Phenylmercuric Chloride Research Articles

Phenylmercury(II) compounds—I: Some novel mononuclear and binuclear phenylmercury(II) compounds with benzimidazole and 2-substituted benzimidazoles

Benzimidazole (BzH) and 2-substituted benzimidazoles [2-methylbenzimidazole (MeBzH), 2-ethylbenzimidazole (EtBzH), 2-hydroxymethyl benzimidazole (HOMeBzH) and 2-guanidinobenzimidazole (GBzH)] react with basic phenylmercuric nitrate to form binuclear organo-mercury(II) complexes of the general formula [C 6H 5 · Hg(L)Hg · C 6H 5]NO 3 where LH is a monoprotic benzimidazole ligand. The complexes are insoluble in common organic solvents but are ionic in nitromethane. Phenylmercuric acetate and phenylmercuric chloride give with benzimidazole complexes: [C 6H 5 · Hg(Bz)] and [C 6H 5 · Hg(Bz)Hg(C 6H 5)Cl] respectively. But 2-methyl benzimidazole and phenylmercuric acetate produce [C 6H 5 · Hg(MeBz)Hg · C 6H 5](CH 3COO). 2-(2-Pyridyl) benzimidazole (PyBzH) reacts with phenylmercuric acetate and the basic nitrate to give the same 3-coordinate mononuclear product [C 6H 5 · Hg(PyBz)], while the 2-carboxylic acid derivative of benzimidazole (HBzCOOH) gives with basic phenylmercuric nitrate binuclear [C 6H 5 · Hg(BzCOO)Hg · C 6H 5]. 2-( o-hydroxyphenyl)benzimidazole (HOPhBzH) reacts with basic phenylmercuric nitrate to give a non-electrolyte binuclear complex [C 6H 5 · Hg(OPhBz)Hg · C 6H 5].

Macroreticular copolymer bound analogs of phenylmercuric chloride, phenyllithium, and phenyldi- [formula omitted]-butyltin chloride

Macroreticular copolymers of styrene and 20% divinylbenzene were functionalized with resin-bound analogs of phenylmercuric chloride, phenyllithium, and phenyldi- n -butyltin chloride at levels lower than 0.05 meq per gram of resin. Resino-phenylmercuric chloride was formed by the reaction of mercuric trifluoroacetate with the resin followed by trifluoroacetate -- chloride exchange. Resino-phenyllithium was formed by the action of n -butyllithium on resino-phenylmercuric chloride and also by direct lithiation using the tetramethylethylenediamine complex of n -butyllithium. Resino-phenyllithium reacted with di- n -butyltin dichloride to form resino-phenyldi- n -butyltin chloride. In this case, relatively large quantities of resino-phenyltri- n -butyltin are also produced as a result of n -butyllithium adsorbed on the reacting polymer.

The influence of selenium on the level of mercury and metallothionein in rat kidneys in prolonged exposure to different mercury compounds.

Mercuric chloride, phenylmercuric chloride, ethylmercuric chloride /0,23 mg Hg/kg/ and methylmercurycyan guanidine /0,46 mg Hg/kg/ were orally administered to rats every second day for 14 weeks. The same doses of the above mentioned mercury compounds were administered alternately with sodium selenite /0,18 mg Se/kg/ to parallel groups of rats at the same time. The level of total and inorganic mercury and of metallothionein was determined. All mercury compounds increased the level of metallothionein in rat kidneys. In rats which received only selenium the level of metallothionein was twice lower in the kidneys in relation to the physiological level of this protein. Selenium eliminated the stimulation of biosynthesis of metallothionein by mercury.

Aminopeptidase N from Escherichia coli

The subcellular localization of aminopeptidase N (previously called aminoendopeptidase) has been investigated. This enzyme was found to be partially released (30-40%) by osmotic shock or by converting Escherichia coli K10 cells to spheroplasts. However, in all other E. coli strains (K12, B/r, MRE 600, ML 308) tested, this enzyme is not released at all by these procedures and thus behaves like a cytoplasmic enzyme. The crypticity of aminopeptidase N is surprisingly low, 75-85% of the enzyme activity is directly assayable in intact cells of any E. coli strain. Various inhibitors of transport systems do not interfer with this assay. Aminopeptidase activity could also be assayed in spheroplasts, even when an insolubilized substrate was used, which suggests a surface location of this enzyme. As well, N-ethylmaleimide (0.4 mM), under conditions which do not allow penetration in the cytoplasm, caused 70% inhibition of aminopeptidase N. Binding of 125I-labeled antiaminopeptidase N antibody to spheroplasts (from K12 strain) was used to assay the orientation of aminopeptidase N in the membrane. This enzyme is exposed on the outer surface of the cytoplasmic membrane. Confirmation of this orientation was obtained by comparing the accessibility of aminopeptidase, alkaline phosphatase and beta-galactosidase to fluorescamine in intact cells. Only 16% of the total beta-galactosidase was labeled with this fluorescent reagent whereas 44-45% of the aminopeptidase N and 59% of the alkaline phosphatase were labeled. Electron microscopic visualization of insolubilized reaction products of aminopeptidase N within the cells showed that these products are located at the poles of the cells. Neither mutant cells which were devoid of aminopeptidase N activity nor parental strains with the enzyme activity inhibited with phenylmercuric chloride contained the characteristic black caps. Thus, it appears that the periplasm is enlarged at the poles of the cells and that the reaction product is mainly located in these places. Investigation of the type of interactions of aminopeptidase N with the plasma membrane only revealed that aminopeptidase N has mainly an electrostatic interaction with the outer surface, probably mediated by magnesium ion bridges. Additional interactions are involved since disruption of the integrity of the cytoplasmic membrane is required to totally release this enzyme.

ChemInform Abstract: SYNTHESIS AND BROMODEMERCURATION OF SOME PERMERCURATED ARENES

AbstractReaktion von überschüssigem, geschmolzenem Hg‐trifluoracetat (I) (in situ aus HgO/Trifluoressigsäure) mit Arenen wie (II) gibt die perrnercurierten Derivate (III), die durch Bromdemercurierung mit Brg‐Ionen Pentabrombenzole wie (IV) liefern.

Synthesis and bromodemercuration of some permercurated arenes

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.

Rapid method for the determination of lysine in cereal grains without hydrolysis

A rapid spectrophotometric method for lysine determination in cereal grains is reported. The reagent is sodium dinitrobenzene sulfonate (DNBS). The absorbance of the acid solution of the DNBS derivative is read at 385 nm. Under prescribed conditions, the reagent is sensitive and specific for free or protein-bound lysine. The conditions: For rice, the reaction medium is a urea-phosphate-HgCl 2 solution (pH 10.5); reaction at 60°C for 1 hr. For other grains, the reaction medium is a urea-phosphate-phenylmercuric chloride (PMC) solution (pH 12.3); reaction at 40°C for 1 hr. Interferences are eliminated by ether extraction after color development and acidification and addition of formic acid and the sulfhydryl masking agents, HgCl 2 or phenylmercuric chloride (PMC). NaOH extracts of cereal proteins are used for analysis. Values are in agreement with those of the ion-exchange amino acid analyzer.

Halomethyl-metal compounds LXXVII. An organomercury route to tetrafluoroethylidene

Phenyl(1-bromo-1,2,2,2-tetrafluoroethyl)mercury has been prepared by reaction of phenylmercuric chloride and 1-bromo-1,2,2,2-tetrafluoroethane with sodium methoxide in THF at -35°. This mercurial readily transferred CF 3CF to carbenophiles at 155°. With olefins good yiels of gem-fluoro(trifluoromethyl) cyclopropanes were obtained and with triethylsilane Si insertion gave Et 3SiCHFCF 3. On reaction with thiobenzophenone, the intermediate thurane underwent loss of sulfur to give Ph 2CCFCF 3. A similar observation was made in the reactions of PhHgCFBrCO 2Et with thiobenzophenone and thiofluorenone. Phenyl(1-bromo-1,2,2,-trifluoro-2-ethoxyethyl)mercury also was prepared, but this compound did not exhibit divalent carbon transfer reactivity.

The action of metal halides on tetra-, penta-, and hexa-coordinated organotin compounds : III. The action of mercuric halides on organotin oxinates

The reactions of mercuric halides with some organotin oxinates have been examined. The penta-coordinated compound triphenyltin oxinate, Ph 3SnOx (Ox = Oxinate), has been shown to react readily with mercuric halides at room temperature to produce halo(phenyl)tin dioxinates, PhSn(Ox) 2X, phenylmercuric halides, PhHgX, and triphenyltin halides, Ph 3SnX. Similarly, the penta-coordinated compound, chloro(diphenyl)tin oxinate, Ph 2Sn(Ox)Cl, reacts with mercuric chloride to give dichlorotin dioxinates, Sn(Ox) 2Cl 2, phenylmercuric chloride and diphenyltin dichloride. The hexa-coordinated compound diphenyltin dioxinate, Ph 2Sn(Ox) 2, is attacked by mercuric halides only when refluxed in benzene or ether to produce halo(phenyl)tin dioxinate, PhSn(Ox) 2X, and phenylmercuric halides, PhHgX.

Pigments induced by organomercurial compounds in Cephalosporium diospyri.

Summary: The major pigments induced by parahydroxymercuribenzoate and parachloromercuribenzoate (both SH group inhibitors) in the fungus Cephalosporium diospyri have been characterized as carotenoids. Those present in both chemically-induced and light-induced cells include phytoene, β-carotene, γ-carotene, lycopene, torulene and neurosporaxanthin. Two other organomercurial compounds, phenyl mercuric acetate and phenyl mercuric chloride, were also found to induce pigment formation. These pigments have the absorption properties of carotenoids, but have not been fully characterized. A range of other SH group inhibitors tested failed to induce any pigment formation.

ChemInform Abstract: THE OXYPHENYLATION OF CYCLIC OLEFINS CONJUGATED TO THE BENZENE RING BY MEANS OF PALLADIUM CHLORIDE

AbstractDie Reaktion von 1,2‐Dihydronaphthalin (I), Inden (IV) und Acenaphthylen (VII) mit Phenyl‐PdCl, dargestellt in situ aus Phenyl‐HgCl und Li‐tetrachloropalladat(II) in wäßrigem Aceton, führt zu den 2‐Phenyl‐1‐hydroxy‐Derivaten (IIa), (Va) bzw. (VIIIa) neben den phenylierten Olefinen (III), (VI) bzw. (IX).

ChemInform Abstract: THE HECK REACTION OF 2‐VINYLPYRIDINE

AbstractIn Gegenwart vongLi‐tetrachloropa1ladat(II) reagiert Vinylpyridin (II) mit den Aryl‐ Hg‐chloriden (I) unter Bildung der Arylpyridyläthyl‐Pd‐Dirneren (III) und der Diaryl‐ Verbindungen (IV).

The Oxyphenylation of Cyclic Olefins Conjugated to the Benzene Ring by Means of Palladium Chloride

Abstract The reaction of 1,2-dihydronaphthalene, indene, and acenaphthylene with phenylpalladium chloride prepared in situ from phenylmercuric chloride and lithium chloropalladate in aqueous acetone afforded 2-phenyltetrarol, 2-phenylindanol, and 2-phenylacenaphthenol respectively, accompanying by the corresponding phenylated olefins. Acetoxyphenylation products were also obtained in the reactions in acetic acid. The configurations of these oxyphenylated compounds were determined to be trans.

Pustules on wood as sources of inoculum in apple scab and their response to chemical treatments

SUMMARYThe green stems and leaves of potted Cox's Orange Pippin trees were susceptible to infection by Venturia inaequalis from June to August. Some isolates of the fungus showed conspicuous ability to attack the wood.In the orchard, many conidia were released from pustules in early March (2—3 wk before bud‐burst) but in the 3 years examined (1967—9) most were liberated in April and May. In 1969 it was shown that a decline in numbers in June was accompanied by a decrease in viability of conidia.Infections near the tips of leading shoots were partially controlled by a single treatment with 5% urea (aqueous solution) in October 1966 or 2% urea or 0·01% phenylmercuric chloride (PMC) in March 1967. The subsequent reduction in inoculum was correlated with a reduction in the numbers of primary infections developing on leaves. Basal infections on leading shoots were not susceptible to treatment in October 1967 or March 1968, but in 1969 similar infections were controlled with PMC applied mid‐April when the pustules had burst and were actively sporulating.

Organomercury compounds : XIX. The preparation of pentafluorophenylmercurials by mercuration under basic conditions

Mercuration of pentafluorobenzene under basic conditions in aqueous tertbutanol by tetrabromomercurate(II) ions, phenylmercuric chloride, and p-tolylmercuric chloride yields bis(pentafluorophenyl)mercury, (pentafluorophenyl)-phenylmercury, and (pentafluorophenyl)- p-tolymercury respectively, in a single simple preparative step. Cleavage of bis(pentafluorophenyl)mercury with iodide or bromide ions in alcohols or aqueous alcohols gives pentafluorobenzene, tetrahalogenomercurate(II) ions, and base. Under alkaline conditions, tetrahalogenomercurate(II) ions are reduced to mercury by ethanol or methanol. Decomposition of (pentafluorophenyl)phenylmercury by iodide ions has also been studied.

The toxicity of three mercurials to Pteronarcys californica newport, and some possible physiological effects which influence the toxicities

There is little information available on the toxicity of mercurials to aquatic insects. The information that is available is confined to field observations or medium tolerance limit (TLm) values using only one form of mercury. The TLm values were determined for three different forms of mercury (phenylmercuric-, and methylmercuric-, and mercuric chloride) to the stonefly Pteronarcys californica. The order of toxicity of the three forms was found to be phenylmercuric chloride > methylmercuric chloride > mercuric chloride. The in vivo effect of the three forms of mercury on isolated gylceraldehyde-3-phosphate-dehydrogenase was also measured. Two possible physiological factors involved in determining the toxicity of mercury (or other metals) to aquatic insects may be the catabolic pathways being employed at any period during the year, particularly during periods of molting, and age of the instar.

Effect of selected mercurials on glyceraldehyde-3-phosphate-dehydrogenase in Pteronarcys californica

Glyceraldehyde-3-phosphate-dehydrogenase (GAPDH) was extracted from Pteronarcys californica (Plecoptera) by ammonium sulphate fractionation. The enzyme was treated with three forms of mercury (mercuric chloride, methylmercuric chloride, and phenylmercuric chloride) and their in vitro and in vivo effects on GAPDH were studied. It was found that the orders of toxicity were reversed in the in vivo-in vitro experiments. Electrophoresis was conducted on both treated and untreated enzyme, and showed no differences in mobilities between the two. The enzyme was not found to be inhibited by 0·1 mM iodoacetic acid and required cysteine for activity.

The Heck Reaction of 2-Vinylpyridine

Abstract In the presence of lithium chloropalladite, 2-vinylpyridine reacted with phenylmercuric chloride to give di-μ-chloro-bis[2-phenyl-2-(α-pyridyl)ethyl]dipalladium (II). Similar complexes were obtained from p-toy-, p-anisyl-, or m-nitrophenylmercuric chloride. The σ-bonded structures of these complexes have been confirmed by a study of their absorption and of the NMR spectra.

Phenyl (1-bromo-1,2,2,2-tetrafluoroethyl)mercury: a useful tetrafluoroethylidene source

The reaction of phenylmercuric chloride, 1-bromo-2,2,2-tetrafluoroethane and methanolic sodium methoxide in THF at −35° gave PhHgCFBrCF 3 in good yield. Thermolysis of this mercurial at 155° for 24 h in the presence of olefins gave gem-fluoro(trifluoromethyl)cyclopropanes, while its reaction with triethylsilane produced Et 3SiCHFCF 3.

Halomethyl-metal compounds : LXI. Phenyl(fluorodibromomethyl)mercury, a fluorobromocarbene precursor

Phenyl(fluorodibromomethyl)mercury has been prepared by reaction of fluorodibromomethane, phenylmercuric chloride and sodium methoxide or potassium tert-butoxide in THF at low temperature. This organomercury reagent is an excellent source of fluorobromocarbene, releasing CFBr within 20 min at 80° or within 4 days at room temperature. The addition of PhHgCFBr 2-derived CFBr to the CC bond of 10 olefins and to the CO bond of (CF 2Cl) 2CO and the insertion of CFBr into the SiH bond of triethylsilane are described. Reduction of Et 3SiCHFBr with tri-n-butyltin hydride gave Et 3SiCH 2F.