A method for preparing amides by oxidative cleavage of alcohols
By using MnOx catalyst and molecular oxygen to oxidatively break down alcohols into amides in a pressure autoclave, the problems of harsh reaction conditions and high cost of precious metal catalysts in the prior art are solved, and efficient and economical amide synthesis is achieved.
Patent Information
- Application Number
- CN202111535429.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-12-15
- Publication Date
- 2025-09-26
- Estimated Expiration
- 2041-12-15
AI Technical Summary
The existing technology has the disadvantages of harsh reaction conditions, complex operation, high cost and limited applicability of precious metal catalysts in the process of oxidative cleavage of alcohols to form amides, making it difficult to achieve efficient and economical amide synthesis.
MnOx catalyst is used, molecular oxygen is used as oxidant, the reaction is carried out in a pressure autoclave, the catalyst can be regenerated and recycled, the reaction conditions are mild, and the cheap solvent 1,4-dioxane is used. The catalyst can maintain high activity and selectivity at 130-150°C.
The high selectivity and high yield of alcohol oxidation cleavage to form amide are achieved, and the catalyst can be regenerated and recycled, which reduces costs and meets the requirements of green chemistry.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of chemistry and chemical engineering, and in particular to a method for continuously oxidizing and cleaving alcohol to generate amide. Technical Background
[0002] Amides and their derivatives are a class of compounds with important commercial value and are widely used as intermediates for biopharmaceuticals. In the process of moving towards green and sustainable chemistry, the synthesis of amides from readily available alcohols through oxidative cleavage has attracted great interest. Since Milstein et al. reported the synthesis of secondary amides from primary alcohols and amines with PNN pincer-type Ru complexes, many efforts have been made in this direction, most of which have used precious metals such as homogeneous Ru. 13 and Rh 14 Complexes and heterogeneous Ag / γ-Al2O3. In addition, although heterogeneous Au-based catalysts have excellent catalytic performance in the synthesis of amides from alcohols and amines under molecular oxygen conditions in the presence of excess essential base additives, their large-scale application is difficult due to their high cost. When reacting with inorganic ammonia, the applicability of the above-mentioned Au-based system is limited to benzamide, with a low yield (50%). Despite significant progress in precious metal-based catalysts, non-precious metal catalytic methods remain highly desirable from an economic and ecological perspective, but also very challenging. Summary of the Invention
[0003] The problem to be solved by the present invention is to provide a pathway for the continuous breakdown of alcohols into amides, which has mild reaction conditions, simple operation, high activity and selectivity.
[0004] The reaction involved in the invention can be represented by the following general formula:
[0005]
[0006] Wherein R is a 2-, 3- or 4-substituted aromatic or heteroatom aromatic hydrocarbon, and the substituent is selected from an aryl group, a halogen group, a nitro group, an alkoxy group, an alkyl group or a hydrogen atom.
[0007] In the present invention, the catalyst used in the invention is MnO x The catalyst was prepared using a grinding method familiar to researchers in the field. The manganese precursors in the catalyst were manganese acetate, manganese chloride, manganese sulfate, or manganese nitrate, and one or two of potassium permanganate, preferably potassium permanganate and manganese acetate. The catalyst dosage during the reaction was controlled at 30 to 50 mg, preferably 40 mg.
[0008] The oxidant involved in the present invention is molecular oxygen, including air or oxygen, and the reaction process adopts a pressure autoclave to pressurize the oxygen supply pressure to 0.5 MPa.
[0009] The present invention prefers 1,4-dioxane as the reaction solvent. Conventional solvents such as tert-butylbenzene, n-heptane, tert-amyl alcohol, and butyl acetate yield poor results. The solvent dosage is 1-3 mL, preferably 2 mL.
[0010] The temperature used in the present invention is preferably 130-150° C. In the regeneration cycle, the catalyst can be used after conventional filtration, washing and drying.
[0011] The catalyst of the present invention can be recycled and reused at least 9 times while still maintaining good activity and selectivity. The catalyst of the present invention has the characteristics of simple preparation, low cost, high reaction selectivity, and environmental friendliness. DETAILED DESCRIPTION
[0012] The following examples will help to understand the present invention, but the present invention is not limited thereto.
[0013] Example 1
[0014] 40 mg of MnO2 catalyst, 0.5 mmol of phenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The reaction was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining a constant pressure. GC-MS analysis of the reaction products revealed 100% phenylethanol conversion and 97% benzamide yield.
[0015] Comparative Example 1
[0016] 40 mg of MnO2 catalyst, 0.5 mmol of phenylethanol, and 0.5 mL of 1,4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining a constant pressure. GC-MS analysis of the reaction products revealed 100% phenylethanol conversion and 28% benzamide yield.
[0017] Table 1 Phenylethanol fragmentation into amides
[0018]
[0019] Table 2 Comparison of phenylethanol fragmentation into amide-ammonium sources
[0020]
[0021] Example 11
[0022] 40 mg of MnO2 catalyst, 0.5 mmol of 4-methoxyphenylethanol, and 3 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 88% yield of 4-methoxybenzamide.
[0023] Example 12
[0024] 40 mg of MnO2 catalyst, 0.5 mmol of 4-methylphenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 89% yield of 4-methylbenzamide.
[0025] Example 13
[0026] 40 mg of MnO2 catalyst, 0.5 mmol of 3-methylphenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 83% yield of 3-methylbenzamide.
[0027] Example 14
[0028] 40 mg MnO x The catalyst, 0.5 mmol / L 1-methylphenylethanol, and 2 mL 1.4-dioxane were added to a 10 mL reaction flask. The reaction was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed a 70% yield of 2-methylbenzamide.
[0029] Example 15
[0030] 40 mg of MnO2 catalyst, 0.5 mmol of 4-nitrobenzylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed a 95% yield of 4-nitrobenzamide.
[0031] Example 16
[0032] 40 mg of MnO2 catalyst, 0.5 mmol of 4-trifluoromethylphenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 130°C oil bath for 12 hours, maintaining a constant pressure. GC-MS analysis of the reaction product revealed a 94% yield of 4-trifluoromethylbenzamide.
[0033] Example 17
[0034] 40 mg of MnO2 catalyst, 0.5 mmol of 4-chlorophenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed a 95% yield of 4-chlorobenzamide.
[0035] Example 18
[0036] 40 mg of MnO2 catalyst, 0.5 mmol of 3-chlorophenylethanol, and 3 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 89% yield of 3-chlorobenzamide.
[0037] Example 19
[0038] 40 mg of MnO2 catalyst, 0.5 mmol of 2-chlorophenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 87% yield of 2-chlorobenzamide.
[0039] Example 20
[0040] 40 mg of MnO2 catalyst, 0.5 mmol of 3-chlorophenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 85% yield of 2-chlorobenzamide.
[0041] Example 21
[0042] 40 mg of MnO2 catalyst, 0.5 mmol of 4-bromophenethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 140°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 88% yield of 4-bromobenzamide.
[0043] Example 22
[0044] 40 mg of MnO2 catalyst, 0.5 mmol of 4-fluorophenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 86% yield of 4-fluorobenzamide.
[0045] Example 23
[0046] 40 mg of MnO2 catalyst, 0.5 mmol of 2-pyridineethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The reaction was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed a 92% yield of 2-pyridinecarboxamide.
[0047] Example 24
[0048] 40 mg of MnO2 catalyst, 0.5 mmol of 3-pyridineethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 85% yield of 3-pyridinecarboxamide.
[0049] Example 25
[0050] 40 mg of MnO2 catalyst, 0.5 mmol of 2-thiopheneethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed a 90% yield of 2-thiophenecarboxamide.
[0051] Example 26
[0052] 40 mg of MnO2 catalyst, 0.5 mmol of 3-thiopheneethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining a constant pressure. GC-MS analysis of the reaction product revealed an 84% yield of 3-thiophenecarboxamide.
[0053] Example 27
[0054] 40 mg of MnO2 catalyst, 0.5 mmol of 2-furanethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 80% yield of 2-furancarboxamide.
[0055] Example 28
[0056] 40 mg of MnO2 catalyst, 0.5 mmol of 1-hydroxyindane, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The mixture was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed an 81% yield of phthalimide.
[0057] Example 29
[0058] 40 mg of MnO2 catalyst, 0.5 mmol of 1,2,3,4-tetrahydro-1-naphthol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction flask. The reaction was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia. The reaction was stirred in a 150°C oil bath for 12 hours, maintaining the pressure constant. GC-MS analysis of the reaction product revealed a 78% yield of phthalimide.
Claims
1. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L phenylethanol and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150°C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction products were analyzed by GC-MS. The conversion of phenylethanol was 100%, and the yield of benzamide product was 97%.
2. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L of phenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 130°C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 70%.
3. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L of phenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 140°C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 80%.
4. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L of phenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150°C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 96%.
5. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 30 mg of MnO2 catalyst, 0.5 mmol / L of phenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150°C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 73%.
6. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 50 mg of MnO2 catalyst, 0.5 mmol / L of phenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150°C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 90%.
7. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol of phenylethanol, 2 mL of 1.4-dioxane, and 6 equiv of NH3﹒H2O were added to a 10 mL reaction bottle. The reaction was then transferred to a stainless steel autoclave, filled with 0.5 MPa of oxygen, and placed in a 150°C oil bath. The reaction was stirred for 12 h while maintaining the pressure constant. The reaction product was analyzed by GC-MS, revealing a 60% yield of benzamide.
8. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol of phenylethanol, 2 mL of 1.4-dioxane, and 6 equiv of NH4HCO3 were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen, placed in a 150°C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 65%.
9. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol of phenylethanol, 2 mL of 1.4-dioxane, and 6 equiv of (NH4)2CO3 were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen, placed in a 150°C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 55%.
10. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol of phenylethanol, 2 mL of 1.4-dioxane, and 6 equiv of NH4OAc were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen, placed in a 150°C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the benzamide product was 56%.
11. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 4-methoxyphenylethanol, and 3 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 4-methoxybenzamide was 88%.
12. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 4-methylphenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 4-methylbenzamide was 89%.
13. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 3-methylphenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 3-methylbenzamide was 83%.
14. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 1-methylphenylethanol, and 2 mL 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa oxygen and 0.5 MPa ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 2-methylbenzamide was 70%.
15. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 4-nitrobenzylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 4-nitrobenzamide was 95%.
16. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 4-trifluoromethylphenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 130 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 4-trifluoromethylbenzamide was 94%.
17. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 4-chlorophenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 4-chlorobenzamide was 95%.
18. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 3-chlorophenylethanol, and 3 mL 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa oxygen and 0.5 MPa ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 3-chlorobenzamide was 89%.
19. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 2-chlorophenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 2-chlorobenzamide was 87%.
20. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 4-bromophenethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 140 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 4-bromobenzamide was 88%.
21. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 4-fluorophenylethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 4-fluorobenzamide was 86%.
22. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmolL 2-pyridineethanol and 2 mL 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa oxygen and 0.5 MPa ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of 2-pyridinecarboxamide product was 92%.
23. A method for the continuous cleavage of alcohols into amides catalyzed by a manganese oxide, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 3-pyridineethanol, and 2 mL 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa oxygen and 0.5 MPa ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 3-pyridinecarboxamide was 85%.
24. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 2-thiopheneethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 2-thiophenecarboxamide was 90%.
25. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 3-thiopheneethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 3-thiophenecarboxamide was 84%.
26. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 2-furanethanol, and 2 mL of 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa of oxygen and 0.5 MPa of ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was maintained constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of 2-furancarboxamide was 80%.
27. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 1-hydroxyindane, and 2 mL 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa oxygen and 0.5 MPa ammonia, placed in a 150 °C oil bath, and stirred for 12 h. The pressure was kept constant during the reaction. The reaction products were analyzed by GC-MS, and the yield of the phthalimide product was 81%.
28. A method for the continuous cleavage of alcohols into amides catalyzed by manganese oxides, characterized in that: 40 mg of MnO2 catalyst, 0.5 mmol / L 1,2,3,4-tetrahydro-1-naphthol and 2 mL 1.4-dioxane were added to a 10 mL reaction bottle, then transferred to a stainless steel high-pressure reactor, filled with 0.5 MPa oxygen and 0.5 MPa ammonia, placed in a 150 °C oil bath, and stirred for 12 hours. The pressure was kept constant during the reaction. The reaction product was analyzed by GC-MS, and the yield of the phthalimide product was 78%.