Study on Electrooxidation of Benzophenone Hydrazone to Diphenyldiazomethane

doi:10.6023/cjoc202312005

Abstract

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

Cite this article

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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Fig. & Tab. 24

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

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

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

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

Table 2. pH of iodine and electrolyte in different solutions

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

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

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

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

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

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

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

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

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

Table 5. Proportional amplification experiment

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

Table 6. Scale-up experiment to increase BPH concentration

Figure 10. Experimental phenomena of electrolysis with different BPH concentrations

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

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

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

Figure 13. Cyclic voltammetry experiment

Scheme 4. Control experiments

Scheme 5. Reaction mechanism

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