Sodium azide reaction with acid anhydrides

The acyl azide intermediates are prepared either by reaction of sodium azide with a reactive acylating agent or by diazotization of an acyl hydrazide. An especially convenient version of the former process is treatment of the carboxylic acid with ethyl chloroformate to form a mixed anhydride, which then reacts with azide ion.265... 

Goodman and Chorev 75 found that the required a-aminoacyl azides 14 are best prepared by reaction of the mixed anhydride of the amino acid with sodium azide. This method led to slightly better yields than the nitrosylation of TV-formylaminoacyl hydrazide. Curtius rearrangement of the a-aminoacyl azide 14 yielded the isocyanate 16, which was subsequently trapped as 17 or 18 as shown in Scheme 2. Comparable yields were obtained by nitrosylation with tert-butyl nitrite. 76 Other methods of acyl azide formation have rarely been employed for PMRI-peptide synthesis. Only Fincham et al. 11 reported the use of trimethylsilyl azide to synthesize an acyl azide en route to a PMRI-peptide. 

Treatment of phthalic acid (145) with sodium azide under acidic conditions has been reported" to give various products anthranilic acid (147) and a trace of o-phenylenediamine (148) in concentrated sulfuric acid and anthranilazide (149) and benzimidazol-2-one (150) in 90% sulfuric acid. Analogously, phthalic anhydride (146) gives the following products anthranilic acid (147), benzimidazol-2-one (150) and some 3,l-benzoxazine-2,4(l//)-dione (isatoic anhydride) (151) in sulfuric acid and benzimidazol-2-one (150) in acetic acid. A recent report" has revealed that Ae Schmidt reaction of phthalic acid (145) in 90-98% sulfuric acid gives anthranilic acid (147) and anthranilazide (149) (major products) by a process thought to involve 3,l-benzoxazine-2,4(l//)-dione (151) as an intermediate. Benzimidazol-2-one (150) is produced in this reaction by a secondary process from anthranilazide (149). Photolysis of (149) also produces (150). 

The Curtius rearrangement has been extensively utilized for the synthesis of numerous cyclo-propylamines 4 from cyclopropanecarboxylic acids 1. The necessary acyl azides 2 are most conveniently obtained by reaction of sodium azide with the mixed anhydride of the cyclopropanecarboxylic acid and ethyl chloroformate. ... 

Apart from the reaction of diazomethane with benzoyl chloride, - diazoacetophenone has been prepared by the reaction of 2-aminoacetophenone hydrochloride with sodium nitrite, from the mixed anhydride of benzoic acid and ethyl carbonate with diazomethane, from benzoyl chloride and potassium methyldiazotate, by treating the enamine formed from 2-formylacetophenone and N-methylaniline with p-toluenesulfonyl azide, and from the reaction of the sodium enolate of 2-formylacetophenone with p-toluenesulfonyl azide. 

CHLOROCHROMIC ANHYDRIDE (14977-61-8) A powerful oxidizer. Violent reaction with water, producing hydrochloric and chromic acids, and chlorine gas. Potentially violent and explosive reaction with reducing agents, acetone, alcohols, calcium sulfide, combustible materials, gaseous or liquid ammonia, ethers, nonmetal halides, fuels, nonmetal hydrides, fluorine, organic matter, organic solvents, phosphorus, phosphorus trichloride, sodium azide, elemental sulfur, sulfur monochloride, turpentine, urea. Decomposes slowly in light. 

MERCURIC NITRATE (10045-94-0) A powerful oxidizer. Violent reaction with reducing agents, combustibles, phosphinic acid, hypophosphoric acid, petroleum hydrocarbons. Forms heat- and/or shock-sensitive compounds with acetylene (forms mercury acetylide), ethanol (forms mercury fulminate), ferrocene, isobutene, phosphine, potassium cyanide, sulfur. Incompatible with strong acids, acetic anhydride, ammonia, ammonium hexacyanofer-rate(II), organic azides, citric acid, hydrazinium perchlorate, isopropyl chlorocarbonate, nitrosyl perchlorate, sodium thiosulfate, sulfamic acid, thiocyanates, hydrozoic acid, methyl isocyanoacetate, sodium peroxyborate, trinitrobenzoic acid, urea nitrate. Aqueous solution corrodes metals. 

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