Phenyl Mercury Research Articles

Halomethyl-metal compounds LV. The synthesis of phenyl(trifluoromethyl)mercury by fluorination of phenyl(tribromomethyl)mercury

The reaction of phenylmercuric hydroxide with aqueous hydrofluoric acid gives a material which appears to be an HF adduct of phenylmercuric fluoride (“PhHgF·HF”). This material has been found to fluorine phenyl(tribromomethyl)-mercury in benzene or toluene medium at room temperature to give phenyl(trifluoromethyl)mercury in yields avaraging 60–65% when the reaction is carried out in the presence of 48% HF. Phenyl(trichloromethyl)mercury can be fluorinated to PhHgCF 3 in this manner, but a reaction temperature of 90° is required. Partial fluorination in good yield of phenyl(bromodichloromethyl)mercury to phenyl-(fluorodichloromethyl)mercury could be achieved at room temperature, but attempted partial fluorination of PhHgCBr 3, PhHgCClBr 2 and PhHgCFBr 2 was unsuccessful, PhHgCF 3 being the major product obtained. The possible mechanism of this novel fluorination process is discussed.

Halomethyl-metal compounds : LIV. Phenyl(dihalocarbomethoxymethyl)mercury compounds as halocarbomethoxycarbene transfer agents

The phenyl(dihalocarboalkoxymethyl)mercury compounds PhHgCCl 2CO 2CH 3, PhHgCClBrCO 2CH 3, PhHgCBr 2CO 2CH 3, PhHgCCl 2CO 2CH 2CHCH 2 and PhHgCCl 2CO 2CMe 3 have been prepared by the reaction of phenylmercuric chloride, the appropriate dihaloacetic acid ester and Me 3COK · Me 3COH in THF at −50° to −65°. The first two mercurials were found to transfer ClCCO 2CH 3 to olefins and to triethylsilane, while the third proved to be a source of BrCCO 2CH 3. The rather high stability of these mercury compounds, however, limits their application in the synthesis of carbomethoxy-substituted cyclopropanes.

Halomethyl-metal compounds. LIII. Reactions of phenyl(trihalomethyl)mercury compounds with thiocarbonyl derivatives

Halomethyl-metal compounds. LIII. Reactions of phenyl(trihalomethyl)mercury compounds with thiocarbonyl derivatives

Further studies on SS bonds in cereal glutelins.

AbstractFlours of wheat, rye, barley, oats, maize and sorghum have been extracted to remove albumins, globulins and prolamins. The SS bonds of the starch‐glutelin residues (4 to 8% protein) have been reduced with sulphite and titrated with phenyl mercury acetate (PMA) in the presence of 3 M‐guanidine hydrochloride at 37 °C and, in its absence, at 2 and 37 °C. Attention has been paid to several possible sources of error including oxidation and the rate of diffusion of PMA into protein particles. Approximate values for the diffusion coefficients of PMA through cellulose and protein films were obtained. Titrations at 37 °C in the absence of guanidine hydrochloride are unsatisfactory due to reaction of intrachain SS links. Evidence in the literature suggests that the SS bonds titratable at 2 °C are inter‐chain, possibly includingsomestrained intra‐chain bonds. The results imply that most of the major polypeptide chains in the cereal glutelins examined, apart from barley and sorghum, contain two such bonds. In the case of barley glutelin probably less than half the chains have two labile SS bonds. Most of the chains in sorghum glutelin appear to have a single labile bond and the polymers may contain only a few chains. The molecular weights (in thousands) of the principal polypeptide chains of the glutelins, deduced from gel electrophoresis in sodium dodecyl sulphate (SDS), are: Cappelle‐Desprez wheat 44, 41; Manitoba wheat, rye and barley, 44; oats, 33, 23; maize, 23, 19; sorghum, 22, 18.

The Reaction of Phenyl(trichloromethyl)mercury with Substituted Norbornenes

AbstractThe addition of phenyl(trichloromethyl)mercury to five substituted norbornenes is described, and the results compared with those obtained with bicyclo[2.2.2]oct‐2‐ene and 3,3,5,5‐tetramethylcyclopentene. The reaction proves to be useful for synthetic purposes, in that it leads usually to ring expansion. However, a possible disadvantage is that the addition step is sensitive to steric hindrance and depends on the reactivity of the double bond.

New reactions of phenyl(trihalomethyl)mercury compounds. Dihalocarbene addition to azodicarboxylate esters

New reactions of phenyl(trihalomethyl)mercury compounds. Dihalocarbene addition to azodicarboxylate esters

Phenyl(trihalomethyl)mercury compounds. Exceptionally versatile dihalocarbene precursors

Phenyl(trihalomethyl)mercury compounds. Exceptionally versatile dihalocarbene precursors

Studies on the germination and field establishment of Summit wheat

Poor field emergence of the wheat cultivar Summit was reported in the Wimmera Region of Victoria after its release to farmers in 1966. In field and laboratory experiments the emergence of Summit was reduced when seed was stored for long periods after being treated with normal rates of a phenyl mercury acetate fungicide commonly used for control of covered smut or common bunt of wheat. A shorter period of storage with higher rates also seriously reduced emergence. Several other fungicides were shown to have varying effects on the emergence of the cultivar and one of these, maneb, gave satisfactory control of bunt. The greater susceptibility of Summit to phenyl mercury acetate demonstrated in these experiments was not associated with the degree of seed coat damage.

The synthesis of 2-silanorcaranes

2,2-Dimethyl-2-silanorcarane has been prepared by the stepwise reduction of 7,7-dibromo-2,2-dimethyl-2-silanorcarane with tri-n-butyltin hydride. Treatment of the dibromonorcarane with silver ion or pyrolysis with quinoline releases hydrogen bromide and decomposs the ring system. Trimethyl(dimethylamino)stannane reduces the dibromo compound to a 1.5/1 mixture of the endo- and exo-isomers of 7-bromo-2,2-dimethy-2-silanorcarane in the first known reaction of the tinnitrogen bond to proceed by a radical mechanism. β-Elimination of bromine is favored endo ⪢ exo in the mass spectrometer. The 7,7-dibromo compound is prepared by a series of steps which include the hydrosilation of 5-chloro-1-pentyne by trichlorosilane, the intramolecular Barbier cyclization of the product, the methylation of the resulting 1,1-dichloro-1-sila-2-cyclohexene, and the action of a dihalocarbene generated from phenyl(tribromomethyl)mercury on this silacyclohexene. The dibromonocarane is formed in 50% yield, but a side reaction produces 5-(dimethylbromosilyl)-1-pentene, which was identified as its hydrolysis product, [CH 2CH)CH 2) 3Si(CH 3) 2] 2O. Deuteration experiments establish that the process of ring-opening is concerted, and the observation of resonances due to a transient β-addition product in the NMR leads to the proposal of an HBr-addition β-elimination mechanism for ring-opening which appears to apply to several examples of unsaturated sila- and germacarbocycles in general. Hydrostannation of 5-chloro-1-pentyne by dimethyltin hydride chloride leads to the dimethylchlorostannyl-substituted 5-chloro-1-pentene which undergoes alkyl group redistribution to form a mixture of alkyltin chlorides.

Phenyl(iodobromochloromethyl)mercury and phenyl(dibromofluoromethyl)mercury: Two new highly reactive divalent carbon transfer reagents

Phenyl(iodobromochloromethyl)mercury and phenyl(dibromofluoromethyl)mercury: Two new highly reactive divalent carbon transfer reagents

Halomethyl metal compounds. XLIV. Reactions of phenyl (bromodichloromethyl) mercury derived dichlorocarbene with silacyclobutanes. Novel ring expansion reaction

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHalomethyl metal compounds. XLIV. Reactions of phenyl (bromodichloromethyl) mercury derived dichlorocarbene with silacyclobutanes. Novel ring expansion reactionDietmar Seyferth, Robert Damrauer, S. Brian Andrews, and Stephen S. WashburneCite this: J. Am. Chem. Soc. 1971, 93, 15, 3709–3713Publication Date (Print):July 1, 1971Publication History Published online1 May 2002Published inissue 1 July 1971https://doi.org/10.1021/ja00744a026RIGHTS & PERMISSIONSArticle Views139Altmetric-Citations42LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (648 KB) Get e-Alerts Get e-Alerts

Halomethyl-metal compounds. XLVI. Reaction of phenyl(bromodichloromethyl)mercury with heteroatom cumulenes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHalomethyl-metal compounds. XLVI. Reaction of phenyl(bromodichloromethyl)mercury with heteroatom cumulenesDietmar Seyferth, Robert Damrauer, Houng-Min Shih, Wolfgang Tronich, William Edward Smith, and Jeffrey Y. P. MuiCite this: J. Org. Chem. 1971, 36, 13, 1786–1789Publication Date (Print):July 1, 1971Publication History Published online1 May 2002Published inissue 1 July 1971https://doi.org/10.1021/jo00812a014RIGHTS & PERMISSIONSArticle Views87Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (586 KB) Get e-Alerts Get e-Alerts

Halomethyl-metal compounds. XLV. Organomercury CF3CCl transfer reagents: phenyl(1,1-dichloro-2,2,2-trifluoroethyl)mercury and phenyl(1-bromo-1-chloro-2,2,2-trifluoroethyl)mercury

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHalomethyl-metal compounds. XLV. Organomercury CF3CCl transfer reagents: phenyl(1,1-dichloro-2,2,2-trifluoroethyl)mercury and phenyl(1-bromo-1-chloro-2,2,2-trifluoroethyl)mercuryDietmar Seyferth and David C. MuellerCite this: J. Am. Chem. Soc. 1971, 93, 15, 3714–3720Publication Date (Print):July 1, 1971Publication History Published online1 May 2002Published inissue 1 July 1971https://doi.org/10.1021/ja00744a027RIGHTS & PERMISSIONSArticle Views76Altmetric-Citations20LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (959 KB) Get e-Alerts Get e-Alerts

Halometyl-metal compounds : XLVIII. CHCI transfer to olefins via phenyl(dichloromethyl). and phenyl(bromochloromethyl) mercury

Phenyl(dichloromethy)mercury and phenyl(bromochloromethy)mercury were found to transfer CHCl to olefins when these reagents were heated together at temperatures ranging from 84–140°. Phenyl(dichloromethy)mercury was the less reactive of the two mercurials. Product yields were variable and the applications of these reagents in chlorocyclopropane synthesis seems limited. The evidence obtained suggests that free monochlorocarbene is not an intermediate in this CHCl transfer reaction, rather than a direct reaction between the organomercury reagent and the olefin is involved.

Halomethyl-metal compounds : XLVII. Phenyl(1,1-dichloroethyl)mercury, a potential CH 3CCl transfer agent

Phenyl(1,1-dichloroethyl)mercury has been prepared via 1,1-dichloroethyllithium and evaluated as a potential CH 3CCl transfer agent. Although this mercurial reacted with triethylsilane to give Et 3SiCHClCH 3 (35%) and with allyltrimethylsilane to give 1-chloro-1-methyl-2-(trimethylsilylmethyl)cyclopropane (31%), its principal mode of reaction involved elimination of hydrogen chloride. The products resulting from this elimination were benzene (from HCl cleavage of PhHg bonds) and redistributed mercury compounds containing the concomitantly formed HgCClCH 2 moiety. Possible reasons for this unexpected reaction are discussed.

各種水銀化合物の培養神経組織に対する影響

The effect of inorganic, alkyl, aryl and other mercury compounds on the dorsal root ganglia from chick embryos in culture was studied in order to investigate the relationship between the structure of mercury compounds and the toxicity on the nervous tissue. The results obtained are as follows. 1. When chloride was introduced to the hydrophilic moiety of the mercury compounds instead of iodine, the compounds were found to be more toxic for the outgrowth of Schwann cells and nerve fibers. The binding of a hydrophobic group to the hydrophilic moiety of mercury compounds did not show the decrease in the toxicity. 2. The toxicity of mercury compounds was determined principally by the character of hydrophobic moiety. Phenyl mercury was less toxic than alkyl one. Alkyl mercury compounds having short carbon chains was more toxic than those having longer chains. 3. L-Cysteine hydrochloride, DL-penicillamine (DL-β-mercaptovaline), and BAL (2, 3-dimercaptopropanol) did not inhibit the toxic effect of organic mercury compounds. This results indicate that the mechanism of hydrophilic moiety could not be explained only by the binding of the moiety with SH group of the membranes or proteins. 4. Cholesterol, cholesterol palmitate, cephalin, and lecithin did not inhibit the toxic effect of organic mercury compounds. However, sphingomyelin and phosphatidyl-L-serine tended to improve the outgrowth of Schwann cells and nerve fibers in the presence of organic mercury compounds. These results suggest the specific binding of the hydrophobic moiety with the specific binding sites of the membrane. 5. The degree of the toxicity of the compounds having the multiple sizes of methyl mercury chloride was almost the same as that of methyl mercury chloride itself. This result seems to indicate the presence of the regular distribution of binding sites on the surface of the membrane. 6. It was pointed out that the tissue culture technique of the nervous system was useful to test chemicals from many industries to see whether they have neurotoxicity or not.

Carbonyl ylides as possible intermediates in reactions of a mercurial dichlorocarbene precursor with benzaldehyde

The intermediacy of a carbonyl ylide is used to explain why treatment of benzaldehyde with phenyl(bromodichloromethyl)mercury produced phenylmercuric bromide, carbon monoxide, benzal halide, and methyl 2,4-diphenyl-3,5-dioxahexanoate as major products.

Reactions of phenyl(bromodichloromethyl)mercury with α-dicarbonyl compounds

Reactions of phenyl(bromodichloromethyl)mercury with α-dicarbonyl compounds

Stereoselective synthesis of 2,4-bridged pyridinophanes

Reaction of the indole ether 3 with phenyl (trichloromethyl) mercury gives the syn-metacyclophane 5, exclusive of the anti-enantiomer 6. These ethers are new and their structures were established by their independent synthesis from the corresponding alcohols 7 and 8. These data are consistent with the conclusion that the intermediate cyclopropane 4 is formed by stereosperific addition of dichlorocarbene trans to the ethoxy group. Additional results are described providing evidence for the resistance of the benzylic carbon atoms in these highly constrained metacyclophanes to undergo change of hybridization from sp 3 to sp 2.

Studies on microdetermination of total mercury and the dynamic aspects of methyl mercury compound in vivo. II. Behaviour of low concentrated methyl mercury compound in vivo

A considerable number of reports have been published on the experimental symptoms of poisoning by mercury. There have however been very few reports on its behaviour in living bodies when the administrated dose was low.In this paper, some information was obtained at a low concentration of administration---information on absorption, excretion, and accumulation of methyl mercury in living bodies using mice of d.d strain, transformation into fetus using rats of Wisterstrain.Results are as follows;1) Absorption rates from the digestive tract of orally administrated mercury compounds were Methyl mercury choloride (MMC) 73%, Phenyl mercury acetate 45% and Mercury acetate 6% after about 6hrs.2) Accumulation in the bodies of mice given solid foods containing MMC 1.0ppm (mercury equivalent) showed apparent increase. But experiments revealed that there was a certain limiting value in accumulation after about 75 days, the value being about 40μg.3) 23.2% of the total administrated MMC dose taken into the mother body passed into the fetus group. MMC concentrations in brain and liver were higher in the fetus-body than in those of the mothers.4) Contents of mercury in blood and hair apparently showed lower values in pregnant rats than in the non-pregnant.5) In comparison with human mother and their new-borns, mercury content in blood corpuscles was higher and that of serum was lower in the new-born.