Dechlorination of gamma-hexachlorocyclohexane (lindane) is carried out in the multiphase catalytic system, composed by isooctane and aqueous KOH phases, a phase transfer agent (Aliquat 336) and a metal catalyst, e.g. 5% Pd/C, 5% Pt/C, or Raney-Ni. At 50degreesC and atmospheric pressure the full conversion of lindane to 1,2,4-tricholorobenzene (1,2,4-TCB) is achieved in 5-10 min via the base assisted dehydrochlorination, followed by the metal catalyzed hydrodechlorination with hydrogen to benzene. Aqueous KOH and Aliquat 336 strongly affect the reaction: if present together they co-promote both dehydrochlorination and hydrodechlorination steps; if KOH is absent, the reaction is forced to follow a different catalytic pathway, which involves a removal of a pair of chlorines at every reaction step by zerovalent metal followed by reduction of metal with hydrogen. This is proven by the formation of 3,4,5,6-tetrachlorocyclohex-1-ene and 5,6-dichlorocyclohexa-1,3-diene as intermediates in the reaction over Raney-Ni, and by the absence of TCBs in the reactions on all the catalysts studied. The final yield of benzene via this pathway can be achieved in shorter times than in a system with KOH. The presence of Aliquat 336 in the isooctane-water system produces a 10-fold rate increase, the presence of alkaline water is also important since it avoids catalyst poisoning by neutralizing the hydrochloric acid formed. (C) 2003 Elsevier B.V. All rights reserved.