With hydrazoic acid

The conversion of a carboxylic acid into an amine by treatment with hydrazoic acid in concentrated sulphuric acid is known as the Schmidt reaction or rearrangement ... 

Azides have been shown to react with itniniutn salts to give addition products. The same product is obtained if the iminium salt is treated with azide ion or if the enamine is treated with hydrazoic acid 14). The yields of the products were all very high (85-95 %). The interest in this reaction centers on the fact that the azides react with isonitriles to give substituted tetrazoles (83) 44). 

As shown by Oliveri-Mandalli,and by Lieber et al., 5-sub-stituted-amino-l,2,3,4-thiatriazoles are also formed by reaction of isothiocyanates with hydrazoic acid. When sodium azide is used instead of the free acid the isomeric mercaptotetrazoles are formed. 

Reaction of carboxylic acids, aldehydes or ketones with hydrazoic acid... 

The reaction of carboxylic acids, aldehydes or ketones with hydrazoic acid in the presence of a strong acid is known as the Schmidt reaction A common application is the conversion of a carboxylic acid 1 into an amine 2 with concomitant chain degradation by one carbon atom. The reaction of hydrazoic acid with a ketone 3 does not lead to chain degradation, but rather to formation of an amide 4 by formal insertion of an NH-group. 

A1( -octalone, 45, 80 N-nitioso-N-phenylglycine to N-phenylsydnone, 45, 96 Cyclobutanecarboxylic acid, reaction with hydrazoic acid, 47, 28 Cyclobutene, 1,2,3,4-tetrasiethyl-3,-4-dichloro-, 46, 34 reactions of, 46, 36 Cyclobutylamine, 47, 28 Cyclobutyl isocyanide, 46, 77 Cycloheptanone, 45, 31... 

Preparation. It was first prepd by wanning a strongly alk soln of Na azide with Me sulfate (Refs 2 20), and this is the only practical prepn. It has also been prepd by the reactn of diazomethane with hydrazoic acid (Ref 6)... 

Methyl mercuric Azide (Mercuric methylazide). CH3HgN3 cry sts from alc mp 130.5° decompn explosively ca 200°. Was prepd by Perret Perrot (Ref 3) by treating methyl mercuric hydroxide, CH3HgOH (Ref 1) with hydrazoic acid... 

The most general reaction for the preparation of sulphoximines from sulphoxides is simply by reaction with hydrazoic acid (equation 65)178. Highly substituted sulphoxides, such as diethyl sulphoxide with more than two chlorine substituents, do not undergo reaction to form the sulphoximine in this way. 

The mechanism is similar to those of the analogous reactions with hydrazoic acid (18-16 with ketones) and diazomethane (18-8) ... 

Mn(III) in perchloric acid forms a pink complex with hydrazoic acid, which decomposes thermally to give nitrogen with stoichiometry A[Mn(IIl)]/A[HN3] = 1.0 and with kinetics... 

Carboxylic acids and esters can also be converted to amines with loss of the carbonyl group by reaction with hydrazoic acid, HN3, which is known as the Schmidt reaction,278 The mechanism is related to that of the Curtius reaction. An azido intermediate is generated by addition of hydrazoic acid to the carbonyl group. The migrating group retains its stereochemical configuration. 

Isocyanates132 react with appropriate azide salts to yield 1-substituted tetrazoline-5-ones (68) (Eq. 13). By contrast, isothiocyanatesi33,i34 react with hydrazoic acid to yield the aminothiatriazole (69) which rearranges to the thione (70) under mild alkaline conditions (Scheme 8). Ugi and co-worker126,127 found that when the reaction of isonitriles and hydrazoic... 

With hydrazoic acid or (better) trimethylsilyl azide and ImCSIm, 5-(l-imidazolyl)-1,2,3,4-thiatriazole is obtained 11301 11321... 

Sulfoximines are an example of a tetracoordinated chiral compound, and their optical isomers have been isolated. Their stereochemistry was also studied approximately 30 years ago.43 Endocyclic sulfoximines are an example of chiral heteroaromatics. Endocyclic sulfoximines 26 were optically resolved on a chiral column for the first time by Allenmark and co-workers in 1995.44 The stereoisomers were obtained by amination and subsequent cyclodehydration of optically active o-carboxyphenyl sulfoxide with hydrazoic acid or 0-(me-sitylenesulfonyl) hydroxylamine (Scheme 14). 

The reaction of carboxylic acids with hydrazoic acid in concentrated sulfuric acid to give amines is faster with acids whose t-factor equals 4. 

The Schmidt reaction of ketones with hydrazoic acid is believed to be a similar rearrangement, again with concerted trans migration and elimination of nitrogen. 

A one-pot procedure for the conversion of alcohols into alkylamines is by treatment of the former with hydrazoic acid in the presence of triphenylphosphine and diisopropyl azodicarboxylate addition of triphenylphosphine to the resulting azide gives an hninophosphorane, which is hydrolysed to the alkylamine by water (equation 8)35. 

Hydrazoic acid adds readily to acetylenes with electron-withdrawing groups, and less readily to alkyl and aryl acetylenes.Acetylene itself gives a high yield of i -triazole under carefully controlled conditions. Not all acetylenes give triazoles with hydrazoic acid. Open-chain azides have been obtained with ethoxyacetylene and with dimethyl acetylenedicarboxylate... 

The reaction with hydrazoic acid converts ketones to amides. 

A recent endeavor at the total synthesis of isopavines describes a promising novel route to these bases via functionalized dibenzocyclooctadienes (Scheme 27) 148). Dibenzocyclooctadienyl ether 132, formed from homoveratraldehyde (131) by a double Friedel-Crafts alkylation, is converted to dibenzocyclooc-tatrienol 133. Treatment with hydrazoic acid, followed by thermolysis and reduction, supplies ( )-isopavine (35) in good overall yield (53%). Subsequent attempts to prepare pavine bases by this approach have proved to be unsuccessful 148). 

---