Department of Chemistry, Andhra University P. G. Extension Centre, Nuzvid-521 201 Manuscript received 11 July 1986, revised 16 July 1987, accepted 30 October 1987 The transformation of charge transfer complexes of chloranil with three alicyclic secondary amines, piperidine, piperazine and morpholine, leading to the formation of substitution products is investigated spectroscopically and kinetically. Based on the results a plausible mechanism is proposed through outer and inner complexes as inter­mediates, the conversion of outer to inner complex being the rate determining step.