Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

The Zwitterionic Structure of the Parent Amidinium Tetrazolide and a Rare Tetrazole Ring-Opening Reaction

Yosuke Uchiyama A B D , Joshua S. Dolphin A , Richard L. Harlow A , William J. Marshall C and Anthony J. Arduengo III III A D

A Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487-0336, USA.

B Department of Chemistry, School of Science, Kitasato University, 1-15-1 Kitasato, Minami-ku, Sagamihara, Kanagawa 252-0373, Japan.

C DuPont Central Research, Experimental Station, E500/1808, Wilmington, DE 19880-0500, USA.

D Corresponding authors. Email: yosuke@kitasato-u.ac.jp; aj@ajarduengo.net

Australian Journal of Chemistry 67(3) 405-410 http://dx.doi.org/10.1071/CH13460
Submitted: 2 September 2013  Accepted: 19 September 2013   Published: 10 October 2013

Abstract

A crystallization method for 5-amidinium tetrazolide (1) was developed. Crystals of the pure zwitterion 1 enabled the unambiguous assignment of the structure as an inner-salt rather than the amidine tetrazole postulated previously. The solid-state structure of 1 consists of two sets of hydrogen bonds that form a tightly networked two-dimensional sheet. The reaction of amidinium tetrazolide 1 with SOCl2 in the presence of 2.0 equiv. of Et3N produces 3-amino-4-azido-1,2,5-thiadiazole (2) as the sole product. The required tetrazole ring-opening reactivity suggests that the tetrazole moiety may function as a masked geminal azido-nitrene. The thionyl chloride reaction with the amidinium zwitterion 1 occurs not exclusively at the amidine, but rather in the Bay-region of 1, which comprises both the amidinium group and tetrazolide ring. Thiadiazole 2 has a planar structure with a 2D network of hydrogen bonds between the amino group and nitrogen atoms and an S⋯N interaction between the azido group and sulfur.

Graphical Abstract Image


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