Hexamethylenetetramine

Introduction

Hexamethylenetetramine (HMTA) is a heterocyclic organic compound having a symmetric tetrahedral cage-like structure, whose four ‘corners’ are nitrogen atoms and ‘edges’ are methylene groups. It is also known as hex­amine. It behaves like an amine base and known for its versatile role in organic chemistry. It plays an important role in formylation (Duff reaction), [¹] [²] conversion of benzyl ­halides into corresponding aldehydes (Sommelet reaction), [³] and synthesis of amines (Delépine reaction). [4]

HMTA is a useful reagent in the conversion of ethyl 2-(4-hydroxyphenyl)-4-methylthiazole-5-carboxylate into ­ethyl 2-(3-formyl-4-hydroxyphenyl)-4-methylthiazole-5-carboxylate, an important step in the synthesis of febu­xostat (hypouricemic agent). [5] Apart from these applications, hexamethylenetetramine is also known for the synthesis of explosives like RDX (hexogen). [6] Further, it has wide applications in polymer chemistry. [7] HMTA is commercially available and first synthesized by Butlerov via reaction of formaldehyde with ammonia. [8]

References

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