Methyl Phenyl Sulfone Research Articles

The Conversion of Ethyl Dienol Ether and Dienyl Pivalate Derivatives of Hagemanns Ester Into Bicyclic Enones

The cyclization of compounds obtained from ethyl dienol ether and dienyl pivalate derivatives of Hagemann's ester has been examined. The carbanions of methyl phenyl sulfone and methyl phenyl sulfoxide react with the methylated dienol ether (4) to give the β-keto sulfone (8) and sulfoxide (9), the former of which was converted into the oxabicyclo[4.3.0]non-1-en-3-one (16). The iodide (17) with potassium t-butoxide in t-butyl alcohol gave the octahydronaphthalenone (18). With lithium ethoxide in tetrahydrofuran the octahydronaphthalenedione (22) was obtained from the dienyl pivalate (24). Both reactions involve the generation and intramolecular cyclization of a dienolate produced by cleavage of the pivaloyl group in each of (17) and (24). The scope and limitations of these reactions are briefly discussed.

Facile magnesiation of carbon brønsted acids with electrophilic, donor-free alkylmagnesium compounds

A solution of n-butyl (s-butyl)magnesium in an alkane reacts readily between 25 and 110° C with a series of carbon Brønsted acids to produce the corresponding unsolvated diorganomagnesium derivatives in excellent yields. Such facile magnesiations provide a superior preparative route to donor-free compounds of the R 2Mg type, where R is cyclopentadienyl, indenyl, 9-fluorenyl or 1-alkynyl. Furthermore, sulfones form isolable 1/1 complexes with n-butyl (s- butyl)magnesium and these complexes then undergo automagnesiation between 25 and 85° C. Methyl phenyl sulfone undergoes magnesiation on the methyl group, while diaryl sulfones are magnesiated at the ring carbon ortho to the sulfur.

ChemInform Abstract: SYNTHESIS OF PHARMACEUTICALLY IMPORTANT HETEROAROMATICS FROM METHYL PHENYL SULFONE

Chemischer InformationsdienstVolume 16, Issue 10 Heterocyclic Compounds ChemInform Abstract: SYNTHESIS OF PHARMACEUTICALLY IMPORTANT HETEROAROMATICS FROM METHYL PHENYL SULFONE M. YOKOYAMA, M. YOKOYAMASearch for more papers by this authorK. TSUJI, K. TSUJISearch for more papers by this authorT. IMAMOTO, T. IMAMOTOSearch for more papers by this author M. YOKOYAMA, M. YOKOYAMASearch for more papers by this authorK. TSUJI, K. TSUJISearch for more papers by this authorT. IMAMOTO, T. IMAMOTOSearch for more papers by this author First published: March 12, 1985 https://doi.org/10.1002/chin.198510278Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume16, Issue10March 12, 1985 RelatedInformation

Synthesis of Pharmaceutically Important Heteroaromatics from Methyl Phenyl Sulfone

Abstract Some 5-substituted pyrazoles and pyrimethamine were prepared from 3-methylthio-1-phenyl-4-phenylsulfonyl-2-buten-1-one (5a) or (E)-1-p-chlorophenyl-1-cyano-2-methylthio-3-phenylsulfonylpropene (6b) which could be easily synthesized from methyl phenyl sulfone.

Effects of Soil Mixing and Flooding on the Fate and Metabolism of 14C-Fonofos and 14C Parathion in Open and Closed Agricultural Microcosms

The effects of soil surface application and soil incorporation (“tillage”) of 14C-fonofos and 14C-parathion on the metabolic fate of the insecticides in soils and their translocation into oat leaves were investigated in the laboratory, using both open and closed microcosms. The effects of flooding of 14C insecticide-treated soils were also studied. The insecticides were least persistent after their application to the soil surface, whereas mixing the insecticides with the soil increased the persistence of fonofos and parathion by factors of 2 and 5.3. respectively. Most of the organic solvent-soluble radiocarbon in 14C insecticide-treated soils was recovered as the undegraded parent compound, more so with fonofos than with parathion. In oat leaves from fonofos-treated soils, most of the organic soluble 14C recovered (1% of less of the soil-applied radiocarbon) was associated with the non-insecticidal fonofos metabolite methyl phenyl sulfone; in leaves from parathion-treated soil, > 90% of the organic soluble 14C (0.1 % of the soil-applied dose) was associated with parathion. In experiments with closed systems, the amounts of 14CO2 produced from soil-applied 14C-parathion were 30% of the insecticide applied to the soil surface, 23% of that mixed with the soil, and only 0.9% of that mixed with the soil and kept under flooded conditions. With fonofos-treated soils, less 14CO2 was produced, but the general trend was the same as that observed with parathion. Binding of 14C compounds to soils increased after the insecticides had been mixed with the soil and, in particular, after soil flooding when 72% of the soil-applied 14C-parathion was unextractable.

Some Comments on the Conformations of Methyl Phenyl Sulfides, Sulfoxides and Sulfones

Abstract13C‐NMR. and He (Iα) photoelectron spectra of alkyl phenyl sulfides, sulfoxides and sulfones have been used to probe how their conformations depend on the size of the alkyl groups R. The results are interpreted to indicate that in the sulfides the S, R‐bond is twisted out of the planar conformation with increasing size of the alkyl group, whereas in the sulfoxides and sulfones the preferred conformation with the S, R‐bond perpendicular to the phenyl group plane seems to be independent of the size of R. These conclusions are in agreement with previous work on the alkyl phenyl sulfides and provide strong support for previous conjectures concerning the preferred conformations of alkyl phenyl sulfoxides and sulfones.

Effects of Cover Crops on the Movement and Fate of Soil-Applied (14C)-Fonofos in a Soil-Plant-Water Microcosm

The effects of com plants or a “lawn” of ryegrass on the movement and metabolism of soil-applied 14C-fonofos were studied in a microcosm which consisted of terrestrial and aquatic components. Artificial rain, applied to the fallow or plant covered soils, resulted in runoff that accumulated in aquaria containing lake bottom mud and aquatic organisms. The presence and the type of a cover crop had a considerable effect on the mobility and metabolism of soil-applied 14C-fonofos. The insecticide plus its metabolites were least persistent in systems with fallow soils and most persistent in those with ryegrass. Within the terrestrial soil, 14C-compounds moved downwards and also were trans located via the root systems into the leaves of com and ryegrass. Within the plant tops, 86% of the recovered benzene-soluble 14C-compounds were in the form of the detoxified methyl phenyl sulfone and 2% or less as fonofos. Due to rain, considerable runoff of soil and water had been deposited into all the aquaria, but the amounts of soil and 14C transported decreased drastically due to the presence and nature of cover crops. 14C-compounds transported were primarily associated with the runoff soil and most of these were later found in the soil-lake mud sediments. 14C-fonofos was the major constituent in soils and aquatic sediments, while the major metabolite recovered from both the terrestrial and aquatic portion of the microcosm was methyl phenyl sulfone, its amounts ranging from 13 to 92% of all benzene-soluble radiocarbon. Relatively small amounts of the insecticidal oxygen analogue of fonofos were recovered, the exception being in roots of corn and of ryegrass.

On phenylsulfinyl carbenium ion

Phenylsulfinyl carbenium ion, generated by the acid-catalyzed decomposition of phenyl diazomethyl sulfoxide or the silver-assisted solvolysis of phenyl iodomethyl sulfoxide, is trapped by hydroxylic solvents to yield phenyl methyl sulfone. The possibility of the intermediacy of either phenylsulfinyl carbene or phenylsulfinylmethyl acetate has been ruled out.

Metalation of alkyl aryl sulfones: qualitative and quantitative product determination

The metalation of methyl phenyl sulfone (I) and methyl naphthyl sulfone (II) was investigated under a variety of conditions. The product species were determined qualitatively and quantitatively after characterization with some electrophilic agents. After the primary metalation at the methyl position, species of various metalation degrees were prsent simultaneously, including the 1,1,1-trimetalated derivatives. With high LiR/sulfone ratios, in addition to the products of the primary metalation, compounds arising from metalation of the aromatic ring were formed as well as those from reduction, cleavage, etc.

Determination des structures du cyclooctadiene dichloro palladium et du cyclooctadiene-1,5 (phenyl sulfonyl methanato) chloro palladium

A crystalline derivative is formed when lithiated phenyl methyl sulfone is treated with CODPdCl 2. The X-ray structure determination is described. The anionic carbon is tetrahedral.

Deuterium isotope effects during formation of phenols by hepatic monoxygenases. Evidence for an alternative to arene oxide pathway.

The in vivo and in vitro metabolisms of normal and deuterated aromatic substrates have been investigated in ratsmsignificant isotope effects (k(H)/k(d) = 1.3-1.75) were associated with in vivo formation of meta-hydroxylated metabolites from 1:1 mixtures of normal and perdeuterio-(aryl ring) nitrobenzine, methyl phenyl sulfide, and methyl phenyl sulfone. Since isotope effects of this magnitude are incompatible with arene oxides as intermediates in the formation of phenols, the results provide evidence that multiple pathways are responsible for the formation of phenols in mammals. Significant isotope effects were not associated with the formation of the other phenolic isomers of nitrobenzene, methyl phenyl sulfone, or methyl phenyl sulfide or with the formation of phenolic products from anisole, bromobenzene, chlorobenzene, fluorobenzene, benzonitrile, naphthalene, zoxazolamine, acetanilide, biphenyl, diphenylhydantoin, benzene, o- and p-xylene, toluene, and mesitylene. Significant isotope effects might not be observable with the latter substrates if the kinetic parameters for oxidation of substrate change or if the arene oxide pathway greatly predominates. Furthermore, extensive in vivo metabolism of any substrate would make isotope effects unobservable by the procedure employed, namely the analysis of isotope content in metabolites formed from 1:1 mixtures of normal and deuterated substrates.

ChemInform Abstract: A CARBON‐13 NUCLEAR MAGNETIC RESONANCE INVESTIGATION OF SOME SUBSTITUTED METHYL PHENYL SULFIDES, SULFOXIDES, AND SULFONES

Carbon-13 chemical shifts for 33 methyl phenyl sulfides, sulfoxides, and sulfones are reported. Observed trends are discussed in terms of the steric and electronic influences of the substituent gro...

Metabolic behavior of O-ethyl S,S-diphenyl phosphorodithiolate (edifenphos) in female goat.

The determination of residues in fresh milk and the metabolic fate of edifenphos (O-ethyl S, S-diphenyl phosphorodithiolate), the active ingredient of the fungicide HINOSAN® were conducted in female goats using gas-liquid chromatographic techniques. Edifenphos was rapidly metabolized to form polar products which were excreted in the urine. The major metabolites found in the urine were O-ethyl S-phenyl hydrogen phosphorothiolate and O-conjugates of m- and p-(hydroxyphenyl) methyl sulfone. Several other metabolites; S, S-diphenyl hydrogen phosphorodithiolate, S-phenyl dihydrogen phosphorothiolate, O-ethyl dihydrogen phosphate, O-ethyl S-phenyl hydrogen phosphorodithiolate and methyl phenyl sulfone were also identified. In the feces, blood, some organs and tissues, edifenphos was scarcely detected. Oral administration of edifenphos to goat at the rate of 10 mg/kg resulted the secretion of 0.0008 ppm of edifenphos in milk as the maximum level after 6 hr of the administration.

Environmental factors affecting the degradation of Dyfonate by soil fungi.

The ability of selected fungi to degrade the soil insecticide Dyfonate (O-ethyl S-phenyl ethylphosphonodithioate) into water-soluble, noninsecticidal metabolites was found to be dependent on the supply of nutrients, incubation time, temperature, pH, as well as other factors. With yeast extract as the carbon source (5 g/liter) and ammonium nitrate (1 g/liter) as the nitrogen source, both Rhizopus arrhizus and Penicillium notatum degraded the insecticide to a larger extent than with any other combination of nutrients used. With glucose as the carbon source, concentrations of ammonium nitrate above 5 g/liter inhibited the degradation of Dyfonate by R. arrhizus. Time-course studies on the metabolism of the insecticide indicated that Dyfonate was first absorbed by the fungal mycelium, where it was metabolized followed by the release of water-soluble, noninsecticidal, breakdown products into the culture media. The degradation appeared to involve the breakdown of Dyfonate into ethyl acetate soluble metabolites, such as ethylethoxyphosphonothioic acid, ethylethoxyphosphonic acid, methyl phenyl sulfoxide, and methyl phenyl sulfone. These compounds were then further degraded into water-soluble products. The optimum conditions for the degradation of the insecticide by R. arrhizus were observed at pH 6.0 to 7.0 and at 15-25 degrees C. Aged fungal mycelia were as active as mycelia in the logarithmic growth phase.

A Carbon-13 Nuclear Magnetic Resonance Investigation of Some Substituted Methyl Phenyl Sulfides, Sulfoxides, and Sulfones

Carbon-13 chemical shifts for 33 methyl phenyl sulfides, sulfoxides, and sulfones are reported. Observed trends are discussed in terms of the steric and electronic influences of the substituent groups. Additivity correlations for para-disubstituted materials are noted. In general, the shieldings of methyl carbons bonded to sulfur are rather insensitive to the nature of the aromatic substituents. By contrast to the proton shieldings, the CH3SO and CH3SO2 carbons exhibit nearly identical chemical shifts.

Metabolism of Dyfonate by soil fungi

The metabolism and detoxication of 14C-(ethoxy) and 14C-(ring)-Dyfonate were demonstrated with isolated soil fungi. Quantitative and qualitative differences in the production of insecticide metabolites were observed. Among the nine fungal species tested, Mucor plumbeus and Rhizopus arrhizus were most active in degrading the insecticide, while Penicillium notatum was the least active. This activity was evidenced by the production of increasing amounts of water-soluble 14C-compounds in the culture media and the disappearance (degradation) of the originally applied insecticide from the fungal cultures. The water-soluble metabolites were non-toxic to mosquito larvae. Hexane-extractable compounds from cultures of the most active species were non-toxic to fruit flies, while those from cultures of the less active fungal species were insecticidal. Among the metabolites produced and detected by thin-layer chromatography were primarily dyfoxon, ethylethoxyphosphonothioic acid, ethylethoxyphosphonic acid, methyl phenyl sulfoxide, and methyl phenyl sulfone. With Aspergillus niger and 14C-(ring)-Dyfonate, most of the radiocarbon recovered from the TLC-plates was associated with an unknown compound. Production of the metabolites by the fungi was a function of the live mycelia, followed by excretion of water-soluble 14C-compounds into the culture media.

Synthesis of 2-Methyl-3-oxa-A-norestra-1, 5 (10)-dien-17β-ol and 2-Methyl-3-oxa-4, 19-bisnorpregna-1, 5 (10)-dien-20-one

The titled compounds were synthesized from the corresponding 10-propargyl-des-A-9 (10)-en-5-one derivatives through the 3, 5-seco-4-nor-dioxo steroids. The preparation of des-A-19-norpregn-9 (10)-ene-5, 20-dione involving the condensation of phenyl methyl sulfone or dimethyl sulfone with methyl 1β-methoxycarbonyl-5, 5-ethylenedioxy-7amethyl-3aα, 7aβ-hexahydroindan-4x-yl propionate is also described.

Thiosteroids—XXXIII: 10β-methylsulfonyl and 10β-phenylsulfonyl des-a-estr-9(11)-ene derivatives and their alkylation reaction: Synthesis of A-furanosteroids

The titled compounds, 12a, 12 b, 21 a and 21b, were synthesized by the reaction of the α-sulfonyl carbanion generated from dimethyl sulfone or phenyl methyl sulfone with the bisketal 9 of methyl 7a-methyl-1,5-dioxo-3α,7aβ-hexahydroindan-4α-yl propionate prepared by fermentation of 5 and the subsequent oxidation of the product. Desulfurization of ketals of 21a and 21b gave the des-A-steroid 3a. Michael addition of 12a, 12b and 21b to methyl vinyl ketone led to the corresponding adducts with configurationally retained sulfonyl groups which were converted to 10β-methylsulfonyl and 10β-phenyl-sulfonyl steroids 27a, 27b and 27c respectively. On the other hand, reaction of 21b with methyl α-bromoacetate yielded 29, desulfurization of which gave 30 identical with the product of alkylation of the enamine 28 of 3a. A-Furanosteroids 1a and 37a were prepared from 30 and its 1-methyl derivative. The β axial configuration of the sulfonyl groups in the compounds was evidenced by the PMR and CD spectral data.

Electronic absorption spectra of some monosubstituted benzenes in the vapour phase

The near u.v. absorption spectra in the vapour phase and in solution of phenyl methyl sulfone, phenyl methyl sulfonate, benzene sulfonylchloride, benzenesulfonamide, benzoyl chloride, benzoyl bromide, and benzoyl cyanide have been investigated. The various transitions observed are discussed in terms of the frequency shift with respect to benzene transitions, intensity data, solvent effect and vibrational analysis. It is concluded that the absorption at the lower frequency is the same type for all monosubstituted benzene derivatives and it is related to A 1 g → B 2 u transition in benzene. The main absorption of high intensity in the middle spectral region seems to be dominated by charge transfer structures between the benzene ring and the substituent, and thus the analogy with the benzene transition at 1980 A breaks down for strong substituents.

Studies on Acetylenic Compounds. LV. Reactions of Phenyl 2-Propynyl Sulfone and Phenyl 3-Phenyl-2-propynyl Sulfone with Substituted Benzaldehydes

Phenyl 2-propynyl sulfone (IV) and five kinds of benzaldehyde derivatives were treated with sodium hydride to give the corresponding 1 : 1 addition products, respectively. The structures were assigned to 1-phenylsulfonyl-4-substitutedphenyl-trans-3-buten-2-ones (V) based on the spectroscopic data. The confirmation of the elucidated structure was made by an alternative unambiguous synthesis which consisted of treating methyl phenyl sulfone and ethyl cinnamate with sodium hydride, affording V and 1-phenylsulfonyl-4-phenyl-3-penten-2-one (VI). When phenyl 3-phenyl-2-propynyl sulfone (VII) was treated with the five substituted benzaldehydes, were obtained similar products to V, 1 : 1 addition compounds of VII and benzaldehydes. These were assigned to be 1-phenylsulfonyl-3-phenyl-4-substitutedphenyl-3-buten-2-ones (VIII) by the spectroscopic data and the comparison with V. The plausible mechanism of the reaction and the physical properties of these products are presented in some detail.