Phenylmercury Derivatives Research Articles

Spectroscopic study of a series of phenylmercury derivatives of nitroanilines

1. The sequence of changes in the electron-donor properties of the following groups in p-nitroanilines and their PhHg derivatives was established from the positions of the long-wave bands in the electron spectra and the νasNO2 frequencies and integral intensities of the νAr and νsNO2 bands in the IR spectra: 2. The electron-donor properties of the XHgPh groups in phenylmercury derivatives of p-nitrothiophenol, p-nitrophenol, and p-nitroaniline change in the following order: SHgPh < OHgPh <NHHgPh. 3. The H atom is the coordination center with DMSO in the PhHg derivatives of p-nitroaniline; the Hg atom, in the o-nitroaniline derivative. 4. A quantitative evaluation of the complexing process with DMSO and dissociation in DMSO is given for the compounds studied.

Assay of thioinosinic acid, an active metabolite of azathioprine, in human lymphocytes.

1 A specific assay for the measurement of thioinosinic acid, in human lymphocytes, has been developed with a sensitivity of 50 ng of thioinosinic acid per 5 x 10(6) lymphocytes. 2 Thioinosinic acid is precipitated from purified lymphocytes as the lanthanum salt. Acid hydrolysis results in the formation of 6-mercaptopurine which, when converted into its phenyl mercury derivative, can be easily extracted into toluene. Back-extraction of the toluene layer with 0.1N HCl regenerates 6-mercaptopurine which is then assayed fluorometrically. 3 Blood samples were taken from renal transplant recipients 3 h after an oral dose of 50 mg azathioprine. The results from 5 patients gave a range of 54 to 173 ng of thioinosinic acid per 5 x 10(6) lymphocytes, with a mean of 110 ng. 4 In an in vitro incubation of azathioprine, 1mM with fresh human blood, 160 and 180 ng of thioinosinic acid per 5 x 10(6) lymphocytes was formed after 0.5 h and 5 h respectively. 5 The assay is suitable for the study of the kinetics of thioinosinic acid formation in lymphocytes of patients with kidney transplants. It could also prove useful in the study of thioinosinic acid formation in leukaemia patients undergoing 6-mercaptopurine treatment.

Assay of 6-thioguanine in human plasma.

1. A fluorimetric method has been developed for measuring therapeutic concentrations of 6-thioguanine in human plasma. The drug was measured as an oxidized derivative, guanine 6-sulphonate. 2. 6-thioguanine was extracted from plasma by a novel procedure which isolated the drug from an interfering plasma components. This method involved the formation of the thioguanine phenyl mercury derivative in alkaline plasma and its extraction into toluene. The free drug was released by back-extraction into hydrochloric acid. 3. The assay is specific and shows a limit of sensitivity of 5 ng/ml. This was shown to be adequate for measuring plasma concentrations of 6-thioguanine after the administration of a 160 mg dose in a patient with leukaemia.

Assay of azathioprine, 6-mercaptopurine and a novel thiopurine metabolite in human plasma.

1 A simple, specific assay for 6-mercaptopurine (6-MP) in human plasma with a sensitivity of 10 ng/ml (66 nmol/1) has been developed. 2 6-MP was extracted directly from plasma into toluene using a novel extraction procedure. This involves conversion of 6-MP into a phenyl mercury derivative by its reaction with phenyl mercuric acetate in alkaline plasma and extracting into toluene. Back-extraction of the toluene layer with 0.1N HCl regenerates 6-MP, which is then oxidised to purine-6-sulphonate and assayed fluorimetrically. 3 This assay has been modified to measure azathioprine and a new thiopurine metabolite in plasma. 4 In a kidney transplant patient given azathioprine, 50 mg i.v., conversion to 6-MP was rapid and the plasma half-life of 6-MP was 36 min. 5 These assays are suitable for studying the pharmacokinetics of azathioprine in patients with kidney transplants. The 6-MP assay should also prove useful for studying the pharmacokinetics of the drug in patients with leukaemia.

A PMR study of exchange reactions involving diaryltriazenes and their phenylmercury derivatives

Exchange reactions involving 2′-methylbenzenesulphonanilide, substituted diaryltriazenes and their C 6H 5Hg derivatives have been studied by the PMR method in chlorobenzene solution. On the basis of the data obtained, values of equilibrium constants for the exchange reactions involving substituted diaryltriazenes and their C 6H 5Hg derivatives have been calculated. Analysis of the finding has shown that the position of equilibrium is governed by the polar and steric effects of the substituents and the relative intensity of intramolecular coordination of hydrogen and the phenylmercury group with the substituent in the 2-position of the diaryltriazene system. Consideration of the results obtained suggests a non-mesomeric structure for C 6H 5Hg derivatives of diaryltriazenes undergoing rapid metallotropic rearrangement.

Molecular structure of the phenylmercury derivative of 2-chlorodiazoaminobenzene in the crystal

Molecular structure of the phenylmercury derivative of 2-chlorodiazoaminobenzene in the crystal

Phenylmercury derivatives of aminomethylene- and hydroxymethylene-substituted 1-methyloxindoles, 1-indanones, and 1,3-indanediones

A number of phenylmercury derivatives of 3-hydroxymethylene- and 3-aminomethylene-substituted 1-methyloxindoles, 1-indanones, and 1,3-indanediones were synthesized. It is shown that the preferred tautomeric structures of the potentially metallotropic and prototropic hydroxymethylene keto (hydroxy vinyl aldehyde) derivatives of the indicated compounds and 3-hydroxybenzo[b]-2-formylthiophene coincide precisely. An aminomethylene structure with an N-H bond is realized for the phenylmercury derivatives of the corresponding azomethines in all cases.

A spectroscopic study of the reactions of substituted phenols and their organometallic derivatives with amines

1. Electronic spectroscopy has been used to show the similarity of the reactions of the nitrophenols and their phenylmercury and triphenyltin derivatives with triethylamines and diethylamines. 2. Increasing the electron-acceptor activity of the aromatic ring substituent in the nitrophenol or the donor activity of the amine, or altering the polar properties and coordinating ability of the solvent, will shift the complexing equilibrium toward ion pair formation, and by promoting ionization, bypass the stage of molecular complex formation. 3. Data has been obtained on these reactions, and it has been shown that the formation constants for ion pairswith triethylamine fall off in the order: H > SnPh3 > HgPh.

Organometallic compounds containing a guanidinium group. Phenylmercury(II) derivatives of creatine and creatinine

Phenylmercury(II) replaces a proton of creatine, H2NC+(NH2)NMeCH2C02-, in basic solution to form the zwitterionic complex PhHgNHC+(NH2)NMeCH2CO2-. Creatine and creatinine (C4H7N30) react with PhHg((OH)N03)I/2 in aqueous ethanol to form a 2:l complex [(PhHg)2(C4H6N30][N03] which exists in two crystalline forms. Creatinine forms a 1:l complex [PhHg(C4H7N30)][N03].1/2H20 at pH 1.4 on reaction with PhHg((OH)N03)l/2 in the presence of nitric acid. The 1:l and 2:l complexes may be interconverted. Creatinine hydronitrate, [H2NCNMeCH2CONH][NO3], and the PhHg(II) complexes of creatinine have similar infrared (including deuterated derivatives) and 1H NMR spectra, consistent with retention of the creatinine ring and presence of a guanidinium group in the complexes. An X-ray structural analysis of one crystalline form of the 2:l complex shows bonding of PhHg(II) groups to the exocyclic and ring nitrogens of creatinine to form the cation [PhHgNHCNMeCH2CONHgPh]+.

Separation of thiols as phenyl mercury derivatives by thin-layer chromatography : I. Azathioprine and 6-mercaptopurine metabolites

A method is described for converting thiol metabolites of azathioprine and 6-mercaptopurine into phenyl mercury derivatives. Separation of these derivatives was performed by chromatography on silica thin layers and they were detected by low temperature (−196°) fluorescence. The parent compounds were regenerated on the chromatogram by spraying with 2 N HCl and these were detected by low temperature fluorescence. Mercury was also detected in spots by spraying with dithizone. The method provides a simple solution to the problem of oxidation of thiol compounds during isolation procedures.

Kinetics of reaction of phenylmercury hydroxide with anionic ligands in aqueous solution

1. Employing the method of a jump in the temperature, a study was made of the reaction kinetics of replacing the OH in phenylmercury hydroxide by Cl−, Br−, SCN−, N3−, and NO2− ions, both in the direct and reverse directions, in aqueous solution at 25°. 2. The reactions of the phenylmercury derivatives proceed more rapidly than do the analogous reactions of the methylmercury derivatives, but the values of the Bronsted coefficients for the elementary act of the reactions are close to each other in both cases.

Thermogravimetric and gas chromatographic characteristics of some phenylmercury (II) compounds

Phenylmercury (II) derivatives of chloride, bromide, iodide, sulphide and thiocyanate are obtained by treating aqueous acidic anion solutions with aqueous phenylmercury (II) nitrate, and are readily extractable into various organic solvents. Thermogravimetric and gas chroamtography analyses show their potential usefulness for the determination of the halides, notably chloride, at the sub-microgram level after a solvent extraction step. The gas chromatographic resolution obtainable between individual phenylmercurials also indicates the possibilities for simultaneous determination of these anions.

A comparative PMR study of exchange reactions in some substituted N-methylbenzenesulphonamides and their N-phenylmercury derivatives

Protonproton, metalmetal and metalproton exchange type reactions have been studied for a number of substituted N-methylbenzenesulphonamides and their N-phenylmercury derivatives through the use of a PMR technique. It has been found that metalmetal type exchange processes proceed more readily than protonproton processes in some cases. The presence of substituents in the aromatic ring of the benzenesulphonamide moiety has been shown to affect the rate of the metalmetal exchange process to a smaller extent than that of hydrogen exchange. It has been demonstrated that transfer from a chlorobenzene to a pyridine solution accelerates exchange in N-methylbenzenesulphonamides but retards exchange in their phenylmercury derivatives, whereas intramolecular coordination inhibits exchanges in both types of compound. The differences in the influence of substituents and solvents upon the rates of the metalmetal and protonproton exchange processes are discussed in terms of the ease of formation of a transition state in such exchange reactions.

Organometallic derivatives of certain mercapto- and hydroxy-N-heterocycles

1. Organometallic derivatives of mercury, tin, lead, and antimony were synthesized for a number of hydroxy and mercapto-N-heterocycles. 2. The structures of the indicated compounds in solution were established on the basis of the UV spectra. Organometallic derivatives of 4-thiopyridone are S-derivatives in solution, phenylmercury derivatives of hydroxy-N-heterocycles have a lactam structure, while compounds of tin and lead exist in the lactime form. 3. The absence of the band of the amide carbonyl group in the region of 1600–1700 cm−1 cannot serve as a reliable criterion of a lactime structure in the crystal of metallic and Organometallic derivatives of hydroxy-N-heterocycles.

Synthesis and structure of phenylmercury derivatives of 4-arylsulfonylaminopyridines

1. The structure of phenylmercury derivatives of substituted 4-phenylsulfonylaminopyridines in solution was studied by a spectral method. 2. The influence of the nature of the solvent and substituent in the phenylsulfonyl group upon the position of tautomeric equilibrium of the indicated compounds was determined.