Efficient Synthesis of Hydrazones and Oxime Ethers from Amines Involving 3,5-Di-tert-butyl-o-benzoquinone

doi:10.6023/cjoc202601021

Abstract

A 3,5-di-tert-butyl-o-benzoquinone-mediated method has been established for the one-pot and two-step synthesis of hydrazones and oxime ethers from various secondary amines. This method proceeds under mild room-temperature without metal catalysts or additives, providing a facile and streamlined protocol for converting amino compounds into hydrazones and oxime ethers. The method enables the efficient conversion of aromatic, heterocyclic, and aliphatic amines into the corresponding imine derivatives. A substrate screening study indicates that the method is feasible for more than 20 substrates, and in several cases the yield can exceed 80%. The byproduct 6 has great value for practical application, which improves the economy of the method. Preliminary mechanistic studies suggest a dual nucleophilic addition-elimination process of amines with in situ generated carbonyl intermediates.

Key words: aminofunctionalization, Schiff base compounds, acid promoted, dehydration, nucleophilic addition

Cite this article

Ruixiao Yu, Chengyu Li, Yanchao Li, Huibin Zou. Efficient Synthesis of Hydrazones and Oxime Ethers from Amines Involving 3,5-Di-tert-butyl-o-benzoquinone[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3237-3245.

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Fig. & Tab. 6

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Entry	1a/equiv.	2a/equiv.	H₃O^＋	Yield^b/%
1	1.0	2.0	6 mol/L HCl/H₂O	65
2	1.0	2.0	50% TFA/H₂O^c	68
3	1.0	2.0	50% AcOH/H₂O^c	82
4	1.0	2.0	AcOH	31
5	1.1	2.0	50% AcOH/H₂O^c	85
6	1.2	2.0	50% AcOH/H₂O^c	81
7	1.1	1.5	50% AcOH/H₂O^c	86
8	1.1	1.2	50% AcOH/H₂O^c	83

Entry	1a/equiv.	2a/equiv.	H₃O^＋	Yield^b/%
1	1.0	2.0	6 mol/L HCl/H₂O	65
2	1.0	2.0	50% TFA/H₂O^c	68
3	1.0	2.0	50% AcOH/H₂O^c	82
4	1.0	2.0	AcOH	31
5	1.1	2.0	50% AcOH/H₂O^c	85
6	1.2	2.0	50% AcOH/H₂O^c	81
7	1.1	1.5	50% AcOH/H₂O^c	86
8	1.1	1.2	50% AcOH/H₂O^c	83

一种3,5-二叔丁基邻苯醌参与的氨基底物高效合成腙/肟醚的方法