Azidation Azido benzyl

Azides —N3 Acyl azides metal azides nomnetal azides organic azides other compounds containing azide moieties Acetyl azide lead azide ammonium azide benzyl azide azido-2-propanone... 

The benzylic hydrogen atom of alkylarenes is replaced by the azido group on treatment with trimethylsilyl azide in the presence of 2,3-dichloro-5,6-dicyano-l,4-benzoquinone subsequent hydrogenation yields amines (e.g. equation 5)31. 

For the synthesis of amino acids, the reaction of an a-haloalkyl boronic ester 4 with sodium azide and a phase-transfer catalyst in dichloromethane/water requires a large excess of azide in order to form the a-azidoalkyl boronic ester 5 with only 1-2% epimer34. With the exception of R1 = benzyl, where epimerization of 4 is relatively rapid, bromoalkyl boronic esters are preferred. Chloroalkyl boronic esters react so slowly that the azide and dichloromethane may generate hazardously explosive diazidomethane65,66. Chain extension of 5 to 6 proceeds normally. Sodium chlorite, which is known to oxidize aldehydes to carboxylic acids67-69, also oxidizes a-chloroalkyl boronic esters to carboxylic acids34. The azido acid is hydrogenated to the amino acid. 

Benzylazide and Derivatives Benzyiazide(cailed l -Azido-1-methyl-benzol, >-Azido-toluol and w-Triazo-toluol in Ger), C6HS.CH2.N3 mw 133.15, N 31-56% oil, d 1.0655 at 24.5°, nD 1.53414 at 24.9°, bp 82.5° at 16.5mm expl on strong heating with evoln of flame also expl on contact with coned sulfuric acid. Insoi in w, miscibie with ale or eth vol with steam or with ether. Can be prepd by treating benzyl chloride with Na azide in aic or by other methods... 

Aube and co-workers have found that enolizable ketones react with benzyl azide in triflic acid to yield /V-(phenylamino)-methylated products [Eq. (5.354)]. The transformation is an aza-Mannich reaction interpreted with the involvement of the Mannich reagent A -phenyl iminium ion 295 formed in situ in a Schmidt rearrangement. Cyclic tertiary alcohols react with alkyl azides in triflic acid to yield N-alkylamines (296, 297)983 [Eq. (5.355)]. The Schmidt rearrangement was used to transform Merrifield resin into amino-polystyrene resin by reacting the azido derivative in excess triflic acid (CH2CI2, 0°C).984... 

Treatment of the azido diacetal 256 with benzyl bromide and sodium hydride yielded the ether 257 quantitatively (Scheme 33).106,107 And this was subjected to azide reduction to give amine 258, and subsequent deacetonation gave 259. 

Addition to alkenes. Hydrazoic acid ados readily to cnol ethers to give a-azido ethers. Addition to styrenes and 1,1 -disubstituted or trisubstituted alkenes requires a Lewis acid catalyst (TiC or AlCl,). Benzylic, allylk. and tertiary alcohols react with HN, TiCl4 to form azides. 

The addition of lithium azide to ferr-butyldimethylsilyloxy-2-penten-4-olides during the synthesis of a 3 -azido-3 -deoxythymidine derivative66 and the diastereoselective addition of benzy-lamine to (R)-4-0-benzyl-4-hydroxy-2-penten-5-olide giving substituted /9-amino acid derivatives67 have also been reported. 

Pentryl. See 2-(2 , 4, 6-TrInitro-N-nitranilino Ethanol Nitrate under Aniline ethanol and Derivatives A425-L to A42 )-R Pentryl Homologs A429-R Peracetic Acid, Benzylester. See Acetyl-benzyl peroxide A55-L P hen acyl Azide. See a>-Azido acetophenone under Acetophenone A47-R Phenazone. See Antipyrine A471-R Phenetidine. See Aminophenetole A240-R Phenyl Abietate. See under Abietic Acid A4rL... 

Aziridines react with nucleophiles other than carbon nucleophiles. In the presence of TBAF, trimethylsilyl azide react with V-tosylaziridines to give the azido A-tosylamine. A-Benzylic aziridines are opened by trimethylsilyl azide in the presence of a chromium catalyst. Acetic anhydride reacts with N-tosylaziridines, in the presence of PBU3, to give the A-tosylamino acetate. A-Tosylaziridines react with InCls to give the chloro A-tosylamine. ... 

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