Synthesis of two major toxaphene components and their photostabilities.
The synthesis of 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane (B7-1001, Hp-Sed) and 2-endo,3-exo,5-endo,6-exo,8,9,9,10-octachlorobornane (B8-1412) is described. Both compounds are components of toxaphene, an insecticide that has been widely used in the past. B7-1001 is an important toxaphene congener, comprising up to 99% of total toxaphene concentrations found in fish and sediment samples from treated lakes. B8-1412 is also a significant component of toxaphene contamination in samples from biota. In synthesizing the compounds, 2-exo,3-endo,6-endo,8,9,10-hexachlorobornane (B6-913) was obtained by reduction of the well-known toxaphene component P 32 (B7-515, 2,2,5-endo,6-exo,8,9,10-heptachlorobornane), which was itself isolated from the chlorination products of (+)-camphene. Chlorination of B6-913 provided B7-1001 in 49.5% yield, and P 32 and four other heptachlorobornanes were also detected in the reaction mixture. Structures of two of the heptachlorobornanes were elucidated by MS and NMR as 2-exo,3-endo,6-endo,8,9,9,10-heptachlorobornane (B7-1461) and 2-exo,3,3,6-endo,8,9,10-heptachlorobornane (B7-1303). B8-1412 was isolated from the product mixture obtained by chlorination of 2-exo,3-endo,6-endo,8,9,9,10-heptachlorobornane. Photolysis experiments at lambda = 254 nm revealed that B6-913 is photochemicaly the most stable compound of the seven toxaphene compounds studied, with a t(1/2) of 213 h. B7-1001, having a t(1/2) of 82 h, was the second most stable compound. B8-1412 was degraded more rapidly, with a t(1/2) of 28.8 h, than B7-1001, but was still much more stable than P 50 (B9-1679, 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane), which had a t(1/2) of 9.4 h, despite its reputation as a very persistant compound. Under the same experimental conditions hexachlorobenzene (HLB) and octachlorodibenzodioxine (OCDD) were consumed very quickly with t(1/2) = 0.0025 and 0.0015 h, respectively.
Coelhan
Mehmet
M
Research Center for Brewing and Food Quality, Technical University of Munich, 85350 Freising-Weihenstephan, Germany. coelhan@wzw.tum.de
Maurer
Martin
M
D002712:Chlorides / Q000737:chemistry; D007306:Insecticides / Q000138:chemical synthesis* / Q000528:radiation effects; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010777:Photochemistry; D010782:Photolysis; D014112:Toxaphene / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000528:radiation effects; D014466:Ultraviolet Rays
D002712:Chlorides; D007306:Insecticides; D014112:Toxaphene