Hydrazoic acid, reaction with acids

Hydrazoic acid reaction with cyclobu-tanecarboxyhc acid, 47, 28 Hydrogenation of t butylazidoacetate to glycme ( butyl ester, 46,47 Hydrogen bromide 46, 43 reaction with y butyrolactone, 46, 43 Hydrogen fluoride anhydrous, precautions in use of, 46, 3 in preparation of mtromum tetra-fluoroborate 47, 57 reaction with benzoyl chloride, 46,4 with boron tnfluonde in conversion of p cymene to m cymene, 47, 40 in bromofluorination of 1 heptene, 46, 11... 

A1( -octalone, 45, 80 N-nitioso-N-phenylglycine to N-phenylsydnone, 45, 96 Cyclobutanecarboxylic acid, reaction with hydrazoic acid, 47, 28 Cyclobutene, 1,2,3,4-tetrasiethyl-3,-4-dichloro-, 46, 34 reactions of, 46, 36 Cyclobutylamine, 47, 28 Cyclobutyl isocyanide, 46, 77 Cycloheptanone, 45, 31... 

There are actually three reactions called by the name Schmidt reaction, involving the addition of hydrazoic acid to carboxylic acids, aldehydes and ketones, and alcohols and alkenes. The most common is the reaction with carboxylic acids, illustrated above.Sulfuric acid is the most common catalyst, but Lewis acids have also been used. Good results are obtained for aliphatic R, especially for long chains. When R is aryl, the yields are variable, being best for sterically hindered compounds like mesi-toic acid. This method has the advantage over 18-13 and 18-14 that it is just one laboratory step from the acid to the amine, but conditions are more drastic. Under the acid conditions employed, the isocyanate is virtually never isolated. 

In the reaction of hydrazoic acid with carboxylic acids the amine is probably formed by way of an intermediate identical with that... 

For this purpose the reaction of hydrazoic acid with nitrous acid is utilized (P- 168). 

The UV spectroscopy is a good experimental method for the determination of the concentration of nitrile and formanilide in the reaction. The absorption maxima of the nitrile and the formanilide in Figure 8 do not shift with the increase in the concentration of sulphuric acid and the characters of the spectra are virtually unchanged. The lgF values calculated from the experimental data are given in Table 15. The dependence of the extinction coefficients of the products from the reaction of benzaldehyde with hydrazoic acid on the acidity of the medium is shown in Figure 9. 

FIGURE 9. The dependence of the extinction coefficients of the products from the reaction of ben-zaldehyde with hydrazoic acid on the acidity of the medium (reproduced from Reference 96)... 

The Sohmidt reaction of l,2-(a-ketotetramethylene)ferrocene (16) with hydrazoic acid and sulfuric acid in benzene9 or the Beckmann... 

Substituted salicylaldehydes react with hydrazoic acid in sulfuric acid to give indoxazenes 50,51 up to 15% of the corresponding 2-aminobenzoxazole (32) may be obtained as a by-product. The reaction is a variant of the Schmidt reaction, in which the intermediate nitre-nium ion may cyclize at once to the indoxazene, or rearrange and react with more hydrazoic acid, ultimately providing the benzoxazole. 

Chlorine, bromine, and iodine azide can act as donors of positive halides. The reaction of chlorine azide with water yields hydrazoic acid and hypochloric acid ... 

The reaction of equimolar quantities of hydrazoic acid with an acid or ketone affords a convenient method for preparing certain amines. The reaction is carried out by treating the organic compound in an inert solvent in the presence of sulfuric acid with gaseous hydrogen azide, hydrazoic acid in solution, or sodium azide directly. An excess of hydrazoic acid should be avoided in the reaction of ketones, for then tetrazoles are formed. It should be recalled that hydrazoic acid is toxic and explosive. A discussion of the method including scope and limitations, experimental conditions and procedures, and compounds prepared thereby has been presented. ... 

Among other kinetic studies in aqueous solutions are those of the reaction of chlorate with vanadium(II) and with chromium (II) °. The reactions of bromate with hydrazoic acid" and with hypophosphite" have been examined. 

Cyclopropylamines were also obtained from cyclopropanecarboxylic acids (73, R = OH), hydrazoic acid and sulfuric acid in a Schmidt reaction Cyclopropyl ketones (73, R = alkyl, aryl) as starting materials in the Schmidt reaction gave rise to a mixture of two isomeric amides (74 and 75) (equation 12). From ketones with an... 

Direct conversion of cyclopropanecarboxylic acid (16) into cyclopropylamine (17) is realized by application of the Schmidt reaction. Treatment of the acid with hydrazoic acid in sulfuric acid provides cyclopropylamine (bp 48-50 C/760 Torr) in 60-76% yield. -... 

A Schmidt rearrangement when azoimide (hydrazoic acid) reacts with a steroidal 4-en-3-one (416), under acidic catalysis, is followed by reaction with a... 

EXPLOSION and FIRE CONCERNS flammable in powder form NFPA rating Health 3, Flammability 2, Reactivity 0 reacts violently when heated with ammonium nitrate vigorous reaction when heated with nitryl fluoride explodes on contact with hydrazoic acid incompatible with ignition sources, dust generation, moisture, and excess heat cadmium and its salts are highly toxic when heated to decomposition, emits toxic fumes use dry chemical and carbon dioxide for firefighting purposes. 

AH° (s) + 46 kJ/mol not sensitive to shock explodes on heating at 150°C (302°F) reactions with acids can form hydrazoic acid (explosive) susceptible to the formation of many heavy metal azides when mixed with their salts solutions... 

Dimethyl-4-chromanones (34) were treated with hydrazoic acid in acetic acid (Schmidt reaction) to afford 2,3-dihydro-2,2-dimethyl-1,4-benzoxazepines (35) in good yields (Scheme 13) <92H(34)1523>. 

Hydrazoic acid reacts with Ag+ ions to form white insoluble AgNg. Red soluble Fe(N3)3 is produced by reaction with ferric salts. Since the acid, liberated from its soluble salts by the addition of dilute mineral acids, is completely expelled at 37° C, it can be easily detected in its vapor state through the formation of its ferric salt. 

The Reaction of Hydrazoic Acid with Organic Acids.310... 

The conversion of a carboxylic acid into an amine by treatment with hydrazoic acid in concentrated sulphuric acid is known as the Schmidt reaction or rearrangement ... 

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