5-Aminotetrazole, oxidation with

Substituted 5-aminotetrazoles Reactions with electrophiles and oxidation... 

Diazotetrazole (16) was obtained by dropwise addition of 2-pentyl nitrite to a solution of 5-amino-l//-tetrazole in a 4 1 mixture of tetrahydrofuran and aqueous hydrochloric acid. The diazonium chloride can be extracted into ether. Shevlin obtained the extremely explosive solid diazonium salt (16) by evaporation of that solution. He has recommended that not more than 0.75 mmol of diazonium salt be isolated at one time. An explosion during the diazotization of 5-aminotetrazole on a laboratory scale was described by Gray and coworkers. The structure 17 (equation 5) indicates clearly that this diazo compound may have the tendency to decompose into atomic carbon and three equivalents of dinitrogen—a reaction which is clearly highly exothermic. The decomposition of the tetrazole-5-diazonium chloride (16) has been studied by Shevlin by coating the salt on the walls of a 500 ml flask in the presence of two substrates, ethene and ethylene oxide. With ethene the products found after heating the flask to 80 °C are shown in equation 6, and with ethylene oxide in equation 7. The products correspond to those found with atomic carbon formed by completely different methods (see references cited by Shevlin). 

The synthesis of BENZYL ISOCYANIDE from benzaldehyde via reductive amination with 5-aminotetrazole followed by oxidation of the resultant amine with sodium hypobromite provides a general method for the synthesis of isocyanides. The preparation of BIS(2,2,2-TRICHLOROETHYL) AZODICARBOXYLATE makes available an alternative to dimethyl azodicarboxylate that is not only more reactive in Diels-Alder reactions but whose ester groups can be removed under neutral conditions. 

Nitrotetrazole has been obtained by the diazotiation of 5-aminotetrazole with following addition of 20% H2S04 [469], 2-Methyl-5-nitrotetrazole has been prepared by the oxidation of the 5-amino derivative by dinitrogen peroxide [470],... 

An odd reaction is the well known, once industrially used, preparation of 5-aminotetrazole from thiohydantoin by treatment with sodium azide and lead oxide in an atmosphere of carbon dioxide (reaction... 

According to Thiele (154) oxidation of 5-aminotetrazol with potassium permanganate in the presence of an excess of sodium hydroxide yielded sodium salt of azotetrazol ... 

Resin-bound benzonitriles 189 were reacted with trimethylsilyl azide in the presence of dibutyltin oxide followed by acidic cleavage to give 5-biphenyl-2-yl-l//-tetrazoles 190 <04OL1143>. Resin-bound thioureas 191 reacted with sodium azide in the presence of mercury(II) chloride followed by acidic cleavage to give 5-aminotetrazoles 192 <04TL7787>. 

Violent reaction with acids, trans-acetylene dichloride, alcohols, organic anhydrides, aldehydes, alkylene oxides, aminotetrazole, /j-bis(l,3-dibromoethy )benzene, bromoform, captrolactam solution, chlorine dioxide (explodes), chloroform, cresols, cyclopentadiene, cis-dichloroethylene, epichlorohydrin, ethylene dichloride, germanium, glycols, halogenated hydrocarbons, iodine pentafluoride, isocyanates, maleic anhydride, nitrogen trichloride,... 

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