Synlett 2015; 26(08): 1121-1123
DOI: 10.1055/s-0034-1380276
letter
© Georg Thieme Verlag Stuttgart · New York

A Novel Approach to N′,N′-Diarylhydrazides from N′-Arylhydrazides

Jun Yu
a  College of Pharmaceutical Sciences, Zhejiang University of Technology, Zhaohui Liuqu, 310014 Hangzhou, P. R. of China
,
Shuguang Wang
a  College of Pharmaceutical Sciences, Zhejiang University of Technology, Zhaohui Liuqu, 310014 Hangzhou, P. R. of China
,
Jianming Wen
b  Hangzhou Allsino Chemicals Co., Ltd., Xihu Gongyeyuan, 310000 Hangzhou, P. R. of China   Email: lijh@zjut.edu.cn
,
Jian Wang
a  College of Pharmaceutical Sciences, Zhejiang University of Technology, Zhaohui Liuqu, 310014 Hangzhou, P. R. of China
,
Jing-Hua Li*
a  College of Pharmaceutical Sciences, Zhejiang University of Technology, Zhaohui Liuqu, 310014 Hangzhou, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 13 January 2015

Accepted after revision: 09 February 2015

Publication Date:
12 March 2015 (online)


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.

Supporting Information

 
  • References and Notes

    • 1a Zhan F, Liang G. Angew. Chem. Int. Ed. 2013; 52: 1266
    • 1b Wagaw S, Yang BH, Buchwald SL. J. Am. Chem. Soc. 1999; 121: 10251
  • 2 Han J, Shin Y, Sharma S, Mishra NK, Park J, Kim M, Kim M, Jang J, Kim IS. Org. Lett. 2014; 16: 2494
    • 3a Glamkowski EJ, Fortunato JM, Spaulding TC, Wilker JC, Ellis DB. J. Med. Chem. 1985; 28: 66
    • 3b Unangst PC, Carethers ME, Webster K, Janik GM, Robichaud L. J. Med. Chem. 1984; 27: 1629
    • 3c Unangst PC, Connor DT, Stabler SR, Weikert RJ, Carethers ME, Kennedy JA, Thueson DO, Chestnut JC, Adolphson DO, Conroy MC. J. Med. Chem. 1989; 32: 1360
    • 4a Showalter HD. H, Angelo MM, Berman EM, Kanter GD, Ortwine DF, Ross-Kesten SG, Sercel AD, Turner WR, Werbel LM, Worth DF, Elslager EF, Leopold WR, Shillis JL. J. Med. Chem. 1988; 31: 1527
    • 4b Angelis MD, Stossi F, Carlson KA, Katzenellenbogen BS, Katzenellenbogen JA. J. Med. Chem. 2005; 48: 1135
    • 4c May JA, Dantanarayana AP, Zinke PW, McLaughlin MA, Sharif NA. J. Med. Chem. 2006; 49: 318
    • 5a Entwistle ID, Johnstone RA. W, Wilby AH. Tetrahedron 1982; 38: 419
    • 5b Hong SS, Bavadekar SA, Lee SI, Patil PN, Lalchandani SG, Feller DR, Miller DD. Bioorg. Med. Chem. Lett. 2005; 15: 4691
    • 5c Iskii H, Sugiur T, Akiyama Y, Ichikawa Y, Watanabe T, Murakami Y. Chem. Pharm. Bull. 1990; 38: 2118
  • 6 Wu W, Li X.-L, Fan X.-H, Yang L.-M. Eur. J. Org. Chem. 2013; 862
  • 7 Molina CL, Chow CP, Shea KJ. J. Org. Chem. 2007; 72: 6816
  • 8 Jiang T, Chen S, Zhuang H, Zeng R, Zou J. Tetrahedron Lett. 2014; 55: 4549
  • 9 Jadhav RR, Huddar SN, Akamanchi KG. Eur. J. Org. Chem. 2013; 6779
  • 10 Wei W, Liu C, Yang D, Wen J, You J, Suo Y, Wang H. Chem. Commun. 2013; 49: 10239
  • 11 Xia R, Xie M.-S, Niu H.-Y, Qu G.-R, Guo H.-M. Green Chem. 2014; 16: 1077
  • 12 Hofmann J, Jasch H, Heinrich MR. J. Org. Chem. 2014; 79: 2314
  • 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%).