methylpyrrolidone (20 mL) were added in this order to a reaction vessel of volume 50 mL under carbon dioxide, and CO was passed through 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 42%.
Figure 403129DEST_PATH_IMAGE004
Example 2
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
cerium oxide (4.30 g,0.5 equiv.) potassium phosphate (106 mg,1 mol%), cyclohexylamine (50 mmol) and dried N-methylpyrrolidone (20 mL) were added in succession to a reaction vessel of volume 50 mL under carbon dioxide, CO 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 89%.
Example 3
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
cerium oxide (8.61 g,1.0 equiv.) potassium phosphate (106 mg,1 mol%), cyclohexylamine (50 mmol) and dried N-methylpyrrolidone (20 mL) were added in succession to a reaction vessel of volume 50 mL under carbon dioxide, under CO 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 89%.
Example 4
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
cerium oxide (4.30 g,0.5 equiv.) potassium phosphate (53 mg,0.5 mol%), cyclohexylamine (50 mmol) and dried N-methylpyrrolidone (20 mL) were added in succession to a reaction vessel of volume 50 mL under carbon dioxide, and CO was passed through 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 71%.
Example 5
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
in a carbon dioxide ringTo a reaction vessel of volume 50 mL was successively added cerium oxide (4.30 g,0.5 equiv.), potassium phosphate (159 mg,1.5 mol%), cyclohexylamine (50 mmol) and dried N-methylpyrrolidone (20 mL) under CO 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 85%.
Example 6
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
cerium oxide (4.30 g,0.5 equiv.) potassium phosphate (531 mg,5 mol%), cyclohexylamine (50 mmol) and dried N-methylpyrrolidone (20 mL) were added in succession to a reaction vessel of volume 50 mL under carbon dioxide, under CO 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 84%.
Example 7
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
cerium oxide (4.30 g,0.5 equiv.) potassium phosphate (106 mg,1 mol%), cyclohexylamine (50 mmol) and dried acetonitrile (20 mL) were added sequentially to a reaction vessel having a volume of 50 mL under carbon dioxide atmosphere, followed by CO 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 68%.
Example 8
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
in the carbon dioxide environment, 50 mL of the volume is formedCerium oxide (4.30 g,0.5 equiv.) potassium phosphate (106 mg,1 mol%), cyclohexylamine (50 mmol) and dried tetrahydrofuran (20 mL) were added sequentially to the reaction vessel, and CO was introduced 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 74%.
Example 9
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
cerium oxide (4.30 g,0.5 equiv.) potassium phosphate (106 mg,1 mol%), cyclohexylamine (50 mmol) and dried dimethyl sulfoxide (20 mL) were added in this order to a reaction vessel having a volume of 50 mL under carbon dioxide atmosphere, followed by CO 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction, the temperature is restored to room temperature, the catalyst is collected by filtration, then 100 mL deionized water is added into the anti-filtrate, the mixture is stirred for 30 minutes at room temperature and then filtered, and the target product 1, 3-dicyclohexylurea of white solid is obtained, wherein the yield is 65%.
Comparative examples
A synthesis method of 1, 3-dicyclohexylurea comprises the following steps:
adding cyclohexylamine (50 mmol) and dried N-methylpyrrolidone (20 mL) into a reaction kettle with a volume of 50 mL under the environment of carbon dioxide in sequence, and introducing CO 2 (5 MPa) under 130 ℃ with stirring, reaction 12 h. After the reaction is finished, the temperature is restored to room temperature, 100 mL deionized water is added into the reaction liquid, and the reaction liquid is stirred at room temperature for 30 min, so that the target product 1, 3-dicyclohexylurea can not be obtained.
The above examples show that the process for preparing dialkyl urea of the present invention uses carbon dioxide and organic amine as raw materials to prepare 1, 3-dicyclohexylurea under the combined action of metal oxide and inorganic salt, and uses CO 2 The method is simple and easy to operate, and provides a new process path for the high-valued utilization of carbon dioxideA wire.

Claims (6)

1. A process for the preparation of a 1, 3-dicyclohexylurea compound, comprising the steps of: introducing carbon dioxide for ventilation, adding n-propylamine compound, metal oxide and inorganic salt into an organic solvent, controlling the temperature to be 130-170 ℃ in the carbon dioxide (5 MPa) atmosphere, and reacting 12-48 h under the magnetic stirring condition; after the reaction is finished, the temperature is restored to room temperature after the reaction is finished, a catalyst is collected by filtration, then 100 mL deionized water is added into the filtrate, the mixture is stirred at room temperature for 30 minutes and then filtered, and a white solid target product 1, 3-dicyclohexylurea compound is obtained; the reaction substrate is an organic amine compound, and the structure of the reaction substrate is shown as a formula (I);
wherein R is C3-C6 alkyl or cycloalkyl;
Figure DEST_PATH_IMAGE001
（Ⅰ）。
2. the method for preparing the 1, 3-dicyclohexylurea compound according to claim 1, wherein the organic solvent is acetonitrile (MeCN), tetrahydrofuran (THF), N-methylpyrrolidone (NMP) or Dimethylsulfoxide (DMSO) polar solvent.
3. The method for producing a 1, 3-dicyclohexylurea compound according to claim 1, wherein the metal oxide is CeO 2 、ZnO 2 、ZrO 2 And MnO 2 One of them.
4. The process for the preparation of 1, 3-dicyclohexylurea compound according to claim 1, wherein the inorganic salt is NaOH, KOH, K 3 PO 4 And K 2 HPO 3 One of them.
5. The process for producing a 1, 3-dicyclohexylurea compound according to claim 1, wherein the metal oxide is used in an amount of 0.1 to 1.0 equiv. based on the organic amine as the substrate.
6. The method for producing a 1, 3-dicyclohexylurea compound according to claim 1, wherein the amount of the inorganic salt is 0.5 mol% to 10 mol% based on the organic amine as the reaction substrate.
CN202211593407.0A 2022-12-13 2022-12-13 Preparation method of 1, 3-dialkyl urea compound Pending CN116178215A (en)

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