Abstract: In commercial production，hexanediamine (HDA) is derived from the hydrogenation (reduction) of adiponitrile (ADN)，which is mainly produced from butadiene (BD). According to synthesis methodology，the BD based preparation of ADN and/or HDA can be classified into four methods，i.e.，direct catalytic hydrocyanation of BD to ADN，chlorination-metal cyanation of BD to ADN，thermal dehydration of carboxylic acids with ammonia or of amide，and direct synthesis of HDA via adipic dialdehyde. This review discusses fundamental technical aspects and chemical reaction mechanisms in these synthesis methodologies，and provides comparison.