Methyl Sulphone Research Articles

Electrochemically stimulated S RN1 reactions on aromatic rings substituted by two leaving groups : The case of 4-bromo- and 2-bromo-phenyl methyl sulphones

Etude de la reduction de ces sulfones en presence de benzenethiolate sur une electrode de mercure dans le DMF-tetrafluoroborate de tetrabutylammonium

PCB methyl sulphones and related compounds: identification of target cells and tissues in different species

The tissue-disposition of 28 polychlorinated biphenyls and 6 chlorinated non-PCB xenobiotics is summarized. Tissue-specific, structure- and species-dependent high-affinity bindings and long-term retentions in lung, kidney, brain, uterine fluid, fetal tissue, prostate, large intestinal epithelium and adrenal cortex are demonstrated. A relationship between accumulation of PCB methyl sulphones in lung tissue and development of respiratory distress in Yusho victims is proposed.

Substituent effects on the electronic structure of some styryl methyl sulphones studied by ultraviolet photoelectron spectroscopy

A gas-phase u.v. photoelectron spectroscopic study is reported on some para-substituted styryl methylsulphones in which the para-substituent varies in electronegativity and conjugating ability. The main purpose was to observe the substituent effect on electronic structure. The spectral analysis and the trends in ionization energies relative to the highest MOs show that the substituent has both short- and long- range effects, influencing even the orbitals of the –SO2Me group. Satisfactory linear relationships were found between the spectral data for the three highest MOs and the Hammett σp values, the wavenumbers of the SO2 stretching vibrations, and the 13C n.m.r. shifts for C-1 of the styryl group.

Metabolism of 2,4′,5-trichlorobiphenyl: tissue concentrations of methylsulphonyl-2,4′,5-trichlorobiphenyl in germfree and conventional mice

Whole-body autoradiography of 2,4′,5-[ 14C]trichlorobiphenyl ([ 14C]triCB) indicated that, whereas there was accumulation of radioactivity in the tracheobronchial mucosa of conventional (C) mice 1–7 days after injection, no such effect was observed in germfree (GF) mice 1 day after injection. At days 4 and 7 there was a low, but significant, uptake by the tracheobronchial mucosa of the GF mice. Chemical analysis showed that the concentrations of 4-methylsulphonyl-triCB (4-MeSO 2-triCB) in lung, kidney and liver 7 days after administration of triCB were 6.5, 14.7 and 3.7 times higher, respectively, in C than in GF mice. The results are interpreted as indicating the existence of a major metabolic route to triCB methyl sulphones involving the intestinal microflora, and a minor route, not requiring the flora. Abbreviations: C, conventional; GC, gas chromatography; GF, germfree; GSH, glutathione; MF, mass fragmentography; PCB, polychlorinated biphenyls; triCB, trichlorobiphenyl.

Metabolism of 2,4′,5-trichlorobiphenyl: Role of the intestinal microflora in the formation of bronchial-seeking methyl sulphone metabolites in mice

Groups of germ-free and conventional mice were treated with 2,4′,5-trichlorobiphenyl (triCB) and [ 35S]cysteine or [ 35S]methionine, respectively. Control animals received the labelled amino acids only. Conventional mice accumulated significantly more extractable radioactivity both in lung and kidney tissues when compared to germ-free mice. The extracted radioactivity in lung and kidney tissues was shown to be due to the accumulation of methyl-[ 35S]sulphonyl-triCB. The low radioactivity in lungs of the germ-free mice was also shown to be due to the accumulation of small amounts of the sulphones. The results indicate an involvement of the intestinal flora in the formation of methyl sulphone metabolites of triCB.

Metabolism of 2,4′,5-trichlorobiphenyl: Enrichment of hydroxylated and methyl sulphone metabolites in the uterine luminal fluid of pregnant mice

Autoradiography of 2,4′,5-trichloro-[ 14C]biphenyl ([ 14C]triCB) in mice at different stages of gestation indicated a strong accumulation of radioactivity in the uterine luminal fluid at gestation day 9 and later. From day 10 an uptake of radioactivity occurred also in the yolk sac epithelium. In order to identify the suspected metabolites in the fluid pregnant mice were dosed with unlabelled triCB on gestation day 9. Gas chromatographic (GC) and mass fragmentographic (MF) analysis of extracts of uterine fluid obtained on day 12 showed that hydroxylated, methyl sulphone and conjugated metabolites were present in the fluid. The unchanged triCB could not be detected in the extracts of the fluid. The site of release of the metabolites to the fluid may be the endometrium or, possibly, the yolk sac epithelium. The mechanism behind the concentration of water-insoluble methyl sulphone and hydroxylated metabolites of triCB in an aquatic phase is discussed.

The herbicidal activity of bromoxyside (3,5–dibromo‐4–hydroxyphenyl methyl sulphide), its esters and related compounds

SUMMARYStudies on the herbicidal activity of 3,5–dibromo‐4–hydroxybenzonitrile (bromoxynil) and 3,5–dibromo‐4‐hydroxyphenyl methyl sulphone (bromoxysone) have been extended to include 3,5–dibromo‐4‐hydroxyphenyl methyl sulphide (bromoxyside), its esters and other related compounds.Bromoxyside produced chlorotic effects in barley and wild oat seedlings, the herbicidal activity being similar to that of bromoxysone but quite different to that of bromoxynil. A range of aliphatic and aromatic esters of bromoxyside were prepared and examined as herbicides using barley and wild oat seedlings as test plants. The acetate and propionate were the most active against both species. No compound tested was more herbicidal to wild oat than to barley. Introduction of a further bromo or methyl ring‐substituent into bromoxyside removed herbicidal activity.Spraying plants of differing age showed that the herbicidal effect was greater when the plants were small.

Cysteine and methionine—Precursors of methyl sulphone metabolites of 2,4′,5-trichlorobiphenyl in mice

In order to account for the origin of the sulphur atom in methyl sulphones derived from polychlorinated biphenyls (PCB), groups of mice were treated with 2,4′-5-trichlorobiphenyl and [ 35S]cysteine or [ 35S]methionine, respectively. Control animals received the labelled amino acids only. The radioactive substances extracted from lung tissue were characterized by partition between hexane and sulphuric acid, thin-layer radiochromatography (TLRC), gas chromatography (GC) and mass fragmentography (MF). In lung extracts of both experimental groups sulphuric acid soluble metabolites were present: Their R f-values on TLRC were identical with that of 4-methylsulphonyl-2,4′-5-trichlorobiphenyl and their identity was confirmed by GC and GC-MF, which also indicated the presence of a minor sulphone isomer. The study shows that both cysteine and methionine could function as donors of the sulphur atom in the methyl sulphone metabolites derived from PCB.

Synthesis and transformations of mercaptobicyclo[2.2.2]octanes

The paper describes preparation of 1-mercaptobicyclo[2.2.2]octanes by the isothiouronium method and transformations of 1-mercapto-4-methyl derivative into the corresponding methyl sulphide, methyl sulphoxide, methyl sulphone and disulphide.

Use of a harpacticoid copepod in toxicity tests

The harpacticoid copepod Nitocra spinipes has been tested for acute toxicity of 12 metal chlorides in brackish water. Their order of toxicity, expressed as 96 h LC 50, was in good agreement with other investigations performed in freshwater and seawater. The 96 h LC 50-values were of intermediate levels compared to these two environments. The organochlorines p, p′-DDE and p, p′-DDE methyl sulphone were tested for effects on reproduction and mortality during two weeks, and it was found that p, p′-DDE was the most toxic. It is concluded from the investigation that N. spinipes is a suitable toxicity test organism in brackish water.

Alkyl–oxygen bond formation in the mass spectra of α‐chloromethyl aryl sulphones

AbstractWhen subjected to electron‐impact, chloromethyl aryl sulphones (II, X = Cl) fragment predominantly by the loss of CH2Cl from the molecular ion followed by the loss of SO2 and in most cases the appropriate metastable peaks are present to confirm the transitions. In addition, alkyl–oxygen bond formation in the molecular ion was revealed by the presence of prominent peaks corresponding to the [Rϕ‐SO]+ ions. In most spectra no evidence for aryl–oxygen bond formation could be found and thus the presence of the chlorine atom was able to effectively reverse the direction of skeletal rearrangement reported for aryl methyl sulphones.

Infrared intensities as a quantitative measure of intramolecular interactions. Part XXIX. Methyl phenyl sulphones and sulphoxides

The integrated i.r. intensities of the ν8 band for series of meta- and para-substituted methyl phenyl sulphoxides and sulphones show that whereas MeSO2 is a resonance acceptor σ°R+ 0·06, MeSO is a net resonance donor σ°R– 0·07. However, when para to a strong donor group, both MeSO2 and MeSO become resonance acceptors of considerable magnitude. Intensities of as and SνSO2 are correlated by σ+ values of meta- and para-substituents.

Carbon‐oxygen bond formation in the mass spectra of aryl methyl sulphones

AbstractUpon electron‐impact aryl methyl sulphones (I) rearranged to form aryl‐oxygen bonds. The mode of fragmentation of the intermediate ester (II) to give [aryl O]+ or [aryl OH]+ ions was found to be markedly influenced by the nature of the aryl substituent.

Organosilicon compounds. Part XLIII. Preparation of aryl sulphones by desilylation or destannylation

Treatment of an aryltrimethylstannane (X·C6H4·SnMe3) with a preformed arenesulphonyl chloride–aluminium chloride (Y·C6H4·SO2Cl,AlCl3) complex in methylene chloride has been used to give the diaryl sulphone X·C6H4SO2·C6H4·Y in moderately good yield; examples are the sulphones with X and Y as follows: H, H (62%); p-Me, H (62); H, p-Me (61); p-OMe, H (65); p-F, H (58); H, p-Me3Si (57); H, p-Ph (53). The methanesulphonyl chloride–aluminium chloride complex has been used similarly to give the aryl methyl sulphones p-X·C6H4·SO2Me, with X = H (58%), F (58), or Me (55), and also mesityl methyl sulphone (31%).Aryltrimethylsilanes similarly gave the expected sulphones when treated with Y·C6H4·SO2Cl,AlCl3 complexes, but there was sometimes contamination by isomeric products; e.g. the products from p-tolyl- or p-methoxy-phenyltrimethylsilane and the benzenesulphonyl chloride–aluminium chloride complex included some o-tolyl or o-methoxyphenyl phenyl sulphone. (However, m-tolyltrimethylsilane and benzenesulphonyl chloride in carbon disulphide in presence of aluminium chloride gave phenyl m-tolyl sulphone in 64% yield.) The disulphone 4,4′-bis(phenylsulphonyl)biphenyl was obtained (47%) from 4,4′-bistrimethylsilylbiphenyl and the benzenesulphonyl chloride–aluminium chloride complex, and (63%) from phenyltrimethylsilane and the 4,4′-bis(chloro-sulphonyl)biphenyl–bis(aluminium chloride) complex.Treatment of p-trimethylsilylbenzenesulphonyl chloride with an excess of benzene or toluene in the presence of aluminium chloride gave phenyl p-trimethylsilylphenyl sulphone (87%) and p-tolyl p-trimethylsilylphenyl sulphone (76%), respectively.

Intermediates and dyestuffs for synthetic fibres. Part I. Arylaminonitropyridines

Condensation of 2-chloro-3-nitropyridine-2-chloro-5-nitropyridine and 4-chloro-3-nitropyridine with aniline, o-, m-, and p-anisidine, o-, m-, and p-fluoroaniline and with p-aminophenyl methyl sulphone gives the corresponding arylaminonitropyridines in good yield. These compounds have an ultraviolet absorption band in the 350–420 mµ region, characteristic of the contribution of a “quinonoid” charge-transfer form to the excited state. The position of this band is influenced more by substituents in the nitrated ring than by those in the un-nitrated ring. NH stretching frequencies in the infrared are also recorded, the position of which can be correlated with the conclusions derived from the ultraviolet spectra.

Anti-viral activity of azathymidine and uracil methyl sulphone.

Anti-viral activity of azathymidine and uracil methyl sulphone.

Distribution, metabolism and excretion of percutaneously administered ditophal (‘etisul’)

When 35S-labelled ditophal is rubbed into the skin it is rapidly distributed throughout the body via the circulating blood and radioactivity is concentrated in the skin, both at the site of application and elsewhere. In patients living in a tropical climate, ditophal is largely eliminated from the body in the sweat, togetherwith volatile metabolic products. Urinary metabolites include small amounts of ethyl methyl sulphone and ethyl methyl sulphoxide and much larger amounts of inorganic sulphate and a product which yields sulphate on fairly vigorous acid hydrolysis; the urine probably also contains a little unchanged ditophal.

Free radical addition reactions—IV

Abstract Methanesulphonyl chloride reacts with hept-1-ene under the influence of short wave radiation to give β-chloroheptyl methyl sulphone. Methanedisulphonyl chloride, for which an improved preparation is described, and hept-1-ene react in the presence of benzoyl peroxide to give γ-chlorooctanesulphonyl chloride and 1,3-dichlorooctane, together with lesser amounts of methanesulphonyl chloride and a high boiling sulphone. The feeble nucleophilicity of alkanesulphonate anion is exemplified.

Long-range proton spin-spin coupling in saturated compounds

Long-range proton spin-spin coupling can easily be observed with methyl ketones, methyl sulphones and probably also with methyl sulphoxides, when resolving power is high. In the analysis of NMR spectra the effect can be used to distinguish between the groups CH 3XCH 2R and CH 3XCHR 2 (X: CO, SO 2 or SO).

The thermochemistry of some sulphones. Part 1.—The kinetics of decomposition of dimethyl sulphone, benzyl methyl sulphone and allyl methyl sulphone. The dissociation energies of the bonds R—SO2CH3.

The thermochemistry of some sulphones. Part 1.—The kinetics of decomposition of dimethyl sulphone, benzyl methyl sulphone and allyl methyl sulphone. The dissociation energies of the bonds R—SO₂CH₃.