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Synlett 2015; 26(08): 1121-1123
DOI: 10.1055/s-0034-1380276
DOI: 10.1055/s-0034-1380276
letter
A Novel Approach to N′,N′-Diarylhydrazides from N′-Arylhydrazides
Further Information
Publication History
Received: 13 January 2015
Accepted after revision: 09 February 2015
Publication Date:
12 March 2015 (online)
![](https://www.thieme-connect.de/media/synlett/201508/lookinside/thumbnails/st-2015-w0025-l_10-1055_s-0034-1380276-1.jpg)
Abstract
A novel method for conversion of N′-arylhydrazides to N′,N′-diarylhydrazides via aerobic oxidation has been achieved. The aerobic reaction was performed using CuCl2 as a catalyst in NH3·H2O–MeOH to give good yields under mild conditions. The mechanism of the reaction is also discussed.
Key words
N′-arylhydrazides - N′,N′-diarylhydrazides - aerobic oxidation - CuCl2 - geminal - N′,N′-diarylhydrazinesSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380276.
- Supporting Information
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References and Notes
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- 13 General Procedure for the Preparation of Products 2a–m A mixture of 1 (1 mmol) and CuCl2 (10 mol%) in 25% NH3·H2O (3 mL) and MeOH (15 mL) was stirred at r.t. for 0.5 h in O2 atmosphere (balloon). When the reaction was completed (as monitored by TLC; EtOAc–PE = 1:4 as eluent). The solvent was evaporated under reduced pressure. The resulting mixture was extracted with CH2Cl2 (15 mL) and washed with sat. brine (15 mL) three times. The combined organic layers were dried over anhydrous MgSO4. Then the organic solvent was evaporated. The residue was purified by column chromatography (EtOAc–PE = 1:4 as eluent) to give the desired product 2.
- 14 Procedure for the Preparation of Product 2a on Multigram Scale To a mixture of MeOH (250 mL) and 25% NH3·H2O (50 mL), 1a (100 mmol) and CuCl2 (10 mmol) were added successively in O2 atmosphere (balloon). The mixture was stirred for 3 h at r.t. The solvent was concentrated under reduced pressure. The resulting mixture was poured into H2O (200 mL). The slurry mixture was filtered through Buchner funnel and washed thoroughly with H2O to remove the cupric salts. The white crystals were collected and dried to give the product 2a (9.26 g, yield 81.9%).