Tosyl azide amines

Routes to phosphazenes involving the reaction of phosphines with carbon tetrachloride in the presence of amines have been reviewed44 and it has been shown45 that this type of reaction does not occurwithdiphosphines.lt was, however, successful with a phosphonite and tosylamine (Scheme 3).46 The same product was also obtained with tosyl azide. 

Arylamines and hydrazines react with tosyl azide under basic conditions to yield aryl azides [1] and arenes [2], respectively, by an aza-transfer process (Scheme 5.25). Traditionally, the reaction of anilines with tosyl azides requires strong bases, such as alkyl lithiums, but acceptable yields (>50%) have been obtained under liquidiliquid phase-transfer catalytic conditions. Not surprisingly, the best yields are obtained when the aryl ring is substituted by an electron-withdrawing substituent, and the yields for the corresponding reaction with aliphatic amines are generally poor (-20%). Comparison of the catalytic effect of various quaternary ammonium salts showed that tetra-/i-butylammonium bromide produces the best conversion, but differences between the various catalysts were minimal [ 1 ]. 

Azides and amines from Grignard reagents and tosyl azide [74]. 

When R1 = CN, a molecule of hydrogen cyanide is lost and the 5-amino-triazole is obtained.249 Spontaneous amine elimination also occurs when R2 is hydrogen and an aliphatic secondary amino group is present,214 which is similar to what is observed in the addition of tosyl azide to /3-enamino esters233 and nitriles.402 Thermal elimination of amine proceeds more... 

Tosyl azide has been used as a starting material for the synthesis of alkyl and aryl azides by acting as a diazo donor to amine metal or Grignard compounds. Yields were An example... 

The few examples indicate that sulfone-stabilized carbanions should react normally with electrophilic animating reagents (Eqs. 145158 and 146465) with the caveat that free a-amino sulfones are unstable.158,465 The (3,y-unsaturated sulfone 74 is animated at the y-position (Eq. 147),250 presumably by an ene reaction. The preparation of a-tosyl azides from nitronates was shown above in Eq. 144. The scope of this reaction does not seem to have been determined. Reaction of the anions of nitrobenzyl aryl sulfones with l-oxa-2-azaspiro[2.5]octane (13a) gives nitrobenzaldehydes by cleavage of the initially formed amination products.466 Similarly, reaction of the lithium salt of benzyl phenyl sulfone with phenyl azide gives benzilydeneaniline and phenyl sulfinate.467 No reports on animations of sulfoxide-stabilized carbanions were found. 

Cais2b found that phenyllithium can be replaced by other bases, preferably diethyl-amine or ethanolamine. A mixture of cyclopentadiene, tosyl azide, and diethylamine was allowed to stand at 0° for three days then, after addition of water, diazocyclo-pentadiene was extracted with ether (73% yield). The yield is somewhat higher when acetonitrile is used as solvent.2C... 

Azide synthesis (2, 415). In the definitive paper3 describing the conversion of primary amines into azides by a diazo transfer reaction, methyllithium is preferred to methylmagnesium chloride as the base. The reaction has been extended to hydrazones. Thus, when the hydrazones of benzophenone, fluorenone, and acetophenone are treated with methylmagnesium chloride and then with tosyl azide, the corresponding diazoalkanes are obtained in about 20% yield. 

The transformation of 3-phenylindazol-l-amine (3a) into 4-phenyl-l,2,3-benzotriazine (7a) by reaction with butyllithium and tosyl azide has been reported.115... 

The cyclisation to 1,2,3-triazoles 158 ocurred after treatment with tosyl azide in the presence of a tertiaiy amine. Following removal of solvents, the treatment of the resin-bound 1,2,3-triazoles 158 with 60% TFA in CHjClj afforded triazoles 159 as trifluoroacetates salts in good purities. The mild reaction conditions used in this protocol enabled its application to building blocks with a large number of different functionalities. Only when using electron rich benzylic amines in the enamine forming step, mixtures of products were obtained. 

Diazo transfer. Diazo transfer from tosyl azide to aryl amines can be effected V phase-transfer catalysis. ... 

In another variant of the Niementowski reaction, it was found that this transformation can be carried out under relatively mild, base-catalyzed conditions. Since a variety of substituted anthranilamides (29) can be prepared by a regiospecific ortho metalation-amination sequence, this method appears to be a very versatile modification of the Niementowski quinoline synthesis. Lithiation of 28 with 5-butyllithium was followed by treatment with tosyl azide. Reduction of the azide with sodium borohydride under phase transfer conditions furnished 29. After conversion of 29 into the corresponding imine 30, treatment of 30 with LDA afforded 31 in good yield. 

Di-t-butyl chromate and its pyridine adduct are suitable for large-scale oxidations of alcohols to ketones, thus cyclododecanol was converted into cyclododecanone (97 Alcohols are easily separated from non-hydroxylic compounds via their calcium chloride complexes. This method was used to separate cyclododecanone and cyclododecanol and is suitable for the separation of large quantities of material." All-cis-cyclododecane-l,5,9-triol was converted into the all-cis-tri-amine by tosylation, azide substitution, and reduction, and the amine acylated with 2,3-dimethoxybenzoyl chloride to give the tri-amide, an analogue of enterochelin. ... 

Scheme 3.26 Alkyl azides from amines by treatment with tosyl azide "...

Alkyl azides can alternatively be obtained from amines by treatment with tosyl azide and sodium hydride. This procedure allows for the synthesis of bridgehead azides such as l-azidobicyclo[2.2.2]octane (188) and 1-azidoadamantane (190) in 83% and 92% yield, respectively (Scheme 3.26). 

Aryl azides and heteroaryl azides can be prepared by the reaction of aromatic amines with trifly 1 azide. This straightforward approach to aromatic azides can be carried out under mild reaction conditions. In fact, the reaction of 8-aminoquinoline (262) in dichlorometh-ane/methanol occurs at room temperature in the presence of triethylamine and copper sulfate to afford 8-azidoquinoline (263) in 95% isolated yield. The reaction of aryl amide salts 265, generated from the corresponding anilines 264 and strong bases, with tosyl azide also affords aryl azides 266 (Scheme 3.38). ... 

The inertia of (TMS)3SiH toward azides allows this functionality to be used as a radical acceptor. An example is given in Reaction (52) where the amine product was tosylated before work-up. 

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