Method for preparing aldehyde ketone compound by olefin oxidation
阅读说明：本技术 一种烯烃氧化制备醛酮类化合物的方法 (Method for preparing aldehyde ketone compound by olefin oxidation ) 是由 周海峰 余涛 赵蓉蓉 文思妙妙 刘祈星 王金龙 杜一凡 陈永盛 于 2020-12-03 设计创作，主要内容包括：本发明提供了一种烯烃氧化制备醛酮类化合物的方法,涉及的制备方法为氧气参与的烯烃氧化裂解反应,具体步骤如下：在溶剂与氧化剂存在的条件下,将烯烃原料氧化裂解制得相应的醛酮类产物。与传统方法相比,本发明不需要加入任何催化剂或配体,也不需要使用高压氧气,具有反应条件简单温和、绿色环保、成本低、原子经济性高等优点,而且底物适应范围广,产率高,在合成醛酮类医药中间体和化工原料方面具有广阔的应用前景。(The invention provides a method for preparing aldehyde ketone compounds by olefin oxidation, which relates to a preparation method for olefin oxidative cracking reaction with oxygen participation, and comprises the following specific steps: under the condition of solvent and oxidant, the olefin material is oxidized and cracked to prepare corresponding aldehyde ketone product. Compared with the traditional method, the method does not need to add any catalyst or ligand, does not need to use high-pressure oxygen, has the advantages of simple and mild reaction conditions, environmental protection, low cost, high atom economy and the like, has wide substrate application range and high yield, and has wide application prospect in the aspect of synthesizing aldehyde ketone medical intermediates and chemical raw materials.)
1. A method for preparing aldehyde ketone compounds by olefin oxidation is characterized in that: under the condition of solvent and oxidant, the olefin material is oxidized and cracked to prepare corresponding aldehyde ketone productα-any of substituted arylethenes, monoarylethenes, 1, 2-diarylethenes or triarylethenes.
2. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 1, wherein: saidαThe substituent in the substituted arylethene includes any of aryl, alkyl, cycloalkyl and fused ring.
3. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 1, wherein: the solvent comprises methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, morpholine,N,N-one or more of dimethylformamide, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether M.W = 250, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, ethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600.
4. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 3, wherein: the solvent is polyethylene glycol dimethyl ether M.W = 250.
5. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 1, wherein: the oxidant is air or oxygen.
6. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 1, wherein: the temperature of the oxidation reaction is 100-140 ℃.
7. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 6, wherein: the temperature of the oxidation reaction is preferably 110-130 ℃.
8. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 1, wherein: the time of the oxidation reaction is 2-12 hours.
9. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 1, wherein: the time of the oxidation reaction is preferably 8 to 12 hours.
10. The method for preparing aldehydes and ketones by oxidizing olefins according to claim 1, wherein: the mol/volume ratio of the olefin raw material to the solvent is that 0-1 mL of solvent is added into every 0.5mmol of olefin raw material.
Technical Field
The invention belongs to the technical field of synthesis of aldehyde ketone compounds, and particularly relates to a method for preparing aldehyde ketone compounds by oxidative cracking of olefin.
Background
Olefins widely exist in petroleum cracking gas, natural products and chemical intermediates, carbon-carbon double bonds of the olefins are oxidized into carbon-oxygen double bonds by an oxidative cracking method, the method is a common conversion method in organic synthesis, and the method can synthesize various aldehyde ketone compounds and provides convenience for further functional group conversion. The currently adopted method for preparing aldehyde ketone compounds by olefin oxidative cracking has a plurality of defects: (1) the ozonization-decomposition method needs a special reaction device, has poor safety and high cost; (2) the stoichiometric strong oxidant and complex catalysts such as metal, ligand and the like are used, so that the cost is high and the pollution is large; (3) the photocatalytic oxidation requires special equipment and has larger energy consumption; (4) the substrate adaptability of the biological enzyme catalysis is poor, the product is not single, and the corresponding enzyme engineering bacteria are not easy to obtain. These deficiencies limit the practical application of such methods to a greater or lesser extent.
Disclosure of Invention
The invention provides a practical, mild and green method for preparing aldehyde ketone compounds by realizing the oxidative cracking of olefin.
The technical scheme of the invention is as follows: adding olefin raw materials and a solvent into a reaction vessel, charging an oxidant, and cracking the olefin raw materials through an oxidation reaction to prepare the aldehyde ketone compounds.
The olefin raw material is one of alpha-substituted aryl ethylene (wherein the substituent is one or more of aryl, alkyl, cycloalkyl and fused ring), monoaryl ethylene, 1, 2-diaryl ethylene or triaryl ethylene.
The solvent is one or more of methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, morpholine, N-dimethylformamide, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether (m.w. ═ 250), dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, ethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600, and is further preferably polyethylene glycol dimethyl ether (m.w. ═ 250).
The oxidant is air or oxygen, and more preferably oxygen.
The reaction temperature is 100-140 ℃, and more preferably 110-130 ℃.
The reaction time is 2 to 12 hours, and more preferably 8 to 12 hours.
The invention provides a simple method for preparing aldehyde ketone compounds by olefin oxidative cracking, which is used for preparing corresponding aldehyde ketone compounds by olefin raw materials oxidative cracking only in the presence of a solvent and an oxidant without adding any metal catalyst, ligand and the like.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1: oxidation synthesis of benzophenone from 1, 1-diphenylethylene
0.5mmol of 1, 1-stilbene and 1mL of polyglycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, a balloon filled with pure oxygen was inserted after oxygen substitution, and the reaction was carried out at 130 ℃ for 8 hours, whereby the yield was 93.7%.
Example 2: the effect of different solvents on the reaction was determined as in example 1, except that the reaction was carried out at a boiling temperature at which part of the solvent had a boiling point lower than 130 ℃.
No.
Solvent (1mL)
Temperature/. degree.C
Yield/%)
1
Methyl tert-butyl ether
55(ref)
1.4
2
Tetrahydrofuran (THF)
66(ref)
2.1
3
2-methyltetrahydrofuran
80(ref)
4.9
4
Dioxane (dioxane)
100(ref)
72.5
5
Morpholine
130
43.8
6
DMF
130
4.3
7
Ethylene glycol dimethyl ether
84(ref)
10.7
8
Ethylene glycol diethyl ether
121(ref)
85.3
9
Diethylene glycol monomethyl ether
130
91.0
10
Diethylene glycol dimethyl ether
130
92.5
11
Polyethylene glycol dimethyl ether (PEGDME)
130
93.7
12
Dipropylene glycol methyl ether
130
88.4
13
Dipropylene glycol dimethyl ether
130
91.6
14
Ethylene glycol
130
54.3
15
Triethylene glycol
130
89.2
16
Polyethylene glycol 200
130
87.9
17
Polyethylene glycol 400
130
83.8
18
Polyethylene glycol 600
130
80.5
From the above results, it was found that the preferred solvent for the reaction was dimethyl ether of polyethylene glycol (m.w. ═ 250) and the yield was 93.7%.
Example 3: the other conditions were the same as in example 1, and the influence of different reaction temperatures was determined.
No.
Temperature/. degree.C
Yield/%)
1
100
76.5
2
110
>99
3
120
95.9
4
130
93.7
5
140
91.7
From the above results, it is preferable that the reaction temperature is 110 ℃ and the 1, 1-stilbene is almost completely converted.
Example 4: the reaction temperature was 110 ℃ and other conditions were the same as in example 1, with the following results: the input ratio of the solvent and the influence of the oxidant.
From the above results, it is found that the reaction is preferably carried out for a period of 8 hours or more, starting from: the solvent feed ratio is preferably 0.5mmol:1mL, and the oxidant is preferably oxygen.
Example 5: synthesis of benzophenone
0.5mmol of 1, 1-stilbene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 99%.1H NMR(400MHz,CDCl3):δ＝7.86-7.84(m,4H),7.66-7.62(m,2H),7.55-7.51(m,4H)；13C NMR(100MHz,CDCl3):δ＝196.83,137.59,132.47,130.11,128.32.
Example 6: synthesis of 2-methylbenzophenone
0.5mmol of 1-methyl-2- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 97.5%.1H NMR(400MHz,CDCl3):δ＝7.86-7.84(m,2H),7.63(tt,J1＝6.9Hz,J2＝1.3Hz,1H),7.52-7.42(m,3H),7.37-7.28(m,3H),2.38(s,3H)；13C NMR(100MHz,CDCl3):δ＝198.72,138.61,137.73,136.79,133.19,131.03,130.28,130.17,128.56,128.49,125.22,20.04.
Example 7: synthesis of 3-methylbenzophenone
0.5mmol of 1-methyl-3- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 98.3%.1H NMR(400MHz,CDCl3):δ＝7.86-7.84(m,2H),7.68(s,1H),7.65-7.61(m,2H),7.52(t,J＝7.6Hz,2H),7.46-7.38(m,2H),2.47(s,3H)；13C NMR(100MHz,CDCl3):δ＝197.00,138.18,137.78,137.65,133.23,132.37,130.48,130.07,128.27,128.12,127.39,21.40.
Example 8: synthesis of 4-methylbenzophenone
0.5mmol of 1-methyl-4- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 97.8%.1H NMR(400MHz,CDCl3):δ＝7.84-7.82(m,2H),7.78-7.76(m,2H),7.62(tt,J1＝6.8Hz,J2＝1.1Hz,1H),7.54-7.50(m,2H),7.33(d,J＝7.6Hz,2H),2.49(s,3H)；13C NMR(100MHz,CDCl3):δ＝196.60,143.30,137.95,134.87,132.22,130.36,129.98,129.02,128.25,21.72.
Example 9: synthesis of 2-methoxybenzophenone
0.5mmol of 1-methoxy-2- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 99.3%.1H NMR(400MHz,CDCl3):δ＝7.87-7.85(m,2H),7.61-7.57(m,1H),7.53-7.45(m,3H),7.40(dd,J1＝7.2Hz,J2＝1.6Hz,1H),7.10-7.03(m,2H),3.76(s,3H)；13C NMR(100MHz,CDCl3):δ＝196.54,157.36,137.80,132.98,131.94,129.87,129.61,128.82,128.26,120.51,111.46,55.62.
Example 10: synthesis of 3-methoxybenzophenone
0.5mmol of 1-methoxy-3- (1-phenylvinyl) benzene was added to a test tubeAnd 1mL of polyethylene glycol dimethyl ether (m.w. ═ 250) as a solvent, the test tube was sealed, and after oxygen substitution, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, with a yield of 97.8%.1H NMR(400MHz,CDCl3):δ＝7.86-7.84(m,2H),7.66-7.61(m,1H),7.55-7.51(m,2H),7.45-7.37(m,3H),7.20-7.17(m,1H),3.91(s,3H)；13C NMR(100MHz,CDCl3):δ＝196.60,159.57,138.89,137.61,132.48,130.08,129.25,128.29,122.92,118.91,114.31,55.51.
Example 11: synthesis of 4-methoxybenzophenone
0.5mmol of 1-methoxy-4- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 98.9%.1H NMR(400MHz,CDCl3):δ＝7.89-7.86(m,2H),7.82-7.79(m,2H),7.63-7.59(m,1H),7.54-7.50(m,2H),7.03-6.99(m,2H),3.93(s,3H)；13C NMR(100MHz,CDCl3):δ＝195.63,163.24,138.28,132.61,131.94,130.15,129.77,128.22,113.57,55.54.
Example 12: synthesis of 2-fluorobenzophenone
0.5mmol of 1-fluoro-2- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, giving a yield of 90.9%.1H NMR(400MHz,CDCl3):δ＝7.89(d,J＝8.0Hz,2H),7.67-7.50(m,5H),7.31(td,J1＝7.6Hz,J2＝0.8Hz,1H),7.23-7.18(m,1H)；13C NMR(100MHz,CDCl3):δ＝193.54,160.10(d,J＝250.8Hz),137.39,133.46,133.11(d,J＝8.3Hz),130.79(d,J＝2.9Hz),129.84,128.50,127.03(d,J＝14.7Hz),124.32(d,J＝3.6Hz),116.31(d,J＝21.6Hz).19F NMR(CDCl3,376MHz):δ-111.0.
Example 13: synthesis of 4-fluorobenzophenone
0.5mmol of 1-fluoro-4- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 98.8%.1H NMR(400MHz,CDCl3):δ＝7.91-7.86(m,2H),7.82-7.80(m,2H),7.63(tt,J1＝6.8Hz,J2＝1.3Hz,1H),7.55-7.51(m,2H),7.23-7.17(m,2H)；13C NMR(100MHz,CDCl3):δ＝195.31,165.40(d,J＝252.6Hz),137.49,133.80(d,J＝3.0Hz),132.71(d,J＝9.1Hz),132.52,129.91,128.39,115.49(d,J＝21.7Hz).19F NMR(CDCl3,376MHz):δ-105.89.
Example 14: synthesis of 2-chlorobenzophenone
0.5mmol of 1-chloro-2- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, giving a yield of 90.9%.1H NMR(400MHz,CDCl3):δ＝7.87-7.85(m,2H),7.67-7.63(m,1H),7.53-7.46(m,4H),7.44-7.41(m,2H)；13C NMR(100MHz,CDCl3):δ＝195.36,138.61,136.47,133.76,131.33,131.17,130.12,130.11,129.15,128.65,126.72.
Example 15: synthesis of 4-chlorobenzophenone
0.5mmol of 1-chloro-4- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W.: 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 97.2%.1H NMR(400MHz,CDCl3):δ＝7.83-7.79(m,4H),7.67-7.63(m,1H),7.56-7.49(m,4H)；13C NMR(100MHz,CDCl3):δ＝195.56,138.93,137.24,135.87,132.69,131.50,129.97,128.67,128.44.
Example 16: synthesis of 2-bromobenzophenone
0.5mmol of 1-bromo-2- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, giving a yield of 90.0%.1H NMR(400MHz,CDCl3):δ＝7.87-7.85(m,2H),7.71-7.63(m,2H),7.53-7.45(m,3H),7.43-7.38(m,2H)；13C NMR(100MHz,CDCl3):δ＝195.95,140.67,136.11,133.79,133.23,131.20,130.27,129.02,128.68,127.24,119.55.
Example 17: synthesis of 2-trifluoromethyl benzophenone
0.5mmol of 1- (1-phenylvinyl) -2-trifluoromethylbenzene and 1mL of polyethylene glycol dimethyl ether (M.W.: 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 72.8%.1H NMR(400MHz,CDCl3):δ＝7.84-7.82(m,3H),7.68-7.63(m,3H),7.53-7.49(m,2H),7.45-7.42(m,1H)；13CNMR(100MHz,CDCl3):δ＝195.60,138.32,136.38,133.91,131.42,130.25,129.85,128.56,128.12,126.72(q,J＝4.6Hz),124.98,122.26；19FNMR(CDCl3,376MHz):δ-57.99.
Example 18: synthesis of 3-trifluoromethyl benzophenone
0.5mmol of 1- (1-phenylvinyl) -3-trifluoromethylbenzene and 1mL of polyethylene glycol dimethyl ether (M.W.: 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 99.2%.1H NMR(400MHz,CDCl3):δ＝8.11(s,1H),8.03(d,J＝8Hz,1H),7.90(d,J＝7.6Hz,1H),7.86-7.83(m,2H),7.70-7.66(m,2H),7.58-7.55(m,2H)；13C NMR(100MHz,CDCl3):δ＝195.29,138.26,136.74,133.17,133.07,130.83,130.07,128.99,128.91,128.87,128.60,126.74(q,J＝3.7Hz),125.06,122.35；19F NMR(CDCl3,376MHz):δ-62.70.
Example 19: synthesis of 3, 5-dimethyl benzophenone
0.5mmol of 1, 3-dimethyl-5- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 99.1%.1H NMR(400MHz,CDCl3):δ＝7.85-7.83(m,2H),7.65-7.61(m,1H),7.54-7.51(m,2H),7.45(s,2H),7.27(s,1H),2.42(s,6H)；13C NMR(100MHz,CDCl3):δ＝197.25,137.96,137.91,137.69,134.14,132.30,130.07,128.25,127.86,21.30.
Example 20: synthesis of 2, 4-difluorobenzophenone
On one branch0.5mmol of 2, 4-difluoro-1- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, giving a yield of 90.1%.1H NMR(400MHz,CDCl3):δ＝7.87-7.84(m,2H),7.68-7.62(m,2H),7.54-7.51(m,2H),7.08-7.03(m,1H),6.95(ddd,J1＝10.0Hz,J2＝8.8Hz,J3＝2.4Hz,1H)；13C NMR(100MHz,CDCl3):δ＝192.36,166.19(d,J＝11.6Hz),163.66(d,J＝11.7Hz),162.23(d,J＝12.3Hz),159.68(d,J＝12.3Hz),137.39,133.52,132.59(dd,J1＝10.2Hz,J2＝4.3Hz),129.73,128.55,123.35(dd,J1＝14.6Hz,J2＝3.8Hz),111.91(dd,J1＝21.4Hz,J2＝3.7Hz),104.72(t,J＝25.4Hz)；19F NMR(CDCl3,376MHz):δ-103.71(d,J＝10.4Hz),-105.80(d,J＝10.4Hz).
Example 21: synthesis of 2-fluoro-4-methoxybenzophenone
0.5mmol of 2-fluoro-4-methoxy-1- (1-phenylvinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, a balloon filled with pure oxygen was inserted after oxygen substitution, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 89.8%.1H NMR(400MHz,CDCl3):δ＝7.85-7.83(m,2H),7.64-7.60(m,2H),7.52-7.49(m,2H),6.83(dd,J1＝8.6Hz,J2＝2.4Hz,1H),6.71(dd,J1＝12.0Hz,J2＝2.4Hz,1H),3.92(s,3H).；13C NMR(100MHz,CDCl3):δ＝192.89,163.92(d,J＝11.2Hz),163.22,160.69,138.32,132.89,132.71(d,J＝4.4Hz),129.62(d,J＝1.3Hz),128.32,119.30(d,J＝13.8Hz),110.34(d,J＝2.9Hz),101.89(d,J＝25.6Hz),55.88.
Example 22: synthesis of 2, 6-difluoro-4' -methylbenzophenone
0.5mmol of 1, 3-difluoro-2- (1- (p-tolyl) vinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 85.7%.1H NMR(400MHz,CDCl3):δ＝7.81(d,J＝8.0Hz,2H),7.48(tt,J1＝8.4Hz,J2＝6.4Hz,1H),7.33(d,J＝8.0Hz,2H),7.07-7.01(m,2H),2.48(s,3H)；13C NMR(100MHz,CDCl3):δ＝188.53,161.03(d,J＝7.5Hz),158.53(d,J＝7.8Hz),145.41,134.45,131.71(t,J＝9.8Hz),129.84,129.52,117.26,111.99,111.97,111.93,111.80,111.75,111.74,21.85；19F NMR(CDCl3,376MHz):δ-111.88.
Example 23: synthesis of 4, 4' -dimethoxy benzophenone
0.5mmol of 4-methoxy-1- (1- (p-methoxyphenyl) vinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 94.5%.1H NMR(400MHz,CDCl3):δ＝7.85-7.81(m,4H),7.02-6.98(m,4H),3.93(s,6H)；13C NMR(100MHz,CDCl3):δ＝194.49,162.85,132.25,130.77,113.48,55.50.
Example 24: synthesis of 4-chloro-3' -trifluoromethyl benzophenone
Adding 0.5mmol of 4-chloro-1- (1- (3-trifluoromethylphenyl) vinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) as solvents into a test tube, sealing the test tube, performing oxygen exchange, and inserting a balloon filled with pure oxygenAnd reacting at 110 ℃ for 8h, wherein the yield is 96.7%.1H NMR(400MHz,CDCl3):δ＝8.08(s,1H),7.99(d,J＝7.6Hz,1H),7.91(d,J＝7.6Hz,1H),7.81-7.78(m,2H),7.69(t,J＝8.0Hz,1H),7.56-7.52(m,2H)；13C NMR(100MHz,CDCl3):δ＝194.01,139.63,137.93,135.03,132.98,131.41,129.11,129.06,128.97,126.60(q,J＝4.0Hz).,124.98,122.27.19F NMR(CDCl3,376MHz):δ-62.76.
Example 25: synthesis of 3, 5-dimethyl-4' -trifluoromethyl benzophenone
0.5mmol of 1, 3-dimethyl-5- (1- (4- (trifluoromethyl) phenyl) vinyl) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, a balloon filled with pure oxygen was inserted after oxygen substitution, and the reaction was carried out at 110 ℃ for 8 hours with a yield of 99.1%.1H NMR(400MHz,CDCl3):δ＝7.92(d,J＝8.0Hz,2H),7.79(d,J＝8.4Hz,2H),7.44(s,2H),7.30(s,1H),2.43(s,6H)；13C NMR(100MHz,CDCl3):δ＝195.96,141.08,138.27,136.87,134.78,133.57(d,J＝32.5Hz),130.11,127.87,125.28(q,J＝3.7Hz),122.38,21.24.
Example 26: synthesis of 2-naphthylphenylketone
0.5mmol of 2- (1-phenylvinyl) naphthalene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, giving a yield of 40.6%.1H NMR(400MHz,CDCl3):δ＝8.32(s,1H),8.00-7.96(m,4H),7.92-7.90(m,2H),7.69-7.64(m,2H),7.62-7.55(m,3H)；13C NMR(100MHz,CDCl3):δ＝196.81,137.93,135.30,134.84,132.42,132.28,131.91,130.19,130.13,129.45,128.37,128.33,127.85,126.83,125.81.
Example 27: synthesis of 2-naphthoylthiophene
0.5mmol of 3- (1-phenylvinyl) thiophene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, giving a yield of 58.9%.1H NMR(400MHz,CDCl3):δ＝7.97(dd,J1＝2.8Hz,J2＝1.2Hz,1H),7.90-7.88(m,2H),7.66-7.61(m,2H),7.53(t,J＝7.6Hz,2H),7.43(dd,J1＝5.0Hz,J2＝2.8Hz,1H)；13C NMR(100MHz,CDCl3):δ＝190.07,141.29,138.62,134.02,132.36,129.41,128.64,128.42,126.27.
Example 28: synthesis of 2-benzoylpyridine
0.5mmol of 2- (1-phenylvinyl) pyridine and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 97.3%.1H NMR(400MHz,CDCl3):δ＝8.71(d,J＝4.8Hz,1H),8.09-8.02(m,3H),7.90-7.85(m,1H),7.61-7.56(m,1H),7.50-7.45(m,3H)；13C NMR(100MHz,CDCl3):δ＝193.87,155.03,148.56,137.09,136.27,132.94,130.99,128.18,126.22,124.61.
Example 29: synthesis of 9-fluorenone
0.5mmol of 9-methylene-9H-fluorene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, and oxygen gas was introducedAfter the replacement, a balloon filled with pure oxygen is inserted, and the reaction is carried out for 8 hours at 110 ℃, so that the yield is 87.3%.1H NMR(400MHz,CDCl3):δ＝7.68(d,J＝7.2Hz,2H),7.53-7.48(m,4H),7.31(td,J1＝7.2Hz,J2＝1.6Hz,2H)；13C NMR(100MHz,CDCl3):δ＝193.91,144.42,134.69,134.14,129.08,124.29,120.33.
Example 30: synthesis of 9-thioxanthone
0.5mmol of 9-methylene 9H-thioxanthene and 1mL of polyethylene glycol dimethyl ether (m.w. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, giving a yield of 84.6%.1H NMR(400MHz,CDCl3):δ＝8.65(dd,J1＝8.0Hz,J2＝1.2Hz,2H),7.67-7.59(m,4H),7.53-7.49(m,2H)；13C NMR(100MHz,CDCl3):δ＝179.96,137.29,132.27,129.87,129.24,126.31,125.99.
Example 31: synthesis of acetophenone
0.5mmol of α -methylstyrene and 1mL of polyethylene glycol dimethyl ether (m.w. ═ 250) as a solvent were added to a test tube, the test tube was sealed, and after oxygen substitution, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 99%.1H NMR(400MHz,CDCl3):δ＝δ＝7.93-7.91(m,2H),7.52(tt,J1＝6.8Hz,J2＝1.2Hz,1H),7.44-7.40(m,1H),2.55(s,3H)；13C NMR(100MHz,CDCl3):δ＝198.00,137.05,133.07,128.54,128.26,26.54.
Example 32: synthesis of cyclopropylphenyl ketones
0.5mmol of α -cyclopropylstyrene and 1mL of polyethylene glycol dimethyl ether (m.w. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 90.6%.1H NMR(400MHz,CDCl3):δ＝8.05-8.03(m,2H),7.59-7.55(m,1H),7.50-7.46(m,2H),2.72-2.66(m,1H),1.29-1.24(m,2H),1.07-1.03(m,2H)；13C NMR(100MHz,CDCl3):δ＝200.62,137.96,132.75,128.51,128.01,17.13,11.70.
Example 33: synthesis of 4-bromobenzaldehyde
0.5mmol of 4-bromostyrene and 1mL of polyglycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, a balloon filled with pure oxygen was inserted after oxygen substitution, and the reaction was carried out at 110 ℃ for 8 hours, whereby the yield was 91.8%.1H NMR(400MHz,CDCl3):δ＝10.02-10.01(m,1H),7.80-7.77(m,2H),7.54-7.51(m,2H),7.74-7.71(m,2H)；13C NMR(100MHz,CDCl3):δ＝191.11,135.08,132.46,131.00,129.81.
Example 34: oxidative cleavage of 2- (4-bromophenyl) -1, 1-diphenylethylene
0.5mmol of 2- (4-bromophenyl) -1, 1-diphenylethylene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 130 ℃ for 12 hours to give 4-bromobenzaldehyde and benzophenone in a yield of 88.9%.
Example 35: oxidative cleavage of triphenylethylene
0.5mmol of triphenylethylene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, a balloon filled with pure oxygen was inserted after oxygen substitution, and the reaction was carried out at 130 ℃ for 12 hours to produce benzaldehyde and benzophenone at a yield of 89.7%.1H NMR(400MHz,CDCl3):δ＝10.00-9.99(m,1H),7.86-7.84(m,2H),7.61-7.57(m,1H),7.51-7.47(m,2H)；13C NMR(100MHz,CDCl3):δ＝192.33,136.38,134.43,129.68,128.98.
Example 36: oxidative cleavage of 1, 4-bis (2-methylstyryl) benzene
0.5mmol of 1, 4-bis (2-methylstyrene-based) benzene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, oxygen substitution was performed, a balloon filled with pure oxygen was inserted, and the reaction was carried out at 130 ℃ for 12 hours to produce terephthalaldehyde and 2-methylbenzaldehyde, with a yield of 89.7%. (1)1H NMR(400MHz,CDCl3):δ＝10.18-10.17(m,2H),8.10-8.09(m,4H)；13C NMR(100MHz,CDCl3):δ＝191.52,140.02,130.16.(2)1H NMR(400MHz,CDCl3):δ＝10.28(s,1H),7.81(d,J＝7.6Hz,1H),7.49(td,J1＝7.2Hz,J2＝1.2Hz,1H),7.37(t,J＝7.6Hz,1H),7.27(d,J＝7.6Hz,1H),2.68(s,3H)；13C NMR(100MHz,CDCl3):δ＝192.78,140.59,134.14,133.65,132.05,131.78,126.33,19.59.
Example 37: oxidative cracking of 1, 2-diphenylethylene
0.5mmol of trans-1, 2-stilbene and 1mL of polyethylene glycol dimethyl ether (M.W. ═ 250) were added to a test tube as a solvent, the test tube was sealed, a balloon filled with pure oxygen was inserted after oxygen substitution, the reaction was carried out at 120 ℃ for 10 hours to produce two molecules of benzaldehyde, and 30. mu.L of the reaction solution was taken after the reaction was completed and diluted with 1mL of chromatographic acetonitrile and analyzed by high performance liquid chromatography, and the yield was 95.3%.
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