Application of amorphous iron-copper composite metal oxides as catalysts for the hydration of nitrile to prepare amides
The synthesis of amides by catalytic hydration of nitriles in an aqueous solvent using an amorphous Fe0.7Cu0.3Ox-300 composite metal oxide catalyst solves the problems of high cost of precious metal catalysts and pollution of traditional methods, and realizes efficient, green and simplified amide synthesis.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LANZHOU UNIV
- Filing Date
- 2024-01-22
- Publication Date
- 2026-06-30
AI Technical Summary
Existing precious metal catalysts are costly in the process of hydration of nitriles to prepare amides, which limits their industrial application. Furthermore, traditional methods require organic solvents and acid-base additives, leading to pollution and complex purification processes.
Amorphous Fe0.7Cu0.3Ox-300 composite metal oxide was used as a catalyst. The catalyst was prepared by low-temperature molten salt process under water as solvent. The catalyst was used for the hydration of nitriles to generate amides, which avoided the need for additives and simplified the purification process.
It achieves efficient catalytic hydration of aromatic, aliphatic, and heteroatom aromatic nitriles under mild conditions, reducing costs, simplifying purification steps, and possessing industrial application potential.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis technology, specifically relating to the application of an iron-copper composite metal oxide as a catalyst for the hydration of nitriles to prepare amides. Technical Background
[0002] Amide groups are the basic structural units of polypeptides, enzymes, and proteins, with the chemical formula CO-NH2. Amides and their derivatives play important roles in various fields, including medicine, agriculture, and the chemical industry (see *Science*, 2022, Vol. 10, No. 26, 8433-8442). Acrylamide is a monomer of polyacrylamide and is widely used in water treatment and various industrial processes (see *Nat. Commun.*, 2022, Vol. 13, No. 1, 4362). Cinnamamide has significant pharmacological potential in treating a range of diseases, including cancer and cardiovascular diseases (see *Green Chem.*, 2019, Vol. 21, No. 21, 5803-5807). Nicotinamide is an important B vitamin, and pyrazinamide is an anti-tuberculosis drug (see *Int. J. Biol. Macromol.*, 2024, Vol. 254, 127800). In addition, the antitumor properties of various thiophene and furanamide derivatives have been reported (see *Chem. Bio. Drug Des.*, 2015, Vol. 86, No. 4, pp. 918-925). Given the wide application and inherent value of amide compounds, developing a simple, efficient, and universally applicable synthetic method is of great significance.
[0003] Among various methods for synthesizing amides, nitrile hydration is considered one of the most atomically efficient (see *ACS Sustainable Chem. Eng.*, 2023, Vol. 11, No. 23, 8404-8405). The design of novel nitrile hydration catalysts has attracted considerable attention. Currently reported excellent catalysts are mainly homogeneous or heterogeneous noble metal catalysts, such as palladium (see *ACS Catal.*, 2021, Vol. 11, No. 14, 8716-8726), ruthenium (see *Angew. Chem. Int. Ed.*, 2004, Vol. 43, No. 12, 1576-1580), and platinum (see *J. Am. Chem. Soc.*, 2018, Vol. 140, No. 50, 17782-17789). However, the high cost of noble metal catalysts limits their industrial application. Therefore, there is an urgent need to develop green, environmentally friendly, non-noble metal nitrile hydration catalytic systems. Summary of the Invention
[0004] We developed amorphous Fe using a simple low-temperature molten salt process.0.7 Cu 0.3 O x -300, as a highly efficient and green heterogeneous catalyst, was used for the hydration of nitriles to amides without the need for any additives. Under mild conditions, using water as a solvent, a variety of amides, including aromatic, aliphatic, and heteroatom aromatic amides, were successfully synthesized. Since most amides are insoluble in cold water, the products crystallize out after the reaction, greatly simplifying the purification process and reducing costs. The method is simple, low-cost, safe, and has a high synthesis rate, showing considerable potential for industrial application.
[0005] In a first aspect, this invention provides an application of an iron-copper composite metal oxide as a catalyst for the hydration of nitrile to prepare amides. The catalyst is prepared by adding iron nitrate, copper nitrate, sodium hydroxide, and sodium chloride in a specific ratio to a mortar, mixing thoroughly, and grinding for 1 hour to obtain a molten metal salt. The molten metal salt is then washed three times with deionized water, vacuum dried at 60 °C, and calcined at 200-400 °C to obtain the desired catalyst. The X-ray diffraction pattern of the catalyst is shown below. Figure 1 As shown.
[0006] Preferably, in the method for preparing the iron-copper composite metal oxide, the molar ratio of iron nitrate to copper nitrate is 9:1 to 5:5.
[0007] Secondly, this invention provides an application of amorphous iron-copper composite metal oxide as a catalyst for the hydration of nitrile to prepare amides. The method is as follows: using the nitrile shown in formula (I) as a raw material, water, an organic solvent, or a mixed solvent (water and organic solvent mixed in a certain proportion) as reaction solvents, and using the amorphous iron-copper composite metal oxide as a catalyst, a hydration reaction is catalyzed to synthesize the amide shown in formula (II). The organic solvent includes any one or a combination of several of methanol, isopropanol, tert-butanol, and tetrahydrofuran.
[0008]
[0009] Equation (I) Equation (II)
[0010] Wherein, R is selected from any one of benzonitrile, ortho-benzylmethyl, meta-benzylmethyl, para-benzylmethyl, ortho-benzoxy, meta-benzoxy, para-benzoxy, ortho-phenylchloroyl, meta-phenylchloroyl, para-phenylchloroyl, ortho-phenylnitrol, meta-phenylnitrol, para-phenylnitrol, ortho-phenylaldehyde, meta-phenylaldehyde, para-phenylaldehyde, para-phenylcyano, styryl, pyridyl, pyrazinyl, vinyl, ortho-thiophenyl, ortho-furanyl.
[0011] Preferably, the substrate includes: benzonitrile, 4-chlorobenzonitrile, 2-pyridinecarboxynitrile, nicotinic nitrile, pyrazinonitrile, and acrylonitrile.
[0012] Preferably, the catalyst is an amorphous iron-copper composite metal oxide catalyst.
[0013] Preferably, the catalyst is Fe. 0.7 Cu 0.3 O x -300.
[0014] Preferably, the ratio of the catalyst to the nitrile is 5-50 g: 1 mol.
[0015] Preferably, the mass ratio of the catalyst to the amount of nitrile is 20 g: 1 mol.
[0016] Preferably, the mass ratio of the reaction solvent to the nitric acid is 3-8:1.
[0017] Preferably, the mass ratio of the reaction solvent to the nitric acid is 6:1.
[0018] Preferably, the reaction solvent is water.
[0019] Preferably, the method includes: adding nitric acid and amorphous iron-copper composite metal oxide into a reactor containing solvent, reacting at 80-140 °C for 2-6 h, filtering while hot, and crystallizing at cooling to obtain amide.
[0020] Preferably, the reaction temperature is 80-140 °C.
[0021] Preferably, the reaction temperature is 130 °C.
[0022] Preferably, the reaction time is 0.5-6 h.
[0023] Preferably, the reaction time is 4 hours.
[0024] Compared with existing technologies, the method for preparing amides by catalytic hydration of nitriles according to the present invention has the following advantages:
[0025] (1) This invention innovatively uses amorphous iron-copper composite metal oxide as a catalyst, which exhibits excellent hydration performance for aromatic nitriles, aliphatic nitriles, and heteroatom aromatic nitriles under mild reaction conditions. Compared with traditional noble metal catalysts, the catalyst cost is significantly reduced, and it has the potential for large-scale industrial application.
[0026] (2) The present invention uses water as a solvent, which is green, environmentally friendly and pollution-free compared with traditional organic solvents, and the preparation and separation of amides are completed in one step, simplifying the purification process.
[0027] (3) The reaction system does not require acid or base additives, making it green and environmentally friendly, and reducing the cost of industrial applications.
[0028] (3) The nitrile used in this invention is a basic raw material commonly used in industry, and is inexpensive and readily available. Attached Figure Description
[0029] Figure 1 X-ray diffraction pattern of the catalyst;
[0030] Figure 2 Mass spectrum of benzamide synthesized by the method described in Example 1;
[0031] Figure 3 Mass spectrum of benzamide synthesized by the method described in Example 2;
[0032] Figure 4 Mass spectrum of benzamide synthesized by the method described in Example 3;
[0033] Figure 5 Mass spectrum of benzamide synthesized by the method described in Example 4;
[0034] Figure 6 Mass spectrum of benzamide synthesized by the method described in Example 5;
[0035] Figure 7 Mass spectrum of the product 4-chlorobenzamide synthesized by the method shown in Example 7;
[0036] Figure 8 Mass spectrum of 2-pyridine amide synthesized by the method shown in Example 8;
[0037] Figure 9 Mass spectrum of nicotinamide synthesized by the method shown in Example 9;
[0038] Figure 10 Mass spectrum of pyrazinamide synthesized by the method shown in Example 10;
[0039] Figure 11 Mass spectrum of acrylamide synthesized by the method shown in Example 11; Detailed Implementation
[0040] The present invention will be further described in detail below with reference to specific embodiments. The scope of protection of the present invention is not limited thereto. Unless otherwise specified, all raw materials used in the following embodiments can be purchased commercially. Detailed Implementation
[0042] The present invention will be further described in detail below with reference to specific embodiments. The scope of protection of the present invention is not limited thereto. Unless otherwise specified, all raw materials used in the following embodiments can be purchased commercially.
[0043] Example 1: Synthesis of benzamide using different reaction solvents
[0044] 1. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water. Add a magnetic stirrer and heat to 130 °C. React for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0045] 2. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of isopropanol. Add a magnetic stirrer and heat to 130 °C. React for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0046] 3. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of tert-butanol. Add a magnetic stirrer and heat to 130 °C. React for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0047] 4. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of tetrahydrofuran. Add a magnetic stirrer and heat to 130 °C. React for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0048] 5. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of methanol. Add a magnetic stirrer and heat to 130 °C. React for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0049] 6. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile, 60 g of water and isopropanol solvent (volume ratio 1:1), add a magnetic stirrer and heat to 130 °C, react for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0050] 7. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile, 60 g of water and methanol solvent (volume ratio 1:1), add a magnetic stirrer and heat to 130 °C, react for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0051] 8. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile, 60 g of water and tert-butanol solvent (volume ratio 1:1), add a magnetic stirrer and heat to 130 °C, react for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0052] The yields of benzamide products obtained by the preparation methods described in 1-8 above were calculated, and the results are shown in Table 1 below:
[0053] Table 1. Process parameters and yield of benzamide as described in Example 1.
[0054] Serial Number catalyst solvent reaction temperature reaction time Product yield 1 <![CDATA[Fe 0.7 With 0.3 A x -300]]> water 130 ℃ 4 h 99% 2 <![CDATA[Fe 0.7 With 0.3 A x -300]]> Isopropanol 130 ℃ 4 h 57% 3 <![CDATA[Fe 0.7 With 0.3 A x -300]]> tert-Butanol 130 ℃ 4 h 32% 4 <![CDATA[Fe 0.7 With 0.3 A x -300]]> Tetrahydrofuran 130 ℃ 4 h 11% 5 <![CDATA[Fe 0.7 With 0.3 A x -300]]> methanol 130 ℃ 4 h 15% 6 <![CDATA[Fe 0.7 With 0.3 A x -300]]> Water + Isopropanol 130 ℃ 4 h 59% 7 <![CDATA[Fe 0.7 With 0.3 A x -300]]> water + methanol 130 ℃ 4 h 42% 8 <![CDATA[Fe 0.7 With 0.3 A x -300]]> Water + tert-butanol 130 ℃ 4 h 47%
[0055] The mass spectrum of the main product synthesized in the above reaction is shown below. Figure 2 As shown (the mass spectra of the main products of the above 8 reactions are the same, so only one mass spectrum is provided). The above results show that benzonitrile can be synthesized into benzamide by using water, organic solvent, and mixed solvent (water and organic solvent mixed in a certain proportion) as reaction solvents and iron-copper composite metal oxide as catalyst, all of which showed catalytic activity; and the yield of benzamide obtained by using water as reaction solvent can reach up to 99%.
[0056] Example 2: Synthesis of benzamide with different amounts of reaction solvent
[0057] 1. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 30 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot and cool to crystallize to obtain the product benzamide.
[0058] 2. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 40 g of water solvent, add a magnetic stirrer and heat to 130 °C, react for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0059] 3. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 50 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0060] 4. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent, add a magnetic stirrer and heat to 130 °C, react for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0061] 5. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 70 g of water solvent, add a magnetic stirrer and heat to 130 °C, react for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0062] 6. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 80 g of water solvent, add a magnetic stirrer and heat to 130 °C, react for 4 h, then filter while hot and cool to crystallize to obtain the product benzamide.
[0063] The yields of benzamide products obtained by the preparation methods described in 1-6 above were calculated, and the results are shown in Table 2 below:
[0064] Table 2. Process parameters and yield of benzamide as described in Example 2.
[0065] Serial Number catalyst Solvent volume reaction temperature reaction time Product yield 1 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 30 g 130 ℃ 4 h 81% 2 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 40 g 130 ℃ 4 h 87% 3 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 50 g 130 ℃ 4 h 89% 4 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 4 h 99% 5 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 70 g 130 ℃ 4 h 94% 6 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 80 g 130 ℃ 4 h 90%
[0066] The mass spectrum of the main product obtained from the above reaction is shown below. Figure 3 As shown (the mass spectra of the main products of the above 6 reactions are the same, so only one mass spectrum is provided). The above results indicate that benzonitrile can be catalyzed to synthesize benzamide using different amounts of water (30-80 g) as the reaction solvent and iron-copper composite metal oxide as the catalyst; at the same time, when the volume ratio of benzonitrile to water is 1:3-1:8 (the mass of water is about 3-8 times the mass of aniline), the yield of benzamide obtained is above 80%, and when the volume ratio of benzonitrile to water is 6:1 (the mass of water is about 6 times the mass of aniline), the yield of benzamide obtained reaches 99%.
[0067] Example 3: Synthesis of benzamide with different iron-copper mass ratios and calcination temperatures.
[0068] 1. Add 2 g of CuO-300 catalyst (a composite metal oxide of iron and copper) to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of aqueous solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot and cool to crystallize to obtain the product benzamide.
[0069] 2. Add 2 g of Fe2O3-300 catalyst (iron-copper composite metal oxide) to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of aqueous solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot and cool to crystallize to obtain the product benzamide.
[0070] 3. The iron-copper composite metal oxide Fe 0.7 Cu 0.3 O x -200 catalyst 2 g was added to a 250 mL autoclave, followed by 10.2 g benzonitrile and 60 g aqueous solvent. A magnetic stirrer was added and the mixture was heated to 130 °C and reacted for 4 h. The mixture was then filtered while hot and cooled to crystallize, yielding the product benzamide.
[0071] 4. The iron-copper composite metal oxide Fe 0.7 Cu 0.3 O x 2 g of the -300 catalyst was added to a 250 mL autoclave, followed by 10.2 g of benzonitrile and 60 g of aqueous solvent. A magnetic stirrer was added and the mixture was heated to 130 °C and reacted for 4 h. The mixture was then filtered while hot and cooled to crystallize, yielding the product benzamide.
[0072] 5. The iron-copper composite metal oxide Fe 0.7 Cu 0.3 O x 2 g of the -400 catalyst was added to a 250 mL autoclave, followed by 10.2 g of benzonitrile and 60 g of aqueous solvent. A magnetic stirrer was added and the mixture was heated to 130 °C and reacted for 4 h. The mixture was then filtered while hot and cooled to crystallize, yielding the product benzamide.
[0073] 6. The iron-copper composite metal oxide Fe 0.9 Cu 0.1 O x 2 g of the -300 catalyst was added to a 250 mL autoclave, followed by 10.2 g of benzonitrile and 60 g of aqueous solvent. A magnetic stirrer was added and the mixture was heated to 130 °C and reacted for 4 h. The mixture was then filtered while hot and cooled to crystallize, yielding the product benzamide.
[0074] 7. The iron-copper composite metal oxide Fe 0.5 Cu 0.5 O x 2 g of the -300 catalyst was added to a 250 mL autoclave, followed by 10.2 g of benzonitrile and 60 g of aqueous solvent. A magnetic stirrer was added and the mixture was heated to 130 °C and reacted for 4 h. The mixture was then filtered while hot and cooled to crystallize, yielding the product benzamide.
[0075] The yields of benzamide products obtained by the preparation methods described in 1-7 above were calculated, and the results are shown in Table 3 below:
[0076] Table 3. Process parameters and yield of benzamide as described in Example 3.
[0077] Serial Number catalyst Solvent volume reaction temperature reaction time Product yield 1 CuO-300 60 g 130 ℃ 4 h 1% 2 <![CDATA[Fe2O3-300]]> 60 g 130 ℃ 4 h 1% 3 <![CDATA[Fe 0.7 With 0.3 A x -200]]> 60 g 130 ℃ 4 h 85% 4 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 4 h 99% 5 <![CDATA[Fe 0.7 With 0.3 A x -400]]> 60 g 130 ℃ 4 h 53% 6 <![CDATA[Fe 0.9 With 0.1 A x -300]]> 60 g 130 ℃ 4 h 54% 7 <![CDATA[Fe 0.5 With 0.5 A x -300]]> 60 g 130 ℃ 4 h 61%
[0078] The mass spectrum of the main product obtained from the above reaction is shown below. Figure 4 As shown (the mass spectra of the main products of the above 7 reactions are the same, so only one mass spectrum is provided). The above results indicate that different iron-copper mass ratios (9:1-1:1) and different calcination temperatures (200-400 ℃) in the iron-copper composite metal oxide significantly affect the catalyst activity; simultaneously, the benzamide yield obtained from the reaction of iron-copper composite metal oxides with different iron-copper mass ratios and calcination temperatures is all above 50%, and the catalyst Fe... 0.7 Cu 0.3 O x -300 exhibited optimal activity, and the yield of benzamide obtained from the reaction reached 99%.
[0079] Example 4: Synthesis of benzamide at different reaction temperatures
[0080] 1. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 70 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0081] 2. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 80 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0082] 3. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent, heat to 90 °C, react for 4 h, and then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0083] 4. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 100 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0084] 5. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 110 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0085] 6. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 120 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0086] 7. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0087] 8. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 140 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0088] The yields of benzamide products obtained by the preparation methods described in 1-8 above were calculated, and the results are shown in Table 3 below:
[0089] Table 4. Process parameters and yield of benzamide as described in Example 4.
[0090] Serial Number catalyst Solvent volume reaction temperature reaction time Product yield 1 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 70 ℃ 4 h 11% 2 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 80 ℃ 4 h 15% 3 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 90 ℃ 4 h 17% 4 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 100 ℃ 4 h 74% 5 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 110 ℃ 4 h 88% 6 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 120 ℃ 4 h 90% 7 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 4 h 99% 8 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 140 ℃ 4 h 99%
[0091] The mass spectrum of the main product obtained from the above reaction is shown below. Figure 5 As shown (the mass spectra of the main products of the above 8 reactions are the same, so only one mass spectrum is provided). The above results indicate that, using water as the reaction solvent and iron-copper composite metal oxide as the catalyst, benzonitrile can be catalyzed to synthesize benzamide at a reaction temperature of 70-140 °C; at a reaction temperature of 100-140 °C, the yield of benzamide obtained is above 80%; and at a reaction temperature of 130-140 °C, the yield of benzamide obtained can reach as high as 99%.
[0092] Example 5: Synthesis of benzamide with different reaction times
[0093] 1. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 0.5 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0094] 2. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 1 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0095] 3. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 2 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0096] 4. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 3 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0097] 5. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0098] 6. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 5 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0099] The yields of benzamide products obtained by the preparation methods described in 1-6 above were calculated, and the results are shown in Table 5 below:
[0100] Table 5. Process parameters and yield of benzamide as described in Example 5.
[0101] Serial Number catalyst Solvent volume reaction temperature reaction time Product yield 1 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 0.5 h 23% 2 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 1 h 41% 3 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 2 h 73% 4 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 3 h 84% 5 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 4 h 99% 6 <![CDATA[Fe 0.7 With 0.3 A x -300]]> 60 g 130 ℃ 5 h 99%
[0102] The mass spectrum of the main product obtained from the above reaction is shown below. Figure 6As shown (the mass spectra of the main products of the above 6 reactions are the same, so only one mass spectrum is provided). The above results indicate that, using water as the reaction solvent and iron-copper composite metal oxide as the catalyst, benzonitrile can be catalyzed to synthesize benzamide with a reaction time of 0.5-4 h; at the same time, the yield of benzamide obtained by the reaction is above 80% when the reaction time is 3-5 h; and when the reaction time is 4-5 h, the yield of benzamide obtained by the reaction is higher than 99%.
[0103] Example 6 Synthesis of benzamide with different catalyst addition amounts
[0104] 1. Add 0.5 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0105] 2. Add 1 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0106] 3. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0107] 4. Add 3 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0108] 5. Add 4 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0109] 6. Add 5 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of benzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 4 h. Then filter while hot, cool and crystallize, and filter again to obtain the product benzamide.
[0110] The yields of benzamide products obtained by the preparation methods described in 1-6 above were calculated, and the results are shown in Table 6 below:
[0111] Table 6. Process parameters and yield of benzamide as described in Example 6
[0112] Serial Number catalyst Solvent volume reaction temperature reaction time Product yield 1 0.5 g 60 g 130 ℃ 4 h 19% 2 1 g 60 g 130 ℃ 4 h 68% 3 2 g 60 g 130 ℃ 4 h 99% 4 3 g 60 g 130 ℃ 4 h 99% 5 4 g 60 g 130 ℃ 4 h 98% 6 5 g 60 g 130 ℃ 4 h 99%
[0113] The above results indicate that, using water as the reaction solvent, the dosage of the iron-copper composite metal oxide catalyst at 0.5-5.0 g can catalyze the synthesis of benzamide from benzonitrile; and when the dosage of the iron-copper composite metal oxide catalyst is 1.0-5.0 g, the yield of benzamide obtained is higher than 60%; while when the dosage of the iron-copper composite metal oxide catalyst is 2.0-5.0 g, the yield of benzamide obtained can reach more than 98%, with a maximum of 99%.
[0114] Example 7 Synthesis of amide derivatives using nitrile derivatives
[0115] 1. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of p-methylbenzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 5 h. Then filter while hot, cool and crystallize, and filter again to obtain the product p-methylbenzoamide.
[0116] 2. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of p-4-chlorobenzonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 3 h. Then filter while hot, cool and crystallize, and filter again to obtain the product p-4-chlorobenzoamide.
[0117] 3. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of nicotinamide and 60 g of aqueous solvent. Add a magnetic stirrer and heat to 130 °C. React for 5 h. Then filter while hot, cool and crystallize, and filter again to obtain the product p-nicotinamide.
[0118] 4. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of cinnamonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 8 h. Then filter while hot, cool and crystallize, and filter again to obtain the product p-cinnamamide.
[0119] 5. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of acrylonitrile and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 6 h. Then filter while hot, cool and crystallize, and filter again to obtain the product p-acrylamide.
[0120] 6. Add 2 g of iron-copper composite metal oxide catalyst to a 250 mL autoclave, then add 10.2 g of 2-cyanopyrazine and 60 g of water solvent. Add a magnetic stirrer and heat to 130 °C. React for 8 h. Then filter while hot, cool and crystallize, and filter again to obtain the product pyrazinamide.
[0121] The yields of the benzamide derivatives obtained by the preparation methods described in 1-6 above were calculated, and the results are shown in Table 7 below:
[0122] Table 7. Process parameters and product yield of the preparation method described in Example 7
[0123] Serial Number Substrate solvent reaction temperature reaction time Product yield 1 p-Chlorobenzonitrile water 130 ℃ 5 h 89% 2 2-Cyanopyridine water 130 ℃ 3 h 97% 3 3-Cyanopyridine water 130 ℃ 5 h 99% 4 2-Cyanopyrazine water 130 ℃ 8 h 99% 5 Acrylonitrile water 130 ℃ 6 h 93% 6 Cinnamonitrile water 130 ℃ 8 h 95%
[0124] The mass spectra of the main products in reactions 1-5 above are as follows: Figure 7-11 As shown above, the results indicate that using water as the reaction solvent and an iron-copper composite metal oxide as the catalyst, p-chlorobenzonitrile can be catalyzed to synthesize p-chlorobenzamide with a yield of 89%; 2-cyanopyridine can be catalyzed to synthesize 2-pyridinecarboxamide with a yield of 97%; 2-cyanopyridine can be catalyzed to synthesize 2-pyridinecarboxamide with a yield of 99%; acrylonitrile can be catalyzed to synthesize acrylamide with a yield of 93%; p-2-cyanopyrazine can be catalyzed to synthesize pyrazinamide with a yield of 99%; and cinnamonitrile can be catalyzed to synthesize cinnamamide with a yield of 95%. Therefore, the method described in this invention can catalyze the synthesis of corresponding amides from various nitriles, with product yields all exceeding 89%.
[0125] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.
Claims
1. The application of amorphous iron-copper composite metal oxide as a catalyst for the hydration of nitriles to prepare amides, and the method for preparing the amorphous iron-copper composite metal oxide catalyst, characterized in that... 7 mmol Fe(NO3)3·9H2O, 3 mmol Cu(NO3)2·3H2O, 24 mmol NaOH, and 6 mmol NaCl were added to a mortar and mixed thoroughly. After grinding for 1 h, the system began to exothermic. As the reaction proceeded, the mixture gradually became a paste, and its color changed from blue to brown. The resulting product was then dried in a 60 °C oven for 5 h, washed at least three times with deionized water, dried again at 60 °C for 12 h, and further dried at 120 °C for 3 h. Finally, the sample was placed in a muffle furnace and calcined at 300 °C for 2 h to obtain Fe. 0.7 Cu 0.3 O x -300 catalyst.
2. The application as described in claim 1, wherein amorphous iron-copper composite metal oxide is used as a catalyst to catalyze the hydration of nitrile to prepare amide, characterized in that, The method is as follows: using the nitrile shown in formula (I) as raw material, water as reaction solvent, and amorphous iron-copper composite metal oxide as catalyst, a hydration reaction is catalyzed to synthesize the amide shown in formula (II); Equation (I) Equation (II) Wherein, R is selected from any one of phenyl, ortho-benzylmethyl, meta-benzylmethyl, para-benzylmethyl, ortho-benzyloxy, meta-benzyloxy, para-benzyloxy, ortho-phenylchloroyl, meta-phenylchloroyl, para-phenylchloroyl, ortho-phenylnitrol, meta-phenylnitrol, para-phenylnitrol, ortho-phenylaldehyde, meta-phenylaldehyde, para-phenylaldehyde, para-phenylcyano, styryl, pyridyl, pyrazinyl, vinyl, ortho-thiophenyl, ortho-furanyl.
3. The application as described in claim 2, characterized in that, The mass ratio of the catalyst to the nitrile is 5-50 g: 1 mol; the mass ratio of the reaction solvent to the nitrile is 3-8:
1.
4. The application as described in claim 2, characterized in that, R is selected from phenyl, para-phenylmethyl, 4-chlorophenylmethyl, 2-pyridyl, 3-pyridyl, 3-pyrazinyl, and vinyl, respectively.
5. The application as described in claim 1, characterized in that, The method is as follows: nitriles, amorphous iron-copper composite metal oxides and water are added to a reaction vessel and reacted at 80-140 °C for 0.5-6 h. The mixture is then filtered while hot, cooled to crystallize, and filtered again to obtain the amide.
6. The application as described in claim 2, characterized in that, The mass ratio of the catalyst to the nitrile is 20 g: 1 mol; the mass ratio of the reaction solvent to the nitrile is 6:1; the reaction temperature is 130 °C, and the reaction time is 4 h.