Acid Amide from azide

The Ru(III)-promoted formation of the amide bond permits the synthesis of amides from azides and thio acids at room temperature, and the reaction is applicable to less-reactive azides. Thus the azide, 119 as a model compound, in methanol solution, was transformed in 80% yield into the corresponding acetamide 240 by the action of thioacetic acid (2.5 eq.) and 2,6-lutidine. ... 

Irradiation isopropanol Sulfonic acid amides from sulfonic acid azides... 

Without additional reagents N-Silylcarboxylic acid amides from 1-siloxy-l-azides... 

Via intermediates Subst. carboxylic acid amides from carboxylic acid hydrazides via carboxylic acid azides Peptide synthesis... 

Mercurioferrocenes (290) and (291) are separable by Soxhlet extraction and these may be used to prepare bromoferrocene or dibromoferrocene or the iodo analogs. Alternatively, these halogenated ferrocenes are prepared from the ferrocene boronic acids or from anions (322) or (323). Bromoferrocene is the starting material for cyanoferrocene, azidoferrocene, or aminoferrocenes, generally in the presence of a copper salt. Amtnoferrocene can be acylated to produce an amide, or converted to isocyanoferrocene by a formylation/dehydration sequence (Scheme 96). The 1,T-diisocyanoferrocene is available from the bis(acyl)azide, itself derived from ferrocene dicarboxylic acid. ... 

Tetrakis(dimethylamino)titanium is a useful reagent for preparing amidines from secondary amides. From A X-thionyldiimidazole and secondary amides of boA aromatic and aliphatic carboxylic acids amidines (313 Scheme 50) are formed under mild conditions in moderate to good yields. N-Tosyl-amidines (314) can be obtained by reacting secondary thioamides (aliphatic and aromatic) with tosyl azide. Thiobenzamides have been condensed with anilines to afford amidines (315). Thioamides can be converted to amidines, e.g. (316), by treatment with ammonia in the presence of mercury acetate. ... 

Lithium aminoborohydrides are obtained by the reaction of -BuLi with amine-boranes [FF2, FH5, NT2]. They can be generated in situ as THF solutions or as solids when formed in diethylether or hexane (n-BuLi must then be used in sub-stoichiometric amounts). They are stable under dry air and are slowly decomposed by water [NT2] or methanol so that workup of the reactions mixtures can be carried out with 3M HCl. They reduce alkyl halides (Section 2.1), epoxides (Section 2.3), aldehydes, and ketones (Section 3.2.1) (in the latter case with an interesting stereoselectivity [HFl]), and esters to primary alcohols (Section 3.2.5). a,(3-Unsaturated aldehydes, ketones, and esters are reduced to allyl alcohols (Section 3.2.9) [FF2, FS2]. Depending on the bulkiness of the amines associated with the reagent and to the substrate, tertiary amides give amines or alcohols (Section 3.2.8) [FFl, FF2]. Amines are also formed from imines (Section 3.3.1) [FB1 ] and from azides (Section 5.2) [AFl]. However, carboxylic acids remain untouched. 

Lysergic Acid Azides and Amides from Lysergic Acid Hydrazides... 

Amide formation. Carboxamides including peptides are S3mthesized from carboxylic acids and aUcyl azides, after converting the acids into mixed anhydrides and then selenocarboxylates. Treatment of the mixed anhydrides with a suspension of freshly prepared from LAH and Se completes the first stage of the transformation. 

The dediazoniation of the vinyl azide proceeds via vinyl nitrene. A variant of this synthesis enables the preparation of 3-(dialkylamino)-2//-azirines starting from A,7V-disubstituted acid amides [15] ... 

Benzotriazines are ring-opened by aqueous acid at room temperature yielding o-aminobenz-aldehydes, whereas 4-substituted derivatives require heating to form <9-aminoaryl ketones. 1,2,3-Benzotriazin-4(37/)-ones 1 suffer acid cleavage of the heterocycle producing the diazonium ion 2 derived from anthranilic acid amide. Subsequent reactions of these ions involving the A-amino system 3 lead to the anthranilic acid azide 4 by an internal redox disproportionation ... 

---