Tryptophan reaction with free radicals arisen from carbon tetrachloride in a model system. A mass spectrometric study

SUMMARY

The interaction between free radicals derived from the thermal decomposition of carbon tetrachloride and N-acetyl-d, l-tryptophan ethyl ester (TRPAE) under anaerobic and aerobic conditions was studied. The structure of the reaction products formed was deciphered by the GC/MS analysis of their trimethylsilyl derivatives. Under anaerobic conditions no formation of reaction products was detected. Under aerobic conditions the following products were identified:

• 1. A chloro hydroxy unsaturated adduct of TRPAE (2 isomers).

• 2. A dichloro hydroxy unsaturated adduct of TRPAE.

• 3. 12 products which are different pyrrolo[2,3-b]indol derivatives.

Some of the products appeared to have an hydroxyl group as a substituent, all of them contained chlorine and only one contained carbon from CCl₄. Interestingly, the formation of those adducts not containing CCl₃ would be missed during the regular procedures toxicologists use to determine the so-called ‘covalent binding’ employing ¹⁴CCl₄.

Concerning the potential relevance of these findings, we hypothesize that if interactions similar to those here reported occurred at least in part during CCl₄ poisoning, the resulting critical proteins containing tryptophan, e.g. membrane or other and enzymes containing the amino acid in their active center, might be impaired.