### Abstract

Thermal decomposition of the mercuric arenesulphonate dihydrates Hg(O_{3}SR)_{2},- 2H_{2}0 (R = C_{6}X_{5}, p-HC_{6}X_{4}, or m-HC_{6}Cl_{4}; X = Cl or F) at c. 130-240° gave the corresponding diarylmercurials, the polyhalogenobenzenes RH, and sulphur trioxide (or sulphuric acid) in all cases, together with RSO_{3}H (R = C_{6}F_{5} or p-HC_{6}F_{4}), and p-(p-HC_{6}F_{4}SO_{3}Hg)_{2}C_{6}F_{4}. By contrast, decomposition of Hg(O_{3}SR)_{2}, 2H_{2}O (R = m-HC_{6}F_{4} or o-HC_{6}X_{4}) gave the corresponding (-HgC_{6}X_{4}SO_{3}-)_{n} derivatives, sulphonic acids, polyhalogenobenzenes, and sulphur trioxide in all cases, together with m-HC_{6}F_{4}HgO_{3}S-m-HC_{6}F_{4} and o-(o-HC_{6}Cl_{4}SO_{3}Hg)_{2}C_{6}Cl_{4}. The compounds RHgO_{3}SR (R = C_{6}Cl_{5}, isolated as the monopyridinate, or p-HC_{6}Cl_{4}) were obtained from decomposition of the appropriate mercuric sulphonates at c. 165°. Identities of (-HgC_{6}X_{4}SO_{3}-)_{n} derivatives were established mainly by cleavage with triiodide ions in N, N-dimethylformamide giving the salts M(IC_{6}X, SO_{3}) (M = Na or S-benzylthiouronium), and of (HC_{6}X_{4}SO_{3}Hg)_{2}C_{6}X_{4} derivatives by similar degradation giving I_{2}C_{6}X_{4} and M(HC_{6}X_{4}SO_{3}) (M = Na or Ph4As). Similar degradation of C_{6}Cl_{5}HgO_{3}SC_{6}Cl_{5}, py, p-HC_{6}Cl_{4}HgO_{3}S-p-HC_{6}Cl_{4}, and the known mercurials C_{6}Cl_{5}HgCl, (p-HC_{6}Cl_{4})_{2}Hg, and (o-HC_{6}Cl_{4})_{2}Hg gave the corresponding iodopolychlorobenzenes. The mercurated derivative (-o-HgC_{6}F_{4}SO_{3}-)_{n} gave (-o-HgC_{6}F_{4}-)_{3} on thermal decomposition, and crystallization from water yielded (-o-HgC_{6}F_{4}SO_{3}-)_{n}, 2nH_{2}O, which was converted into (Ph_{4}As)(o-ClHgC_{6}F_{4}SO_{3}) by tetraphenylarsonium chloride. The mercuric sulphonates were prepared from mercuric acetate and the appropriate sulphonic acids in acetic acid (X = Cl) or water (X = F). Sulphonic acids, obtained by sulphonation reactions, were characterized as the dihydrates and in some cases sodium salts (polychloro derivatives) or as barium and tetraphenylarsonium salts (tetrafluoro derivatives).

Original language | English |
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Pages (from-to) | 541-555 |

Number of pages | 15 |

Journal | Australian Journal of Chemistry |

Volume | 26 |

Issue number | 3 |

DOIs | |

Publication status | Published - 1 Jan 1973 |