RADIOLABELLING OF POLYCHLORINATED BIPHENYLS: SYNTHESIS OF [14C]PCB CONGENERS 11 AND 77

The synthesis is described of uniformly 14C-labelled PCB-congeners starting with [14C]benzene (1) via [14C]nitrobenzene (2), [14C]hydrazobenzene (3), [14C]benzidine dihydrochloride (4), N,N'-diacetyl-[14C]benzidine (5), 3,3'-dichloro-N,N'-diacetyl-[14C]benzidine (6), and 3,3'-dichloro-[14C]benzidine dihydrochloride (7). Elimination of the amino groups from 7 leads to [14C]PCB No. 11 (8), and their substitution by chlorine alternatively to [14C]PCB No.77 (9) /1/. Yields obtained for 8 and 9 are 20 % and 30 %, respectively. The specific activity of the products was 1.2 GBq/mmol. This approach, avoiding the isolation of free [14C]benzidine, may allow the synthesis of PCBs with higher specific activity. The described methods are also applicable to 13C-labelling. From the results of capillary GC-MS analysis /2/ of the unrefined PCBs, conclusions may be drawn about the course of chlorinating the 5: 87 % in 3,3'-position, 6 % in 3,3',5-position, 5 % in 3-position and only 2 % in 2,3'-position.
Because only negligible amounts of position isomers are produced by this method of preparation, the reaction products can be purified much easier with HPLC-techniques than the products obtained from other syntheses.