Showing papers on "Organomercury Compounds published in 1971"

The reaction of diborane with organomercury compounds; a synthetic route to phenols and organoboranes

Abstract: Organomercury halides of type ArHgX react with diborane in tetrahydrofuran to give intermediate organoboranes which can be oxidised with alkaline hydrogen peroxide to give high yields of phenols.

Pyrolysis of Organomercury Compounds: Investigation by the Method of Matrix Isolation

Abstract: The method of matrix isolation has been used to investigate mechanisms of gas-phase chemical reactions, in particular the pyrolysis of some organomercury compounds. A molecular beam of pyrolysis products was condensed simultaneously with a large excess of rare gas at temperatures from 5 to 15°K to form a matrix that was subsequently studied by infrared spectroscopy. In the case of C6H5HgCCl3, we found that pyrolysis in the temperature range 220-400°C produced mainly dichlorocarbene. In addition, some trichloromethyl radical was observed and increased in relative importance at increased temperatures. Another identified product of pyrolysis was C6H5HgCl. In general, the same reactive intermediates, CCl2 and CCl3, were found from pyrolysis of Hg(CCl3)2 in the temperature range 250-500°C, along with CCl3HgCl and HgCl2. The identity of CCl2 and CCl2 was demonstrated by measurement of the relative intensities and isotopic splittings of stretching vibrations due to the chlorine isotopes. Isotopic patterns found for CCl2 are: v3 (745.8, 744.0, 741.8 cm-1), v1 (719.5, 717.0, 714.9 cm-1) and for CCl3 are: v3 (897.8, 896.4, 895.2, 893.9 cm-1). Less dilution with the rare gas or warming of the matrix produced a decrease of CCl2 and CCl3 spectral bands and an increase of bands due to C2Cl4, C2Cl6, and other products. These results show the usefulness of matrix isolation in the study of such reactive species as CCl2 produced by pyrolysis in the gas phase.

The mass spectra of organomercury compounds

Abstract: The fragmentation of a number of organomercury compounds under electron impact has been examined. In the symmetrical diarylmercury compounds it seems that the first fragmentation is loss of aryl radical to form arylmercury cation which then loses mercury to give aryl cation. Another important fragmentation is the extrusion of mercury from the parent ion to give a biaryl-type system. Fragmentation of the substituted aromatic compounds before C–Hg bond fission is also observed. In dialkylmercury compounds the dominant path is fission of the C–Hg bond even when an alternative path leading to a very stable cation (C7H7+) is available.In the α-halogenomercurated carbonyl compounds examined the dominant structural feature determining the direction of fragmentation is the carbonyl group, e.g. in α-chloromercuryacetone α fission leads to acetyl and α-chloromercuryacetyl ions of similar intensity. Di-(α-ethoxycarbonylbenzyl)mercury shows only Hg+ and mercury-free organic ions formed by extrusion of mercury and subsequent fragmentation of the extrusion product.When pairs of symmetrical diaryl and dialkyl mercury compounds were introduced into the mass spectrometer, ions of the type R1–Hg–R2 have been observed to accompany R21Hg and R22Hg. This exchange was confirmed by the appearance of mixed extrusion products R1–R2.

Study of the mechanism of the reactions of organomercury compounds by the method of chemically induced dynamic polarization of the nuclei

Abstract: 1. The polarization of the protons of PhCH2CPh3, the product of the “Wurtz reaction” between trityl bromide and XC6H4CH4HgBr, was detected. The one-electron mechanism of the reaction was proved. 2. The polarization of the protons of Ph3CBr during their formation of the complex with XC6H4CH2 · HgBr was detected.

Group viii-b metal organomercury compounds and process of preparation

Abstract: NOVEL COMPOUNDS OF THE FORMULA M(CO)Y(ERR1R2)ZHGR3 WHERE M IS COBALT, RHODIUM OR IRIDIUM, E IS A GROUP V-A ELEMENT EXCEPT BISMUTH R, R1 AND R2 ARE HYDROGEN OR ORGANIC GROUPS, R3 IS AN ORGANIC GROUP, Y IS AN INTEGER FROM 1 TO 3, AND Z IS AN INTEGER FROM 1 TO 3. ALSO DESCRIBED IS A PROCESS FOR THE PREPARATION OF THE ABOVE COMPOUNDS COMPRISING A CARBONYL (ORGANOSUBSTITUTED GROUP V-A ELEMENT) TRANSITION METAL WITH AN ALKALI METAL IN THE PRESENCE OF CARBON MONOXIDE FOLLOWED BY A FURTHER REACTION OF THE PRODUCT SO OBTAINED WITH AN ORGANOMERCURY COMPOUND.

Oxidation of 3- and 4-carenes with mercuric acetate in acetic acid

Abstract: 1. A study was made of the oxidation of 3-carene with Hg(OAc)2 in acetic acid at 23 and 86°, and with (HgOAc)2 at 90°. The action of both of the oxidizing agents leads to the same acetylative oxidation products: the acetates of p-mentha-1,5-dien-8-ol and p-mentha-1(7),5-dien-8-ol. 2. The products of the oxidation of 4-carene with Hg(OAc)2 in acetic acid at 20° contain the acetates of p-mentha-1,5-dien-8-ol and p-mentha-1(7),5-dien-8-ol. 3. The formation of organomercury compounds of composition C18H26O8Hg3 occurs when the 3- and 4-carenes are oxidized with Hg(OAc)2 at room temperature.

Formation of anomalous products in the bromodemercuration of organomercury compounds

Abstract: 1. Together with the bromo derivatives, anomalous products of the involvement of the solvent in the reaction are formed when benzylmercury chloride and the cyclohexyl- and cyclohexylcarbinylmercury bromides are subjected to bromodemercuration in a number of oxygen-containing solvents. 2. The formation of the anomalous products cannot be explained by the solvolytic transformations of benzyl bromide and the cyclohexyl- and cyclohexylcarbinyl bromides.

Iododemercuration of unsymmetrical organomercury compounds

Abstract: 1. A study was made of the kinetics of the iododemercuration of organomercury compounds, containing strong electron-acceptor substituents, in dimethylformamide and in benzene. 2. The increase in the rate of the iododemercuration reaction in the discussed series of organomercury compounds proceeds symbatically with increase in the stability of the carbanion, entering into the composition of the organomercury compound.