Organomercury Compounds. XVI. Thermal decomposition reactions of mercuric arenesulphonate dihydrates

1973 ◽  
Vol 26 (3) ◽  
pp. 541 ◽  
Author(s):  
PG Cookson ◽  
GB Deacon
Keyword(s):  
Thermal Decomposition ◽  
Acetic Acid ◽  
Sulphuric Acid ◽  
Mercuric Acetate ◽  
Sodium Salts ◽  
Decomposition Reactions ◽  
Tetraphenylarsonium Chloride ◽  
Organomercury Compounds ◽  
Sulphur Trioxide

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).

Organomercury compounds. XXII. Syntheses of polybromophenylmercurials by decarboxylation reactions

1977 ◽  
Vol 30 (5) ◽  
pp. 1013 ◽  
Author(s):  
GB Deacon ◽  
GJ Farquharson ◽  
JM Miller
Keyword(s):  
Thermal Decomposition ◽  
Sodium Chloride ◽  
Mass Spectra ◽  
Mercuric Acetate ◽  
Similar Treatment ◽  
Phenylmercuric Acetate ◽  
Pyridine Complexes ◽  
Organomercury Compounds ◽  
Mercuric Halides

The mercuric polybromobenzoates, (C6Br2CO2)2Hg, (XC6Br4CO2)2Hg (X = p-F, p-Cl, p-Me, o-Me, p-MeO or m-MeO) and (2,6-Me2C6Br3CO2)2Hg, and phenylmercuric pentabromobenzoate have been prepared by reaction of mercuric acetate or phenylmercuric acetate with the appropriate polybromobenzoic acids. Thermal decomposition of (C6Br5CO2)2Hg, (XC6Br4CO2)2Hg, (X = p-F, p-Cl or p-MeO) and C6Br5C02HgPh in boiling pyridine gave the new polybromophenylmercurials (C6Br&Hg, (XC6Br4)2Hg and C6Br5HgPh respectively, but similar treatment of (XC6Br4C02)2Hg (X = p-Me, o-Me or m-MeO) and (2,6-Me2C6Br3C02)2Hg yielded pyridine complexes of the mercuric carboxylates. Mercuric p-methyltetrabromobenzoate underwent decarboxylation in boiling nitrobenzenelpyridine giving (p-MeC6Br4),Hg, but the method could not be extended to (0-Mec~Br~C0~)o~r H(2g,6 -Me2C6Br,C02)2Hg. Decarboxylation of XC6Br4C02H (X = o-Me or m-MeO) was effected in molten mercuric trifluoroacetate giving, after treatment of the products with sodium chloride, the corresponding tetrabromophenylmercuric chlorides. All mercurials underwent cleavage with iodine or triiodide ions in hot dimethylformamide to give the corresponding iodopolybromobenzenes, and (C6Br5)2Hg was converted into C6Br5HgX (X = C1 or Br) by the corresponding mercuric halides in hot xylene/nitrobenzene. Thermal symmetrization of C6Br5HgX (X = C1, Br, or Ph) is detectable prior to melting, but (C6Br5),Hg is stable to at least 400'. The mass spectra of the polybromophenylmercurials are discussed.

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

1973 ◽  
Vol 26 (9) ◽  
pp. 1893 ◽  
Author(s):  
PG Cookson ◽  
GB Deacon
Keyword(s):  
Thermal Decomposition ◽  
Decomposition Reactions ◽  
Organomercury Compounds

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.

Organomercury Compounds. XXVII. The Synthesis and Properties of Some Carboxylato- and Carboxy-pyridinylmercurials

1985 ◽  
Vol 38 (3) ◽  
pp. 419 ◽  
Author(s):  
GB Deacon ◽  
GN Stretton
Keyword(s):  
Acetic Acid ◽  
Carboxylic Acid ◽  
Dimethyl Sulfoxide ◽  
Mercuric Acetate ◽  
Major Product ◽  
Aqueous Acetic Acid ◽  
Halide Ions ◽  
Iodide Ions ◽  
Organomercury Compounds

Decarboxylation of mercuric pyridine-2,3-dicarboxylate in hot dimethyl sulfoxide or hexamethylphosphoramide gives a mixture of 2-carboxylatopyridin-3-ylmercury(II) (major product) and 3- carboxylatopyridin-2-ylmercury(II) (minor product). The mixture reacts ( i ) with acidified halide ions ( Cl - or I-) to yield a mixture of the corresponding carboxypyridinyl ( halogeno )mercury(II) derivatives, (ii) with tribromide ions to give the bromo ( carboxypyridinyl )mercury(ii) complexes, 3-bromopyridine-2-carboxylic acid, and 2-bromopyridine-3- carboxylic acid, and (iii) with iodide ions in hot aqueous acetic acid to yield bis (2-carboxypyridin-3-yl)mercury(II) hydrogen triiodomercurate (II). Solutions of the last compound in dimethyl sulfoxide deposit bis (2-carboxypyridin-3-yl)mercury(II). Reaction of pyridine-2,3-dicarboxylate ions with mercuric acetate in boiling aqueous acetic acid at pH 5.0-5.8 gives mercurated acetic acid as the sole organometallic product, and the reported1 decarboxylation yielding 3-carboxylatopyridin-2-ylmercury(II) is not observed.

Non-Isothermal Decomposition Kinetic of Polypropylene/Hydrotalcite Composite

2019 ◽  
Vol 19 (11) ◽  
pp. 7493-7501 ◽  
Author(s):  
Sheng Xu ◽  
Min Zhang ◽  
Siyu Li ◽  
Moyu Yi ◽  
Shigen Shen ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Nitrogen Atmosphere ◽  
Heating Rates ◽  
Decomposition Reactions ◽  
Kinetic And Thermodynamic Parameters ◽  
Málek Method ◽  
Boundary Reaction ◽  
Phase Boundary Reaction ◽  
Thermal Stability Of

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.

Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

1977 ◽  
Vol 55 (20) ◽  
pp. 3596-3601 ◽  
Author(s):  
Michael T. H. Liu ◽  
Barry M. Jennings
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Diazo Compounds ◽  
First Order ◽  
Temperature Range ◽  
Decomposition Reactions ◽  
Consecutive Reactions ◽  
Rate Processes ◽  
Subsequent Decomposition

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.

Preparations, sulphinate coordination, and thermal decomposition of some bismuth triarenesulphinates

1972 ◽  
Vol 25 (10) ◽  
pp. 2107 ◽  
Author(s):  
GB Deacon ◽  
GD Fallon
Keyword(s):  
Thermal Decomposition ◽  
Acetic Acid ◽  
Sulphur Dioxide ◽  
Glacial Acetic Acid ◽  
The Other

Bismuth triarenesulphinates, Bi(02SR)3 [R = Ph, p-MeC6H4, p-ClC6H4, 2,4,6-(Me2CH)3C6H2, and p-MeCONHC6H4], have been prepared by reaction of bismuth triacetate with the appropriate arenesulphinio acids in glacial acetic acid, and the first two compounds have also been obtained by reaction of triphenyl-bismuth with the appropriate mercuric arenesulphinates. The sulphur-oxygen stretching frequencies of the bismuth sulphinates are indicative of O-sulphinate coordination, and the compounds are considered to be polymeric with bridging O-sulphinate groups and six-coordinate bismuth. Thermal decomposition of Bi(O2SR)3 (R = Ph, p-MeC6H4, or p-CIC6H4) under vacuum gave the corresponding triarylbismuth compounds and sulphur dioxide, the preparation of tri-p-chlorophenylbismuth being accompanied by formation of di-p-chlorophenyl sulphone and S-p-chlorophenyl p-chlorobenzenethiosulphonate. Pyrolysis of the other triarenesulphinates did not yield organobismuth compounds.

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