二苯甲酮腙电氧化制备二苯重氮甲烷的研究

doi:10.6023/cjoc202312005

摘要/Abstract

研究了二苯甲酮腙电催化氧化合成二苯重氮甲烷. 针对二苯重氮甲烷的不稳定特性, 通过非均相电解体系设计, 优选卤化合物、电解质种类、反应溶剂的极性以及电极材料、控制电流密度和反应温度等措施, 抑制过氧化副产物二苯甲酮、水解副产物二苯甲醇及偶联副产物二苯甲酮吖嗪的生成, 以74%的高收率获得二苯重氮甲烷. 此外, 还初步探究了二苯甲酮腙电氧化机理.

关键词: 间接电合成, 非均相电解, 二苯重氮甲烷, 碘化合物

The electrocatalytic oxidation of benzophenone hydrazone for the synthesis of diphenyldiazomethane was investigated. To address the instability of diphenyldiazomethane, a heterogeneous electrolytic system was designed, optimizing the halogen compound, electrolyte type, solvent polarity, electrode material, control current density and reaction temperature. These measures effectively suppressed the formation of by-products such as benzylidene acetone peroxide, diphenylmethanol hydrolysis, and diphenylmethanequinone coupling, leading to a high yield of 74% for diphenyldiazomethane. Additionally, preliminary investigations were conducted on the electrochemical oxidation mechanism of benzophenone hydrazone.

Key words: indirect electrosynthesis, heterogeneous electrolysis, diphenyldiazomethane, iodine compound

引用此文

韩璐瑶, 胡硕真, 郭庆春, 郭红永, 高照群, 许颖, 张新胜. 二苯甲酮腙电氧化制备二苯重氮甲烷的研究[J]. 有机化学, 2024, 44(3): 951-965.

Luyao Han, Shuozhen Hu, Qingchun Guo, Hongyong Guo, Zhaoqun Gao, Ying Xu, Xinsheng Zhang. Study on Electrooxidation of Benzophenone Hydrazone to Diphenyldiazomethane[J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 951-965.

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图/表 24

图式1. 二苯重氮甲烷的电化学合成

Scheme 1. Electrochemical synthesis of diphenyldiazomethane

Entry	Catalyst	Conv.^b/%	Yield/%
Entry	Catalyst	Conv.^b/%	1^c	2^d	3^e	4^f
1	TBAI	95.1	59.7	9.8	1.7	1.7
2	TBAB	77.6	22.6	37.0	4.3	1.7

表1. TBAI和TBAB对BPH电合成DDM的影响

Table 1. Effects of TBAI and TBAB on BPH electrosynthesis of DDM

图1. 催化剂种类对BPH转化率(A)、DDM、二苯甲酮、二苯甲醇、二苯甲酮吖嗪收率(B)的影响

Figure 1. Effect of catalyst type on BPH conversion (A), yield of DDM, benzophenone, diphenylcarbinol and benzophenone azine (B)

图2. TBAI物质的量浓度对BPH转化率(A)、产物DDM及副产物二苯甲酮收率(B)的影响

Figure 2. Effect of TBAI molar concentration on BPH conversion (A), product DDM and by-product benzophenone yield (B)

Entry	Electrolyte	pH
Entry	Electrolyte	Aqueous solution^a	DMAc/H₂O^b
1	(NH₄)₂CO₃	10.25	10.28
2	NH₄HCO₃	8.40	8.95
3	CH₃COONH₄	7.58	8.06
4	(NH₄)₂HPO₄	8.88	4.77

表2. 碘单质和电解质在不用溶液中的pH

Table 2. pH of iodine and electrolyte in different solutions

图3. 电解质种类对BPH的转化率(A)、DDM或副产物二苯甲酮的收率(B)的影响

Figure 3. Effect of electrolyte type on BPH conversion (A), DDM or by-product benzophenone yield (B)

Entry	Electrolyte	Conv.^b/%	Yield/%
Entry	Electrolyte	Conv.^b/%	1^c	2^d	3^e	4^f
1	(NH₄)₂CO₃	49.4	39.5	4.8	0	<0.1
2	NH₄HCO₃	54.0	36.3	5.1	<0.1	2.3
3	CH₃COONH₄	47.4	18.2	10.7	2.8	2.9
4	(NH₄)₂HPO₄	67.2	8.8	29.0	3.8	0.1

表3. 碘单质在不用种类的电解质下对BPH的氧化效果

Table 3. Oxidation effect of iodine on BPH in different types of electrolytes

图4. 碳酸氢铵浓度对BPH转化率(A)、DDM、二苯甲酮、二苯甲醇及二苯甲酮吖嗪收率(B)的影响

Figure 4. Effect of ammonium bicarbonate concentration on BPH conversion (A), yield of DDM, benzophenone, diphenylcarbinol and benzophenone azine (B)

图5. 电流密度对BPH转化率(A)、DDM及副产物二苯甲酮的收率(B)的影响

Figure 5. Effect of current density on BPH conversion (A), DDM and by-product yield of benzophenone (B)

图6. 温度对BPH的转化率(A)、DDM和副产物二苯甲酮的收率(B)的影响

Figure 6. Effect of temperature on conversion of BPH (A), DDM and yield of byproduct benzophenone (B)

Entry	Solvent type	Dipole moment/(×10^－30 C•m)	Conv.^b/%	Yield/%
Entry	Solvent type	Dipole moment/(×10^－30 C•m)	Conv.^b/%	1^c	2^d	3^e	4^f
1	DMSO	13.34	100.0	34.7	43.3	16.7	1.7
2	DMF	12.88	100.0	66.3	16.3	6.6	1.0
3	DMAc	12.41	99.4	73.8	3.3	3.1	1.6
4	ACN	11.47	73.2	41.3	3.8	0.8	10.0

表4. 反应溶剂对BPH转化率及DDM、副产物二苯甲酮、二苯甲醇和二苯甲酮吖嗪的收率的影响

Table 4. Effect of reaction solvent on BPH conversion and yield of DDM, yield of benzophenone, benzyl alcohol and benzophenone azine as byproducts

图7. 阳极种类对BPH的转化率(A)、DDM收率、副产物二苯甲酮、二苯甲醇、二苯甲酮吖嗪的收率(B)的影响

Figure 7. Effect of anode type on BPH conversion (A), DDM yield, and by-product yield of benzophenone, diphenylcarbinol and benzophenone azine (B)

图8. 阴极种类对BPH转化率(A)、DDM、二苯甲酮、二苯甲醇和二苯甲酮吖嗪收率(B)的影响

Figure 8. Effect of cathode type on BPH conversion (A), yields of DDM, benzophenone, diphenylcarbinol and benzophenone azine (B)

图9. 最佳条件下DMAc层各组分物质的量浓度变化图(A)、石油醚层各组分物质的量浓度变化图(B)、各组分在DMAc和石油醚层中的浓度分配图(C)和电流效率示意图(D)

Figure 9. Under the optimal conditions, change diagram of molar concentration of each component in DMAc layer (A), the change of molar concentration of each component in petroleum ether layer (B), distribution diagram of each component in DMAc and petroleum ether layer (C), and current efficiency diagram (D)

Entry	Amplification coefficient	Conv.^d/%	Current efficiency/%	Yield^e/%
Entry	Amplification coefficient	Conv.^d/%	Current efficiency/%	1	2	3	4
1^a	1	100.0	58.9	73.7	7.6	2.9	1.2
2^b	5	99.9	57.9	72.4	7.3	2.5	0.2
3^c	10	100.0	56.4	70.5	7.8	2.1	0.4

表5. 等比放大实验

Table 5. Proportional amplification experiment

图式2. 电解装置示意图

Scheme 2. Electrolysis device diagram

Entry	c(BPH)/(mol•L^－1)	Conv.^b/%	Current efficiency/%	Yield/%
Entry	c(BPH)/(mol•L^－1)	Conv.^b/%	Current efficiency/%	1^c	2^d	3^e	4^f
1	0.0975	100.0	58.9	73.7	7.6	2.9	1.2
2	0.1951	100.0	50.8	63.4	7.4	4.1	1.4
3	0.4878	95.9	41.2	51.4	1.8	2.5	1.8
4	0.9756	91.4	39.6	49.5	0.7	1.7	2.2

表6. 提升BPH浓度的放大实验a

Table 6. Scale-up experiment to increase BPH concentration

图10. 不同BPH浓度电解的实验现象

Figure 10. Experimental phenomena of electrolysis with different BPH concentrations

图式3. 通过电合成的DDM衍生制备双苯噁唑酸的路线

Scheme 3. A route for the preparation of dibenzoxazolic acid derived from DDM by electrosynthesis

图11. 通电量对阳极室内DDM生成二苯甲酮的含量的影响(A)及活性氧气对DDM生成二苯甲酮(B)、二苯甲酮吖嗪(C)、二苯甲醇(D)的含量影响

Figure 11. Influence of electric flux on the content of benzophenone (A) from DDM in anode chamber and the influence of active oxygen on the content of benzophenone (B), benzophenone azine (C) and diphenylcarbinol (D) from DDM

图12. 不同扫速下的BPH＋DMAc＋NH4HCO3＋H2O的循环伏安测试

Figure 12. Cyclic voltammetry experiment of BPH＋DMAc＋NH4HCO3＋H2O at different sweep speeds

图13. 循环伏安测试

Figure 13. Cyclic voltammetry experiment

图式4. 对照实验

Scheme 4. Control experiments

图式5. 反应机理

Scheme 5. Reaction mechanism

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