Synlett 2018; 29(02): 189-192
DOI: 10.1055/s-0036-1591311
letter
© Georg Thieme Verlag Stuttgart · New York

Efficient Method to Synthesize Benzhydrazides by In Situ Oxidation/Coupling of Benzylic Alcohols with Azodicarboxylates

Kobra Azizi
Chemistry Department, Tarbiat Modares University, P. O. Box 14155-4838 Tehran, Iran   Email: [email protected]
,
Akbar Heydari*
Chemistry Department, Tarbiat Modares University, P. O. Box 14155-4838 Tehran, Iran   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 11 July 2017

Accepted after revision: 29 August 2017

Publication Date:
16 October 2017 (online)


Abstract

An efficient synthesis of benzhydrazides has been achieved through the direct acylation of azodicarboxylates with benzylic alcohols in moderate to high yields. The method represents the first practical approach to amides containing a hydrazine structural unit from benzylic alcohols.

 
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  • 15 Dialkyl 1-Aroylhydrazine-1,2-dicarboxylates; General Procedure
    The appropriate dialkyl azodicarboxylate (1.5 mmol) was added to a stirred mixture of CuO nanoparticles (10 mol%) and a benzylic alcohol (0.75 mmol) in MeCN (0.5 mL) under argon. A 30% solution of t-BuOOH (2 equiv) was added dropwise, and the mixture was stirred at 80 °C for 6 h. When the benzaldehyde generated in situ had been consumed (TLC; decolorization of the azodicarboxylate was also observed), the mixture was treated with NaBH4 (0.5 mmol, 20 mg) in MeOH (0.5 mL). After 5 min, the reaction was quenched with aq NH4Cl (1 mL) and brine (1 mL). The cooled mixture was centrifuged to separate the catalyst then extracted with EtOAc (2 × 20 mL). The extracts were dried (MgSO4), filtered, and concentrated in vacuo to give a crude product that was purified by column chromatography [silica gel, EtOAc–hexanes (1:4)]. Diisopropyl 1-Benzoylhydrazine-1,2-dicarboxylate White solid; yield: 85%; mp 123 °C. 1H NMR (500 MHz, CDCl3): δ = 7.7 (m, 2 H), 7.52 (t, J = 7.4 Hz, 1 H), 7.4–7.45 (m, 2 H), 7.26 (br s, 1 H), 4.98–5.05 (m, 1 H), 4.8–4.9 (m, 1 H), 1.29 (d, J = 6.0 Hz, 6 H), 1.08 (d, J = 5.4 Hz, 6 H). Diethyl 1-Benzoylhydrazine-1,2-dicarboxylate Colorless oil; yield: 80%. 1H NMR (500 MHz, CDCl3): δ = 7.68 (d, J = 7.2 Hz, 2 H), 7.30–7.50 (m, 3 H), 7.24 (br s, 1 H), 4.23 (q, J = 7.2 Hz, 2 H), 4.15 (q, J = 7.2 Hz, 2 H), 1.29 (t, J = 7.2 Hz, 3 H), 1.07 (t, J = 7.2 Hz, 3 H).