CN115521275B - Method for preparing oxamide compounds by using gold-based catalyst - Google Patents

Method for preparing oxamide compounds by using gold-based catalyst Download PDF

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CN115521275B
CN115521275B CN202211189997.0A CN202211189997A CN115521275B CN 115521275 B CN115521275 B CN 115521275B CN 202211189997 A CN202211189997 A CN 202211189997A CN 115521275 B CN115521275 B CN 115521275B
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oxamide
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CN115521275A (en
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何林
曹彦伟
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Suzhou Kehua Low Carbon Technology Research Co ltd
Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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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
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • 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
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a method for preparing oxamide compounds by using a gold-based catalyst, which comprises the steps of oxidizing and carbonylating amine compounds for 1-24 hours at room temperature-100 ℃ under the pressure of 0.1-2 MPa in the atmosphere of CO and air under the action of a supported gold catalyst to obtain oxamide compounds; the active component of the supported gold catalyst is gold, and the carrier is ZnO. The method for preparing the oxamide compound by catalysis adopts CO and air as raw materials, is low in cost and easy to obtain, has wide sources of amine compounds, can obtain the target oxamide compound with high yield through oxidative carbonylation reaction, has high atomic utilization rate of the reaction, and takes H as a byproduct 2 O. The method has the advantages of mild reaction conditions, reusability, high product yield and the like, is suitable for industrial production, and has wide application prospect.

Description

Method for preparing oxamide compounds by using gold-based catalyst
Technical Field
The invention relates to a method for preparing oxamide compounds by using a gold-based catalyst, in particular to a method for preparing oxamide by using cheap amine and CO as raw materials through amine oxidization and dicarbonylation under the catalysis of an Au-based catalyst, belonging to the technical field of organic synthetic chemistry.
Background
Oxamides are highly valued in academia and industry as a class of high value-added chemicals, which have wide applications, such as being important ligands in organic synthesis, preparing ethylene glycol by hydrogenation, and as slow-release nitrogen fertilizer, etc. The design of efficient catalytic systems, in particular heterogeneous catalytic systems, for the highly active and highly selective synthesis of oxamides is urgent. The amine oxidative dicarbonylation reaction is a very reliable method for preparing the oxamide, and the method has the characteristic of high atom economy and meets the development requirement of green chemistry. Therefore, different amine compounds are selected as substrates, and different types of oxamide products can be obtained through oxidative carbonylation reaction in the presence of a catalyst.
The prior method for preparing the oxamide mainly takes oxalyl chloride and amine as raw materials, and the oxamide is obtained through reaction. However, oxalyl chloride is a colorless fuming liquid, has a pungent smell, generates a large amount of heat during the reaction, generates hydrochloric acid, is liable to cause equipment corrosion, and requires a large amount of alkali for neutralization, so that the oxalamide is not suitable for industrial production. In addition, the method can also be prepared by substitution reaction of oxalic ester and amine, but the selectivity of the method is not easy to control, and excessive amine needs to be added; in addition, oxalate is also produced by carbonylation and is therefore not as economical as the amine oxidative bis-carbonylation process for producing oxamides. Currently, amine oxidative bis-carbonylation is focused mainly on homogeneous Pd catalytic systems, which require the addition of an additional iodine-containing promoter and have problems with catalyst separation (nat. Commun., 2016, 7, 12075). Japanese patent JP2014088380A reports the use of Au/HT (hydrotalcite) for the catalytic oxidative dicarbonylation of amines to oxamides, which reaction needs to be carried out at relatively high temperatures (110-150 ℃). With the rise in the price of other noble metals, the price of gold is now significantly lower than that of palladium. Therefore, it is important to utilize a relatively inexpensive gold catalyst and develop an effective means of catalyst separation for the synthesis of different types of oxamide products by amine oxidative bis-carbonylation reactions.
Disclosure of Invention
The invention mainly aims to provide a method for preparing oxamide compounds by using a gold-based catalyst, so as to overcome the defects of the prior art.
According to the method for preparing the oxamide compound by using the gold-based catalyst, under the action of the supported gold catalyst, the oxamide compound is obtained through oxidative carbonylation reaction for 1-24 hours under the conditions of room temperature and pressure of 0.1-2 MPa in the atmosphere of CO and air; the active component of the supported gold catalyst is gold, and the carrier is ZnO;
。
r in the amine 1 Comprising one of hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compounds with or without heteroatoms, said R 2 Including hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compounds with or without heteroatoms.
In the CO and air atmosphere, the volume fraction of CO is 80 percent, and the pressure ratio of CO and air is more than 4:1.
The molar dosage of the supported gold catalyst is 0.05-5% of the molar dosage of the amine.
In the supported gold catalyst, the loading amount of the active component gold is 0.5-10 wt%.
The oxidative carbonylation reaction is carried out in a reaction solvent comprising one or more of toluene, cyclohexane, tetrahydrofuran, acetonitrile, dioxane.
The supported gold catalyst is prepared by adopting a precipitation method, a coprecipitation method, a liquid phase reduction method or a gas phase reduction method.
Adding a gold source and a ZnO carrier into deionized water, adding a precipitant, standing at room temperature for reaction for 10-15 h, washing and drying to obtain a precursor, and roasting the precursor at 200-700 ℃ for 1-5 h to obtain the supported gold catalyst; the precipitant is at least one of sodium carbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide and ammonia water, and at least one of zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc bromide and zinc phosphate is adopted as the coprecipitation agent in the coprecipitation method;
the liquid phase reduction method is that a gold source and a ZnO carrier are added into deionized water, a reducing agent is added, the mixture is kept stand at room temperature for reaction for 10 to 15 hours, and the mixture is washed and dried to obtain the zinc oxide-zinc oxide composite material; the reducing agent comprises at least one of sodium borohydride, potassium borohydride and hydrazine hydrate;
the gas phase reduction method is to add a gold source and a ZnO carrier into deionized water, then add sodium carbonate, stand at room temperature for reaction for 10-15H, wash and dry, and then introduce H into a tube furnace 2 And N 2 Reducing the mixed gas at 100-500 ℃ for 2-3 hours to obtain the catalyst;
the gold source comprises at least one of chloroauric acid, potassium chloroaurate and triphenylphosphine gold chloride.
In conclusion, the method for preparing the oxamide compound by catalysis provided by the invention adopts CO and air as raw materials, is low in cost and easy to obtain, has wide sources of amine compounds, can obtain the target oxamide compound with high yield through oxidative carbonylation reaction, has high utilization rate of reaction atoms, and takes H as a byproduct 2 O. The method has the advantages of mild reaction conditions, reusability, high product yield and the like, is suitable for industrial production, and has wide application prospect.
Drawings
FIG. 1 is a transmission electron microscopic image of a 1% Au/MnO catalyst obtained in example 1 of the present invention;
FIG. 2 is a view showing the recycling of the catalyst obtained in example 1 of the present invention;
FIG. 3 is a view of oxalyl morpholine 1 H-spectrum;
FIG. 4 is a view of oxalyl morpholine 13 C spectrum.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have made long-term studies and a great deal of practice to propose the technical solution of the present invention. The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The technical scheme of the present invention will be described in further detail with reference to several preferred embodiments, but the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Example 1
Preparation of Au/ZnO catalyst by precipitation method
Weighing 0.2. 0.2g chloroauric acid (HAuCl) 4 ·3H 2 O) adding 100 ml deionized water into a 250 mL three-neck flask, stirring and dissolving at room temperature, slowly adding 10 g of ZnO carrier, fully stirring after the addition, adding a certain amount of sodium carbonate solution, regulating the pH to 8, continuing stirring for 3 hours, aging at room temperature, and standing for 12 hours; and washing the filter cake with deionized water until the filter cake is neutral, putting the filter cake into a 60 ℃ oven for drying for 12 hours, and roasting the filter cake in a muffle furnace at 300 ℃ for 3 hours after the drying is finished to obtain the 1% Au/ZnO-300 catalyst (catalyst 1). Different loadings of 0.5% Au/ZnO-300 (catalyst 2), 2% Au/ZnO-300 (catalyst 3) and 5% Au/ZnO-300 (catalyst 4) catalysts and different calcination temperatures of 1% Au/ZnO-400 (catalyst 5), 1% Au/ZnO-500 catalysts (catalyst 6) were prepared by the same method. The transmission electron microscope image of the 1% Au/ZnO-300 catalyst is shown in figure 1, and the gold nanoparticles can be seen to be uniformly dispersed on the carrier.
Example 2
Preparation of Au/ZnO catalyst by coprecipitation method
Separately, 0.2g of chloroauric acid and 36.4g of zinc nitrate (Zn (NO) 3 ) 3 ·6H 2 O) adding 200 ml deionized water into a 500 mL three-neck flask, stirring and dissolving at room temperature, slowly adding 10 g of ZnO carrier, fully stirring, adding a certain amount of sodium carbonate solution, regulating the pH to 8, continuously stirring for 3 hours, aging and standing for 12 hours; washing the filter cake with deionized water to neutrality, drying in oven at 60deg.C for 12 hr, and calcining at 400deg.C in muffle furnace for 3 hr to obtain 1% Au/ZnO-400 catalyst (catalyst 7). Different loadings of 2% Au/ZnO-400 (catalyst 8) and 5% Au/ZnO-400 (catalyst 9) catalysts and different calcination temperatures of 1% Au/ZnO-500 (catalyst 10) and 1% Au/ZnO-600 (catalyst 11) catalysts were prepared by the same method.
Example 3
Preparation of Au/ZnO catalyst by liquid phase reduction method
0.2g chloroauric acid is weighed and added into a 250 mL three-neck flask, 100 ml deionized water is added, then stirring and dissolving are carried out at room temperature, 10 g ZnO carrier is slowly added, after the addition is completed, stirring is carried out fully, and a certain amount of NaBH is added 4 Reducing gold into gold nano particles, continuously stirring for 3 hours, aging and standing for 12 hours; after washing the filter cake with deionized water to neutrality, it was dried in an oven at 60 ℃ for 12h to give a 1% au/ZnO catalyst (catalyst 12). Different loadings of 2% Au/ZnO (catalyst 13) and 5% Au/ZnO (catalyst 14) catalysts were made using the same method.
Example 4
Preparation of Au/ZnO catalyst by gas phase reduction method
Weighing 0.2g of chloroauric acid, adding into a 250 mL three-neck flask, adding 100 ml of deionized water, stirring at room temperature for dissolution, slowly adding 10 g of ZnO carrier, fully stirring after the addition, adding a certain amount of sodium carbonate solution, adjusting the pH to 8, continuing stirring for 3 hours, aging, and standing for 12 hours; washing the filter cake with deionized water to neutrality, drying in oven at 60deg.C for 12 hr, and introducing H into tubular furnace 2 And N 2 Mixed gas (H) 2 Volume fraction 5%) was reduced at 300 ℃ for 3 hours to give a 1% au/ZnO catalyst (catalyst 15).
Comparative example 1
Au/MO x Catalyst
0.2g of chloroauric acid is weighed and added into a 250 mL three-neck flask, 100 ml deionized water is added, then stirring and dissolving are carried out at room temperature, and 10 g of TiO is slowly added 2 Fully stirring the carrier after the material addition is completed, adding a certain amount of sodium carbonate solution, adjusting the pH to 8, continuously stirring for 3 hours, aging and standing for 12 hours; washing the filter cake with deionized water to neutrality, and drying in oven at 60deg.C for 12h, after drying, roasting for 3 hours at 300 ℃ in a muffle furnace to obtain 1% Au/TiO 2 Catalyst (catalyst 16). The carrier is changed to prepare 1 percent Au/MgO (catalyst 17) and 1 percent Au/CeO with different loading amounts by adopting the same method 2 (catalyst 18), 1% Au/HT (catalyst 19), 1% Au/Al 2 O 3 (catalyst 20) catalyst.
Comparative example 2
Weighing 0.17 g g palladium chloride, adding the palladium chloride into a 250 mL three-neck flask, adding 100 g ml deionized water, stirring at room temperature for dissolution, slowly adding 10 g of ZnO carrier, fully stirring after the addition, adding a certain amount of sodium carbonate solution, adjusting the pH to 8, continuing stirring for 3 hours, aging and standing for 12 hours; the filter cake was then washed with deionized water to neutrality, dried in an oven at 60 ℃ for 12h, and after drying, calcined in a muffle furnace at 300 ℃ for 3h to give a 1% Pd/ZnO catalyst (catalyst 21).
Comparative example 3
Weighing 0.2g g rhodium chloride, adding the rhodium chloride into a 250 mL three-neck flask, adding 100 g ml deionized water, stirring at room temperature for dissolution, slowly adding 10 g ZnO carrier, fully stirring after the addition, adding a certain amount of sodium carbonate solution, adjusting the pH to 8, continuing stirring for 3 hours, aging and standing for 12 hours; the filter cake was then washed with deionized water to neutrality, dried in an oven at 60 ℃ for 12h, and after drying, calcined in a muffle furnace at 300 ℃ for 3h to give a 1% rh/ZnO catalyst (catalyst 22).
Examples 5 to 19
0.25 mmol of morpholine and 3 mL toluene were charged into a 10mL autoclave, and the Au/ZnO catalysts prepared in examples 1-4 were added, respectively (the molar amount of the catalyst was 2% of the molar amount of morpholine, calculated as gold content). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting at room temperature for 12h, centrifuging the reaction liquid after the reaction is finished, quantitatively analyzing the oxalyl morpholine product by gas chromatography, and qualitatively analyzing the oxalyl morpholine product by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 3.70 (t, 8H), 3.64 (t, 4H), 3.46 – 3.49 (m, 4H).
13 C NMR (101 MHz, Chloroform-d) δ 162.86, 66.95, 66.64, 46.64, 41.59.
the experimental results under different reaction conditions are summarized in table 1. The catalyst obtained in example 1 was recycled, as shown in fig. 2, and it can be seen that the catalyst had good stability. FIG. 3 is a view of oxalyl morpholine 1 H spectrum, FIG. 4 is oxalyl morpholine 13 C spectrum.
Comparative examples 4 to 10
0.25 mmol of morpholine and 3 mL toluene were added to a 10mL autoclave, and the M/MO prepared in comparative examples 1-3 were added, respectively x Catalyst (amount of catalyst is 2 mol% of substrate). And (3) respectively charging 0.1 MPa air and 0.4 MPa CO, reacting for 12 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the oxalyl morpholine product by using gas chromatography. The experimental results under different reaction conditions are summarized in table 1.
Example 23
50 mmol of morpholine and 50 mL of toluene were added to a 300 mL autoclave with Au/ZnO (catalyst 1, catalyst amount 0.01 mol% of substrate). Filling 0.4 MPa air and 2MPa CO respectively, reacting at room temperature for 240 h, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by gas chromatography to obtain the oxalyl morpholine with the yield of 86%.
Example 24
0.25 mmol of piperidine and 3 mL toluene were added to a 10mL autoclave as Au/ZnO (catalyst 1, catalyst amount 2 mol% of substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 24 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by using gas chromatography to obtain 98 percent of yield; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 3.63 – 3.49 (m, 4H), 3.42 – 3.22 (m, 4H), 1.80 – 1.41 (m, 12H).
13 C NMR (101 MHz, Chloroform-d) δ 163.65, 47.30, 41.85, 26.53, 25.43, 24.53.
example 25
0.25 mmol of 4-methoxypiperidine and 3 mL toluene were charged into a 10mL autoclave as Au/ZnO catalyst 1 (the amount of catalyst is 2 mol% of the substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 24 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by using gas chromatography to obtain the yield of 95%; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 3.84 – 3.71 (m, 2H), 3.63 – 3.41 (m, 2H), 3.35 (s, 6H), 3.24 (dtd, 2H), 1.96 – 1.79 (m, 4H), 1.72 – 1.56 (m, 5H).
13 C NMR (101 MHz, Chloroform-d) δ 163.46, 74.85, 55.93, 43.19, 37.84, 31.06, 31.02, 29.90, 29.87.
example 26
0.25 mmol of hexamethyleneimine and 3 mL toluene were added to a 10mL autoclave as Au/ZnO (catalyst 1, catalyst amount 2 mol% of substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 24 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by using gas chromatography to obtain 98 percent of yield; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 3.60 – 3.51 (m, 4H), 3.49 – 3.35 (m, 4H), 1.84 – 1.71 (m, 8H), 1.66 – 1.54 (m, 8H).
13 C NMR (101 MHz, Chloroform-d) δ 165.46, 48.25, 44.87, 29.20, 28.08, 27.24, 26.67.
example 27
0.25 mmol of N-methylpiperazine and 3 mL toluene were charged into a 10mL autoclave as Au/ZnO (catalyst 1, catalyst amount 2 mol% of substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 12 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by using gas chromatography to obtain the yield of 94%; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 3.65 (t, 4H), 3.41 (t, 4H), 2.43 (s, 8H), 2.30 (s, 6H).
13 C NMR (101 MHz, Chloroform-d) δ 163.01, 55.06, 54.33, 46.02, 45.97, 40.86.
example 28
0.25 mmol of N-methylallylamine and 3 mL toluene were added to a 10mL autoclave as Au/ZnO (catalyst 1, catalyst amount 2 mol% of substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 24 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, quantitatively analyzing the product by using gas chromatography, and obtaining 85 percent of yield; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 5.97 – 5.59 (m, 2H), 5.37 – 5.07 (m, 4H), 4.03 (tt, J = 6.3, 1.4 Hz, 2H), 3.87 (ddt, J = 11.1, 6.0, 1.4 Hz, 2H), 3.13 – 2.70 (m, 6H).
13 C NMR (101 MHz, Chloroform-d) δ 165.11, 165.06, 164.80, 164.74, 132.54, 132.38, 131.65, 131.63, 119.08, 118.90, 118.69, 118.59, 52.90, 52.68, 48.63, 48.54, 34.85, 34.50, 31.45, 31.37.
example 29
0.25 mmol of N-methylbenzylamine and 3. 3 mL toluene were charged into a 10mL autoclave as Au/ZnO (catalyst 1, catalyst amount: 2 mol% of substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 24 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by using gas chromatography to obtain 97 percent of yield; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 7.60 – 6.94 (m, 10H), 4.68 – 4.28 (m, 4H), 3.17 – 2.57 (m, 6H).
13 C NMR (101 MHz, Chloroform-d) δ 165.34, 165.21, 165.12, 165.10, 136.02, 135.90, 135.58, 135.56, 128.95, 128.92, 128.40, 128.32, 128.21, 128.03, 127.93, 127.87, 53.95, 53.79, 49.67, 49.59, 34.83, 34.49, 31.71, 31.68.
example 30
0.25 mmol dimethylamine and 3 mL toluene were added to a 10mL autoclave as Au/ZnO (catalyst 1, catalyst amount 2 mol% of substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 12 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by using gas chromatography to obtain the yield of 95%; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 2.98 (s, 12H).
13 C NMR (101 MHz, Chloroform-d) δ 165.08, 36.92, 33.56.
example 31
0.25 mmol of diethylamine and 3 mL toluene were charged into a 10mL autoclave as Au/ZnO (catalyst 1, catalyst amount 2 mol% of substrate). Filling 0.1 MPa air and 0.4 MPa CO respectively, reacting for 24 hours at room temperature, centrifuging the reaction liquid after the reaction is finished, and quantitatively analyzing the product by using gas chromatography to obtain 96 percent of yield; it was qualitatively analyzed by NMR.
The structure of the product is as follows:
1 H NMR (400 MHz, Chloroform-d) δ 3.43 (q, J = 7.1 Hz, 4H), 3.27 (q, J = 7.1 Hz, 4H), 1.18 (dt, J = 11.3, 7.1 Hz, 12H).
13 C NMR (101 MHz, Chloroform-d) δ 164.86, 42.41, 38.43, 14.11, 12.69.
in summary, the method for preparing the Au/ZnO catalytic amine oxidative dicarbonylation adopts amine with wide sources, CO and air as raw materials, has wide sources, can obtain high-yield target oxamide through catalytic amine oxidative dicarbonylation reaction, has high reaction atom utilization rate, adopts a stable gold-based catalyst, is suitable for industrial production, and has wide application prospect.
In addition, the inventor also refers to the modes of examples 1-31, and tests are carried out on other raw materials, conditions and the like listed in the specification, so that corresponding effects can be achieved, the yield of the synthesis method is high, the method is suitable for industrial production, and the application prospect is wide.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims (7)

1. A method for preparing oxamide compounds by using a gold-based catalyst is characterized in that: under the action of a supported gold catalyst, an amine compound is subjected to oxidative carbonylation reaction for 1-24 hours in the atmosphere of CO and air at the room temperature and the pressure of 0.1-2 MPa to obtain an oxamide compound; the active component of the supported gold catalyst is gold, and the carrier is ZnO;
；
r in the amine compound 1 Is one of hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compound containing or not containing hetero atom, R 2 Is one of hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compounds with or without heteroatoms.
2. The method for preparing an oxamide compound using a gold-based catalyst according to claim 1, wherein: in the CO and air atmosphere, the volume fraction of CO is 80 percent, and the pressure ratio of CO and air is more than 4:1.
3. The method for preparing an oxamide compound using a gold-based catalyst according to claim 1, wherein: the molar amount of the supported gold catalyst is 0.05-5% of the molar amount of the amine calculated by the gold content.
4. The method for preparing an oxamide compound using a gold-based catalyst according to claim 1, wherein: in the supported gold catalyst, the loading amount of the active component gold is 0.5-10 wt%.
5. The method for preparing an oxamide compound using a gold-based catalyst according to claim 1, wherein: the oxidative carbonylation reaction is carried out in a reaction solvent comprising one or more of toluene, cyclohexane, tetrahydrofuran, acetonitrile, dioxane.
6. The method for preparing an oxamide compound using a gold-based catalyst according to claim 1, wherein: the supported gold catalyst is prepared by adopting a precipitation method, a coprecipitation method, a liquid phase reduction method or a gas phase reduction method.
7. The method for preparing an oxamide compound using a gold-based catalyst as claimed in claim 6, wherein: adding a gold source and a ZnO carrier into deionized water, adding a precipitant, standing at room temperature for reaction for 10-15 h, washing and drying to obtain a precursor, and roasting the precursor at 200-700 ℃ for 1-5 h to obtain the supported gold catalyst; the precipitant is at least one of sodium carbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide and ammonia water, and at least one of zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc bromide and zinc phosphate is adopted as the coprecipitation agent in the coprecipitation method;
the liquid phase reduction method is that a gold source and a ZnO carrier are added into deionized water, a reducing agent is added, the mixture is kept stand at room temperature for reaction for 10 to 15 hours, and the mixture is washed and dried to obtain the zinc oxide-zinc oxide composite material; the reducing agent comprises at least one of sodium borohydride, potassium borohydride and hydrazine hydrate;
the gas phase reduction method is to add a gold source and a ZnO carrier into deionized water, then add sodium carbonate, stand at room temperature for reaction for 10-15H, wash and dry, and then introduce H into a tube furnace 2 And N 2 Reducing the mixed gas at 100-500 ℃ for 2-3 hours to obtain the mixed gas;
the gold source comprises at least one of chloroauric acid, potassium chloroaurate and triphenylphosphine gold chloride.
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