The Formation of Tin-Nitrogen Bonds. V. The Selective 1-Substitution Reaction of Tetrazoles by the Reaction of 5-Substituted 2-(Tri-n-butylstannyl)tetrazoles with Methyl Iodide, Methyl p-Toluenesulfonate, Dimethyl Sulfate, and Ethyl Bromoacetate

Abstract

The selective 1-substitution reaction of tetrazole was developed by the treatment of 5-substituted 2-(tri-n-butylstannyl)tetrazoles with methyl iodide, methyl p-toluenesulfonate, dimethyl sulfate, or ethyl bromoacetate at room temperature. This selectivity was introduced by blocking the 2-nitrogen with the tri-n-butyltin group against the 2-substitution. In the case of 5-substituted 2-(trimethylstannyl)tetrazoles, a low selectivity was observed. The possible reaction pathways have been discussed.

Studies on monocyclic .BETA.-lactam antibiotics. III. Synthesis and antibacterial activity of N-(aromatic heterocyclic substituted)azetidin-2-ones.

“…Scheme 2 describe the synthetic route to 3-amino-4-methyl-l-(]H-tetrazol-5-yl)-2-azetidinones (14). Cyclization of compounds 9j and 9k obtained from N-CBZ-L-threonine and N-CBZ-L-allothreonine, respectively, in a similar manner as in Scheme 1, gave only 20% of 13.…”

“…The alkylation of 2h with p-nitrobenzyl bromoacetate and Et3N in dimethylformamide gave the N-1 isomer (17) and the N-2 isomer (18) in a ratio of 1 to 2. Structural confirmation of the N-1 and N-2 substituted tetrazole isomers were made according to the report of ISIDA et al 14) in that the chemi- cal shift of methylene group at the N-2 position was reported to appear at lower field than that at the N-1 position. The 'H NMR spectrum of the N-1 substituted tetrazole (17) in CDCl3 -CF3OOOD…”

Azide Chemistry – An Inorganic Perspective, Part II[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

“…1,3,5-trimethyltetrazolium species with excess methyl iodide. [108,158,215,221,294] On the other hand, there are reports on alkylation reactions even of 2-(tri-n-butylstannyl)tetrazoles which predominantly result in N 2 -substituted isomers, one example being shown in Equation (3a). Here, a large excess of α,ω-dibromoalkanes was employed giving rise to a mixture of N 2 ,N 2 '-(a) and N 1 ,N 2 '-isomers (b) in a ratio of ca.…”

Arylation of Tetrazolide With Diaryliodonium Halides: Evidence for Intermediacy of Benzyne

“…As a continuation of our investigation on the chemistry of nitrogen heterocycles, 1) we sought to arylate tetrazolides by means of iodonium halides. After heating sodium 5-phenyltetrazolide (II) with di-p-tolyliodonium bromide (I) 2a) under reflux in t-BuOH for 24 hr, usual work-up gave compounds (III-V)(eq.…”