Effects ofortho-substituents in SE1 protonolysis of phenylmercuric chloride

2007 ◽  
Vol 20 (2) ◽  
pp. 138-143 ◽  
Author(s):  
Yulan Wang ◽  
Jinli Zhang ◽  
Yangjie Wu
Keyword(s):  
Phenylmercuric Chloride

Protodemercuration of organomercuric chlorides. I. Aromatic mercuric chlorides

1965 ◽  
Vol 18 (10) ◽  
pp. 1507 ◽  
Author(s):  
RD Brown ◽  
AS Buchanan ◽  
AA Humffray
Keyword(s):  
Hydrochloric Acid ◽  
Correlation Coefficient ◽  
Chloride Ion ◽  
Zero Order ◽  
Hydrogen Ion ◽  
First Order ◽  
Phenylmercuric Chloride ◽  
Kinetics Of

The kinetics of protodemercuration, or displacement of the HgCl group by hydrogen, have been measured for phenylmercuric chloride, and also for its meta and para methyl-, chloro-, and methoxy-substituted derivatives. The reactions of the compounds with aqueous alcoholic hydrochloric acid were first order in RHgC1, first order in hydrogen ion, and zero order in chloride ion. At 70" the relative rates, which were largely determined by entropy factors, were: phenyl, 1; p-tolyl, 7; m-tolyl, 2.4; p-chlorophenyl, 0.67; m-chlorophenyl, 0.26; p-methoxy, 150; m-methoxy, 0.71. A plot of log k against σ+ gives a ρ value of -2.44, and correlation coefficient of 0.986.

Organomercury Compounds. XXXI. Preparations and 199Hg N.M.R. Spectra of Organomercury Derivatives of 2-Phenylpyridine, Benzo[h]quinoline, 1-Phenylpyrazole and 3,4,5-Trimethyl-1-phenylpyrazole, and the X-Ray Crystal Structure of Bis[2-(pyridin-2'-yl)phenyl]mercury

1993 ◽  
Vol 46 (9) ◽  
pp. 1323 ◽  
Author(s):  
DS Black ◽  
GB Deacon ◽  
GL Edwards ◽  
BM Gatehouse
Keyword(s):  
Crystal Structure ◽  
Chemical Shifts ◽  
Monoclinic Space Group ◽  
Initial Product ◽  
X Ray ◽  
Square Planar ◽  
Phenyl Rings ◽  
Organomercury Compounds ◽  
Phenylmercuric Chloride ◽  
Phenyl Mercury

2-(Pyridin-2'-yl) phenylmercuric acetate has been prepared by mercuration of 2-phenylpyridine. Symmetrization of the corresponding chloride by alkaline sodium stannite gave bis [2-(pyridin-2'-yl)phenyl]mercury, which was also prepared from 2-(2'-aminophenyl)pyridine by the diazo method and treatment of the initial product with copper powder and aqueous ammonia. Mercuration of benzo [h] quinoline and 3,4,5-trimethyl-1-phenylpyrazole with mercuric acetate followed by treatment with lithium chloride yielded benzo [h]quinolin-10-ylmercuric chloride and 2-(3',4',5'-trimethylpyrazol-1'-yl) phenylmercuric chloride respectively. Treatment of the former product with tribromide ions gave 10-bromobenzo[h] quinoline. The exchange Grignard reaction between 1-phenylpyrazole and ethylmagnesium bromide to give 2-(pyrazol-1'-yl) phenylmagnesium bromide has been monitored by reactions with benzonitrile and D2O to establish optimum conditions for reaction with mercuric bromide giving bis [2-(pyrazol-1'-yl)phenyl]mercury. The 199Hg n.m.r. chemical shifts of the majority of mercurials are shifted substantially downfield relative to the corresponding simple phenylmercurials consistent with weak intramolecular coordination by the heterocyclic nitrogen donor atoms, but a small upfield shift is observed for bis [2-(pyrazol-1'-yl)phenyl]mercury. The X-ray crystal structure of bis [2-(pyridin-2′-yl)phenyl]mercury [monoclinic, space group P21/n, a 12.746(2), b 11.660(2), c 5.698(1) Ǻ, β 92.81(1)′, V 845.8 Ǻ3] shows a centrosymmetric molecule with strong linear two coordination [Hg-C 2.098(8) Ǻ; C-Hg-C 180.0°] and significant but much weaker Hg-N interactions [Hg-N 2.798(7) Ǻ; N-Hg-N 180.0°] giving overall distorted square planar stereochemistry. The phenyl rings are mutually coplanar, whilst the two pyridin-2'-yl rings are parallel and inclined at 10.8° to the phenyl groups.

Synthesis and bromodemercuration of some permercurated arenes

1976 ◽  
Vol 29 (3) ◽  
pp. 627 ◽  
Author(s):  
GB Deacon ◽  
GJ Farquharson
Keyword(s):  
Good Yield ◽  
Benzene Derivative ◽  
Phenylmercuric Chloride ◽  
Methoxybenzoic Acid

Pentabromonitrobenzene, pentabromobenzoic acid, pentabromobenzamide, pentabromoacetanilide, barium pentabromobenzenesulphonate, 1,2,4,5 - tetrabromo -3-chloro-6-(trifluoromethyl)benzene, 2,3,5,6-tetrabromo-4-methoxytoluene 2,3,5,6-tetrabromo-4-methoxybenzamide, methyl 2,3,5,6-tetra- bromo-4-methoxybenzoate, and 1,2,5-tribromo-3,4-dichloro-6-fluorobenzene have been synthesized in good yield by bromodemercuration of the corresponding fully mercurated (permercurated) arenes, e.g. C6(HgO2CCF3)5NO2, which were prepared by reaction of an excess of molten mercuric tri- fluoroacetate with suitable arenes at c. 180-245�. Permercuration of p-methoxybenzoic acid was accompanied by complete decarboxylation giving, after bromodemercuration, pentabromo(methoxy)- benzene, which was also obtained in low yield from preparations of methyl 2,3,5,6-tetrabromo-4- methoxybenzoate and 2,3,5,6-tetrabromo-4-methoxybenzamide. Conditions have been devised for conversion of phenylmercuric chloride into either a pentamercurated or a hexamercurated benzene derivative, and hence into pentabromo-or hexabromobenzene. The results establish permercuration/bromodemercuration as a simple and versatile route to polybromobenzene.

The vibrational spectra of some phenylmercuric halides and diphenylmercury

1977 ◽  
Vol 30 (9) ◽  
pp. 1905 ◽  
Author(s):  
CG Barraclough ◽  
GE Berkovic ◽  
GB Deacon
Keyword(s):  
Force Field ◽  
Raman Spectra ◽  
Infrared Spectra ◽  
Vibrational Spectra ◽  
Infrared And Raman Spectra ◽  
Normal Coordinate ◽  
Valence Force ◽  
Valence Force Field ◽  
Phenylmercuric Chloride ◽  
Good Agreement

The Raman spectra of phenylmercuric chloride, phenylmercuric bromide, phenylmercuric iodide and diphenylmercury, and the infrared and Raman spectra of diphenylmercury in solution are reported. Using the previously reported infrared spectra of these compounds, vibrations were assigned, normal coordinate analyses were performed and frequencies were calculated using a valence force field. Good agreement was achieved between observed and calculated frequencies. The structure of diphenyl-mercury in solution is discussed.

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