Organomercury compounds. XVIII. Thermal decomposition reactions of mercuric arenesulphonate pyridinates

1973 ◽  
Vol 26 (9) ◽  
pp. 1893 ◽  
Author(s):  
PG Cookson ◽  
GB Deacon

The mercuric arenesulphonate pyridinates, Hg(O3SR)2,(py)2 (R = C6X5, p- HC6X4, o-HC6X4, or m-HC6Cl4; X = Cl or F) and Hg(O3S-m-HC6F4)2,(py)3, have been prepared by treatment of the appropriate mercuric arenesulphonate dihydrates with pyridine. Thermal decomposition of the compounds Hg(O3SR)2,(py)2 (R = C6X5, p-HC6X4, or m-HC6Cl4) and Hg(O3S-m-HC6F4)2,(py)3 at c. 120-240� under vacuum gave the corresponding diarylmercurials (yields: 45-90%) and the complex (py),SO3 in all cases, together with (- m-HgC6F4SO3-)n, and low yields of polyfluorobenzenes and/or polyfluorobenzenesulphonic acids. Similar decomposition of the compounds Hg(O3S-o-HC6X4)2,(py)2 gave (-o-HgC6X4SO3-)n, (py),SO3, o- HC6X4SO3H, and o-H2C6X4, and there was some evidence for formation of a trace of o-(o-HC6Cl4- SO3Hg)C6Cl4SO3HgO3S-o-HC6Cl4. The derivatives (- HgC6X4SO3-)n, were identified by established degradation procedures.

1973 ◽  
Vol 26 (3) ◽  
pp. 541 ◽  
Author(s):  
PG Cookson ◽  
GB Deacon

Thermal decomposition of the mercuric arenesulphonate dihydrates Hg(03SR)2,- 2H20 (R = C6X5, p-HC6X4, or m-HC6C14; X = C1 or F) at c. 130-240" gave the corresponding diarylmercurials, the polyhalogenobenzenes RH, and sulphur trioxide (or sulphuric acid) in all cases, together with RS03H (R = C6F5 or p-HC6F4), and p-(p-HC6F4S03Hg),C6F4. By contrast, decomposition of Hg(03SR)2,2H20 (R = m-HC6F4 or o-HC6X4) gave the corresponding (-HgC6X4S03-), derivatives, sulphonic acids, polyhalogenobenzenes, and sulphur trioxide in all cases, together with m-HC6F4HgO3S-m-HC6F4 and o-(o-HC~C~~SOJH~),C~C~~. The compounds RHg03SR (R = C6C15, isolated as the monopyridinate, or p-HC6C14) were obtained from decomposition of the appropriate mercuric sulphonates at c. 165'. Identities of (-HgC6X4S03-), derivatives were established mainly by cleavage with triiodide ions in N,N-dimethylformamide giving the salts M(IC6X,S03) (M = Na or S-benzylthiouron- ium), and of (HC6X4S03Hg)2C6X4 derivatives by similar degradation giving 12C6X4 and M(HC6X4S03) (M = Na or Ph4As). Similar degradation of C6C15Hg03SC6C15,py, p-HC6Cl,Hg03S-p-HC6C14, and the known mercurials C6C15HgCl, (p-HC6C14),Hg, and (0-HC6C14),Hg gave the corresponding iodopolychlorobenzenes. The mercurated derivative (-o-H~C,F~SO~-)~ gave (-0-HgCsF4-)3 on thermal decomposition, and crystallization from water yielded ( - o - H ~ C ~ F ~ S ~ ~ - ) , , ~ ~ H ~ ~ , which was converted into (Ph4As)(o-C1HgC6F4S03) by tetraphenylarsonium chloride. The mercuric sulphonates were prepared from mercuric acetate and the appro- priate sulphonic acids in acetic acid (X = C1) 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).


2019 ◽  
Vol 19 (11) ◽  
pp. 7493-7501 ◽  
Author(s):  
Sheng Xu ◽  
Min Zhang ◽  
Siyu Li ◽  
Moyu Yi ◽  
Shigen Shen ◽  
...  

P3O5-10 pillared Mg/Al hydrotalcite (HTs) as a functional fire-retarding filler was successfully prepared by impregnation-reconstruction, where the HTs was used to prepare polypropylene (PP) and HTs composite (PP/HTs). Thermal decomposition was crucial for correctly identifying the thermal behavior for the PP/HTs, and studied using thermogravimetry (TG) at different heating rates. Based on single TG curves and Málek method, as well as 41 mechanism functions, the thermal decompositions of the PP/HTs composite and PP in nitrogen atmosphere were studied under non-isothermal conditions. The mechanism functions of the thermal decomposition reactions for the PP/HTs composite and PP were separately “chemical reaction F3” and “phase boundary reaction R2,” which were also in good agreement with corresponding experimental data. It was found that the addition of the HTs increased the apparent activation energy Ea of the PP/HTs comparing to the PP, which improved the thermal stability of the polypropylene. A difference in the set of kinetic and thermodynamic parameters was also observed between the PP/HTs and PP, particularly with respect to lower ΔS≠ value assigned to higher thermal stability of the PP/HTs composite.


1977 ◽  
Vol 55 (20) ◽  
pp. 3596-3601 ◽  
Author(s):  
Michael T. H. Liu ◽  
Barry M. Jennings

The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80–130 °C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes.


1991 ◽  
Vol 177 ◽  
pp. 273-284 ◽  
Author(s):  
Kenzo Nagase ◽  
Hiroko Yokobayashi ◽  
Kazuo Muraishi ◽  
Masae Kikuchi

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