The Newman-Kwart rearrangement of O-thiocarbamates to S-thiocarbamates is a versatile method for the conversion of phenols into thiophenols. The triple rearrangement of the O-trithiocarbamate 2,4,6-triacetyl-1,3,5-tri-(dimethylthiocarbamoyloxy)benzene (2) to the S-trithiocarbamate 2,4,6- triacetyl-1,3,5-tri-(dimethylthiocarbamoylthio)benzene (3) is performed, which is unprecendented for fully substituted benzene rings. The synthesis and characterization of the O-trithiocarbamate 2 and the S-trithiocarbamate 3 including the single-crystal X-ray structure analysis of compound 3 are presented