tert-Butyl nitrite is employed as a reagent for diazotization and nitrosation of alcohols, thiols, amines and cycloalkanes. It plays an important role in photocatalyzed conversion of aryl and heteroarylamines to selenides. It finds application in the preparation of aryl azides from aryl amines. It is also useful for radical multifunctionalization reactions of aliphatic alkenes and source of nitric oxide.
If it is free from OH bands (IR) then distil it through a 12inch helices packed column under reduced pressure, otherwise wash with aqueous 5% NaHCO3 (effervescence), then H2O, dry (Na2SO4) and fractionate it through a 10 theoretical plates column at ca 10mm pressure. [Allen J Chem Soc 1968 1954, Coe & Doumani J Am Chem Soc 70 1516 1948, UV: Ungnade & Smiley J Org Chem 21 993 1956, IR: Terte Bull Soc Chim Belg 60 240 1951, Beilstein 1 IV 1622.]
