Sodium azide, reaction with acids

Azolo[l,8]naphthyridines. The reactions of the chloronaphthyridine 229 with o-phenylenediamine at 200 °C and with sodium azide in acetic acid give the fused-ring products 230 and 231, respectively (Scheme 54) <2003IJB192>. Amino acid-substituted naphthyridines can be cyclized to the fused imidazolones 232 upon treatment with phosphorus oxychloride and under microwave irradiation (Equation 62) <2002SC857>. Acylation of 2-hydrazino-naphthyridines followed by heating gives W-acyl compounds which are cyclized intramolecularly to the [l,2,4]tri-azolo[4,3- ][l,8]naphthyridines 233 (Scheme 55) <1996IJB106>. The same compounds may also be obtained from... 

The high nitrogen content and the endothermic nature of the tetrazole ring lends itself to the synthesis of energetic materials. Compounds such as -H tetrazole and 5-aminotetrazole can be used as nucleophiles to incorporate the tetrazole ring into other molecules. 5-Aminotetrazole is synthesized from the reaction of dicyandiamide with sodium azide in hydrochloric acid. 

Acetylcarbazole and 9-ethyl-3-propionylcarbazole underwent normal Wilgerodt reactions. The ketone 174 reacted with sodium azide-poly-phosphoric acid with migration of the alkyl substituent generating lactam 203. ... 

The presence of the propionamide fragment in the stmcture of the anti-inflammatory agent broperamole (125-1) is reminiscent of the heterocycle-based NSAID propionic acids. The activity of this agent may trace back to the acid that would result on hydrolysis of the amide. Tetrazoles are virtually always prepared by reaction of a nitrile with hydrazoic acid or, more commonly, sodium azide in the presence of acid in a reaction very analogous to a 1,3-dipolar cycloaddition. A more recent (and safer) version of the reaction noted later (see losartan, 77-4) uses tributyltin azide. In the case at hand, reaction of the anion of mefa-bromobenzonitrile (125-1) with sodium azide and an acid affords the tetrazole (125-2). Condensation of the anion from that intermediate with ethyl acrylate leads to the product from Michael addition saponiflcation gives the corresponding carboxylic acid (125-3). This is then converted to the acid chloride reaction with piperidine affords broperamole (125-4) [136]. 

Consideration of the mechanism has to account for the fact, that hydrazoic acid and dinitrogen is liberated during the course of the reaction. The similarity to the Schmidt reaction is obvious, and it should be mentioned that quinisatine (2,3,4-trioxo-tetrahydroquinoline) reacts with sodium azide and sulfuric acid at 0 °C in moderate yield to give 14 [96TH000],... 

Schmidt reactions with sodium azide and strong acids, if they occur through tetrahedral reaction intermediates, lead primarily to nitrogen insertion adjacent to methylene rather than methine groups. There are no really satisfactory reasons for preferential methylene migration in this case [81]. 

Nitrites give a similar reaction and may be removed most simply with the aid of sulphamic acid (see reaction 3). Another, but more expensive, procedure involves the addition of sodium azide to the acid solution the solution is allowed to stand for a short time and then boiled in order to complete the reaction and to expel the readily volatile hydrogen azide ... 

The thietane ring of the carboxylate derivative 352 is apparently opened by loss of carbon dioxide. possibly via a thiete intermediate. Isonitriles and ynamines effect ring-expansions of 2,4-bis(imino)thietanes, and similar reactions of enamines and ynamines with tris(imino)thietane, 353 have been reported. The nucleophiles — methanol, ethanethiol, and diethylamine — attack the a-carbon atom of 353, which bears the iminosulfonyl group, to give ring-opened products, for example, 353a. The reactions with sodium azide or hydrazoic acid take a different course. ... 

The addition of hydrazoic acid to quinones follows the general pattern for addition to a,)3-unsaturated carbonyl compounds as previously discussed, with necessary modification to allow for the special interrelationships between quinonoid and benzenoid compounds. The product from reaction of /(-benzoquinone and hydrazoic acid in benzene is 2-azido-l,4-benzohydroquinone, which arises by addition of the reagent followed by enolization ° °. When oxidation of the product is permitted, further addidon to the resulting azidoquinone may occur . Hence, with excess sodium azide in acetic acid, /(-benzoquinone affords 2,5-diazido-l,4-benzohydroquinone (equation 81). 

The reaction of thyinoquinone (74) to yield the y-alkylidene-A -butenolide (79) illustrates the interesting chemistry that 1,4-quinones exhibit upon reaction with sodium azide in trichloroacetic acid . Intermediates 75, 76 and 78 were synthesized and shown to... 

Reaction with adamantanone. Japanese chemists1 treated adamantanone (1) with sodium azide in methanesulfonic acid with the expectation of achieving the Schmidt reaction. However, the unexpected 4-methylsulfonoxyadamantanone was obtained in 90% yield. Alkaline hydrolysis cleaves (2) to A2-bicyclo[3.3.1]-mmcnc-7-carboxylic acid (3) in 85% yield by a quasi-Favorsky reaction. Adaman-lanc itself does not undergo this unusual substitution reaction. 

The reaction of naphthoquinones with sodium azide and acetic acid was reported148 to give only aminonaphthoquinones. Folkers and coworkers149 were able to carry out the normal Schmidt rearrangement with 1,4-naphthoquinones using concentrated sulfuric acid 130 (R1 = H R2 = Me) gave a lactam claimed to be 131 (R1 = H R2 = Me). However,... 

AZOTURE de SODIUM (French) (26628-22-8) Reacts with hot water. Explosive decomposition in elevated temperatures above 525°F/274°C. Forms ultra-sensitive explosive compounds with heavy metals copper, copper alloys, lead, silver, mercury, carbon disulfide, trifluoroacryloyl fluoride. Violent reaction with acids, forming explosive hydrogen azide. Violent reaction with bromine, barium carbonate, chromyl chloride, dimethyl sulfate, dibro-momalononitrile. Incompatible with caustics, cyanuric chloride, metal oxides, metal sulfides, methyl azide, phosgene. 

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