Sodium Nitrite (NaNO₂)

Introduction

The well-known NaNO₂ (mp 271 °C, d = 2.17) has ­multiple applications in organic synthesis but also in ­medicine as a vasodilator, bronchodilator and antidote against cyanide and H₂S poisoning. It is produced in the human body from saliva and sodium nitrate to control bacteria in the stomach.

The synthetic utilities of NaNO₂ have been extensively investigated in organic chemistry. Nitrosation of primary amines with nitrous acid (generated in situ from sodium nitrite and a strong acid) leads to diazonium salts. These salts are useful synthetic intermediates used in named ­reactions like Sandmeyer, Balz-Schiemann, [1] Pschorr, [2] and Heck [3] or in the manufacture of diazo dyes. [4] NaNO₂ is also used in the synthesis of alkyl nitrites, [5] reagents used for the synthesis of diazonium salts in non-aqueous media [6] or for the diazotization of primary aliphatic amines [7] in DMF.

NaNO₂ reacts with SO₂ and potassium hydrogen carbonate to afford potassium hydroxylaminedisulfonate salt, which gives after oxidation nitrosodisulfonic acid di­potassium salt. This Fremy’s salt is a useful reagent for the selective oxidation of phenols and aromatic amines to quinones (the Teuber reaction). [8]

Hydroxylamine hydrochloride is synthesized from NaNO₂ in a three-step procedure. [9]

References

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