Acid azides

Mn04 Reduction with arsenate(III), ascorbic acid, azide, hydrazine, hydroxylamine, oxalic... 

The reactions of amides fall into hydrolysis, dehydration and degradation (to amines) acid hydrazides and acid azides undergo additional reactions. 

Terephthalazide (VIII) Acid azide N2 85-112 207-311 Generates a di-isocyanate on decomposition which may cross-link some polymer species. Subsidiary reactions may increase blowing power. 

The initial 2-iodopropyolanilides are rather inaccessible compounds. Their preparation requires a three-stage synthesis with diphenylphosphinic acid azide as the starting material. 

To a freshly prepared solution of 2 parts of d-isolysergic acid azide in 300 parts of ether is added an ethereal solution of 2 parts of d-2-aminobutanol-1 and the mixture is left to stand at room temperature during 12 hours. The yellowish clear solution is then washed several times with some water, dried over sodium sulfate and the ether evaporated in vacuo. The crystallized residue is treated with a small quantity of acetone and filtered. Yield ... 

Oxamic Acid Azide (Azido Oxamate, Oxamido-azide, Oxamidsaureazid or Oxalsaure-amid-azid in Ger). H2N.CO.CO.N3, mw 114.02, N 49.11%, OB to C02 —42.09%, crystals from acet+petr eth mp, explds violently ca 115° or on rubbing. Can be prepd by treating the hydrazide of oxamic acid with Na nitrite in w Refs 1) Beil 2, (244) 2) T. Curtius, JPraktChem [2] 91, 426 (1915) 3) Urbanski 3... 

T rimath oxy phenanth rene-5-carboxy I ic acid azide. 

Nitrophthalic Acid Azide [3-Nitrophthalsaure azid (1), in Ger]. H02C.C6H3(N02).C0.N3, mw 236.16, N 23.73%. Scales from eth petr eth, mp explds on heating. Can be prepd by treating the hydrazide of 3-nitrophthalic acid, with nitrous acid under cooling conditions Refs 1) Beil 9,(370) 2) T. Curtius A. 

The y-nitrogen atom of a sulfonic acid azide is electrophilic and reacts in an electrophilic aromatic substitution with an activated benzene or naphthalene derivative, e.g., a phenoxide ion, forming a l-tosyl-3-aryltriazene (2.47). The 1,4-quinone diazide is obtained by hydrolysis (Scheme 2-30, Tedder and Webster, 1960). The general applicability of this reaction seems to be doubtful. With 1-naphthol the 1,2-naphthoquinone diazide was obtained, not the 1,4-isomer. 

The so-called transdiazotizations are mechanistically related to the introduction of diazonio groups using sulfonic acid azides. An aromatic diazonium ion forms a triazene (diazoamino compound) with an aromatic amine the triazene tautomerizes and dissociates at the Na-Np bond of the original diazonium ion. This reaction is important for the synthesis of the 4-aminobiphenyl-4,-diazonium ion, which cannot be obtained by direct (mono-)diazotization of 4,4 -diaminobiphenyl (Allan and... 

Polymerization of a stable intermediate prepared from two monomers can produce an alternating copolymer. The amino acid azide hydrobromide method and the amino acid succinimidyl ester hydromide method were applied to prepare ordered copolyamides277) and sequential copolypeptides278-280). 

The carboxylic acid group is converted by CDI and sodium azide into an acid azide, which via a Curtius rearrangement gives the corresponding amine.[135a3... 

Tetraacetyl-/ -D-glucosamine with Acyl Amino Acid Azides. J. Amer. chem. Soc. 75, 3469 (1953). 

A convenient method was developed for the synthesis of 4-amino-3-furoxancarboxylic acid azide, which is a universal synthon for the preparation of furoxan derivatives 320 (Scheme 81). This method was used for the synthesis of new azo-, azoxy-, azido-, cyano-, nitro-, carbonylamino-, and hydroxylamino-substituted furoxan derivatives that are difficult to prepare using alternative procedures <2003RCB1822>. 

In remembrance of the isolation of carbene 78 (Section m.C) it seems acceptable that 141, formed from 140 by a [l,2]-migration of the substituent, functions as a second intermediate. Carbene 141 can subsequently fragment into a nitrene 143 and carbon monoxide or open to an isocyanate 144, which alternatively may also be generated from an acid azide via acylnitrene 142. In comparison to calculated reaction pathways 75 78 and 82 81 (Schemes... 

Active ester Mixed anhydride Mixed anhydride Acid azide... 

Phcnylcyclopentylamine, by hydrolysis of phenylcyclo-pentyl isocyanate, 51, 49 Phenylcyclopentyl isocyanate, by thermolysis of phenyl-cyclopentane-carboxylic acid azide, 51, 49... 

Thermolysis, 1-phenylcyclopen-tanecarboxylic acid azide to 1-phenyl-cyclopentyl isocyanate, 51, 49 4i/-l,4-THIAZINE 1,1-DIOXIDE,... 

M Crisma, V Moretto, G Valle, F Formaggio, C Toniolo. First characterization at atomic resolution of the C-activating groups in a peptide synthesis acid chloride, acid azide and carboxylic-carboxylic mixed anhydride. Int J Pept Prot Res 42, 378, 1993. 

Ring-chain tautomerism caused by the migration of an azido group has been observed rather rarely. By means of IR spectroscopy, the equilibrium 19A 19B was detected [81JCS(P1)2884] in benzene solutions of N,N-disubstituted tetrahalogenophthalamic acid azides. Mixtures of open-chain and cyclic isomers of 2-benzoylbenzoyl azide were obtained [88JCS(P1)2149], from which only isolation of the cyclic isomer succeeded. 

Thermolysis, 1-phenylcyclopentanecar-boxylic acid azide to 1-phenylcy-... 

Kinetic studies using the water-soluble nitrile li revealed first-order dependence in both nitrile and azide and one-half order dependence for zinc bromide. The mechanism of the addition of hydrazoic acid/azide ion to a nitrile to give a tetrazole has been debated, with evidence supporting both a two-step mechanism (Scheme 1, eq 2) and a concerted [2 + 3] cycloaddition (Scheme 1, eq 3). Our mechanistic studies to date imply that the role of zinc is not simply that of a Lewis acid a number of other Lewis acids were tested and caused little to no acceleration of the reaction. In contrast, Zn exhibited a 10-fold rate acceleration at 0.03 M, which corresponds to a rate acceleration of approximately 300 at the concentrations typically used. The exact role of zinc is not yet clear. 

The usual procedure of preparing acid azides, which involves treating an acid chloride with sodium azide,8,9 suffers from the disadvantage that it is often difficult to obtain pure acid chlorides in good yields from acids which either decompose or undergo isomerization in the presence of mineral acids.7 Synthesis of the azide by way of the ester and hydrazide10 has been used to circumvent this difficulty but is much less convenient. The present procedure permits ready formation of acid azides in excellent yields from mixed carboxylic-carbonic anhydrides and sodium azide under very mild conditions. 

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