Sulphonic Derivatives Research Articles

One-step synthesis of mixed carboxylate sulphonate esters of diols

Reaction between 1,2- or 1,3-diols, sulphonic acids and carboxylic acid derivatives leads directly to mixed carboxylate sulphonate esters. The process is believed to involve 1,3-dioxolan-2-yl cation or 1,3-dioxan- 2-yl cation intermediates.

Chromatographic separation of selenohypotaurine, selenotaurine, selenohomohypotaurine and selenohomotaurine

By either paper or ion-exchange chromatography the two seleninic compounds selenohypotaurine and selenohomohypotaurine, and the two selenonic compounds selenotaurine and selenohomotaurine may be all separated from each other. On paper chromatography seleninic derivatives may be separated from the corresponding sulphinic compounds, while selenonic compounds show R F values similar to those of the corresponding sulphonic derivatives. These two latter types of compounds may be differentiated, however, since selenonic compounds liberate iodine from HI, while sulphonic compounds do not. Also by automated ion-exchange chromatography seleninic derivatives are well separated from the analogous sulphinic compounds, while selenonic compounds are eluted together with the corresponding sulphonic compounds.

Degradation of Carboxin and Oxycarboxin by a Species of Pseudomonas Isolated from Soil

An unidentified species of Pseudomonas capable of utilising Carboxin and Oxy- carboxin as sole source of carbon and nitrogen was isolated from red sandy loam soil perfused with solutions of these fungicides. The bacterium hydrolyzed Oxycarboxin to aniline and oxidised Carboxin to the corresponding sulphoxide and then to the sul- phone. The sulphone derivative was further hydrolyzed liberating aniline. Further, deg- radation of aniline by the organism resulted in the accumulation of ammonium which was partly oxidized to nitrite. Nitrite accumulated in the media without further oxidation to nitrate.

Biotransformation of 10-(3-quinuclidinylmethyl)phenothiazine (LM 209), a new anti-allergy agent and the distribution and excretion of its metabolites

1. Metabolism of 10-(3-quinuclidinylmethyl)phenothiazine and the distribution and excretion of the metabolites, especially the sulphoxides, were studied in rat and dog after oral and intravenous administration. 2. Urine and bile contained relatively little unchanged drug. The sulphoxide, sulphone, N-oxide and N-oxide sulphoxide derivatives were identified as well as glucuronide and sulphate conjugates, suggesting the formation of hydroxylated products. Faeces contained mainly unchanged drug but also some sulphoxide and N-oxide. In the lung, brain and cerebro spinal fluid only unchanged drug and traces of sulphoxide were found, whereas in liver sulphone and N-oxide were also present. 3. After administration of the 35S-labelled sulphoxide, the distribution of radio-activity was very different from that observed with LM 209. The biological half-life (t0-5) of SM 209 was 3 to 4 times higher than that of the sulphoxide. LM 209 is better absorbed and its diffusion in the organism is superior. 4. Metabolism of LM 209 by liver microsome preparation was more rapid than metabolism of the sulphoxide. 5. These findings indicate that the activity of LM 209 is due more to the molecule itself than to its major metabolite.

Use of Thin‐Layer and Paper Chromatography for Detection of Ortho‐ and Para‐Quinones Formed in the Course of Phenol Oxidation

AbstractIn order to detect the labiles in the aqueous solution of the benzene‐ and naphthoquinones, they were preliminarily transformed with the aid of the benzene sulphinic acid into stable sulphonic derivatives. Methods were developed of the chromatographic detection on paper and in a thin layer of the β‐naphthol, phenol, ortho‐, para‐dioxybenzenes and their sulphonic derivatives with joint presence in the solution of ortho‐ and para‐isomers of the dioxyderivatives.For the chromatographic separation of the ortho‐ and para‐derivatives, the ability of ortho‐isomers to form chelate complexes with boric acid or to precipitate with mean laed acetate salt was made use of.With the aid of the given method, the stage of the quinone formation in the course of abiogenic and biochemical (under the action of Nitella sp.) oxidation of benzene, phenol, β‐naphthol, pyrocatechol, hydroquinone has been proved. Oxidation under the action of Nitella sp. leads to the formation of the dioxybenzene ortho‐isomers and their derivatives.

Organometallic complexes in synthesis. Nucleophilic reactions on tricarbonylcyclohexadienyliron cations: Some cyclohexadienyl phosphinic, phosphonic and sulphonic acid derivatives

Organometallic complexes in synthesis. Nucleophilic reactions on tricarbonylcyclohexadienyliron cations: Some cyclohexadienyl phosphinic, phosphonic and sulphonic acid derivatives

Reactions of heterocycles with thiophosgene. Part V. 7-Chloro-1,2-dihydro-4-methoxy-2-thioxoquinoline-3-carbaldehyde, a product from 7-chloro-4-methoxyquinoline

7-Chloro-4-methoxyquinoline undergoes ring scission on treatment with thiophosgene and barium carbonate. The resulting 4-chloro-2-isothiocyanato-β-methoxycinnamaldehyde (3) undergoes ready ring closure to 7-chloro-1,2-dihydro-4-methoxy-2-thioxo-quinoline-3-carbaldehyde (4). Some reactions of the thioxoquinoline (4) and the corresponding ethylthio-(7) and sulphone (44) derivatives are described which give rise to other heterocyclic systems.

Aryl versus alkyl and vinyl migration in the mass spectra of sulphone derivatives

AbstractThe 2‐acetoxyethyl aryl sulphones were found to be unsuitable for a comparative study with the corresponding chlorides and alcohols as their predominant fragmentation involved cleavage of the aliphatic carbon‐sulphur bond with charge retention on the aliphatic part of the molecule The expected McLafferty rearrangement to yield an intermediate vinyl species was only a minor fragmentation path.Indirect evidence for alkyl migration in the molecular ion was found in the spectrum of 2‐acetoxyethyl 1‐paranitro phenyl sulphone. The spectra of the aryl vinyl sulphones revealed intense [Aryl SO]+ ions resulting from preferred migration of the vinyl group from sulphur to oxygen.

AN INVESTIGATION INTO SOME OF THE METHODS AVAILABLE FOR THE DETERMINATION OF THE SULPHONATE CONTENT OF OIL‐SOLUBLE PETROLEUM SULPHONATES

The present situation in the industry demands reliable and rapid methods of material control, from the raw materials to the final product. New methods and techniques are constantly being introduced to fulfil this requirement; it is essential, particularly for the routine analyst, to choose a method of control which is both precise and rapid. It is the purpose of this paper to investigate some of the methods applicable to the determination of the sulphonate content of the oil soluble petroleum sulphonates. These are believed to consist of the mono sulphonic derivative of hydrocarbons of an approximate formula CnH2n‐13SO3H, containing an aromatic naphthenic nucleus with a long side chain. A brief outline of the manufacture and use of the petroleum sulphonates will be given, together with a brief survey of some of the analytical methods available for their determination; this will be developed to include an investigation of the precision and comparison of two of these methods.

Nuclear-magnetic-resonance spectrum of a sulphone derivative of chlorogenoquinone.

Nuclear-magnetic-resonance spectrum of a sulphone derivative of chlorogenoquinone.

The binding of aromatic sulphonic acids to bovine serum albumin

The partitioning of several naphthylamine sulphonate derivatives between water and solutions of dodecylamine in hexane and between water and detergent micelles was studied as an aid to understanding the binding of these dyes to bovine serum albumin. The data obtained indicate that the distribution of the dyes between the two phases depends both on non-polar and electrostatic interactions. A similar dependence was found in the binding of these dyes to bovine serum albumin. Further studies with l-thyroxine and Trypan blue showed that these molecules are bound to bovine serum albumin at the sites where naphthalymaine binding occurs. The binding of Trypan blue showed interaction effects and an explanation for this is suggested in terms of a competition by the functional groups of Trypan blue for a limited number of sites.

Blood levels of isoniazid and of its methan sulphonate derivative in rapid and slow inactivators after oral administration

Blood levels after oral administration of isoniazid and its metharesulphonate derivative (methaniazid) were compared in a group of 20 subjects consisting of 10 ‘rapid’ and 10 ‘slow’ inactivators. The two drugs were administered orally at the dose of 5 mg/kg., calculated as isoniazid: blood samples were withdrawn after three, six and nine hours and assayed with the vertical diffusion method using Mycobacterium tuberculosis H37Rv as test organism. Statistical analysis of the data showed that in rapid inactivators the blood levels reached after administration of methaniazid were significantly higher than those obtained with isoniazid (P<0.001). In slow inactivators the difference of the blood levels obtained with the two drugs did not reach a significant level (0.10>P>0.05). Sur un groupe de 20 individus, dont 10 inactivateurs ‘rapides’ et 10 ‘lents’, on a recherché les avantages de l'administration ‘per os’ du derivé methanesulfoné de l'isoniazide par rapport à l'isoniazide. Les deux produits ont été administrés à la posologie de 5 mg/kg d'isoniazide et les taux sanguins de produit actif ont été comparé 3. 6 et 9 heures après l'administration. L'analyse statistique des résultats montre que chez les inactivateurs rapides les taux sanguins après administration de methaniazide sont significativement plus élevés que ceux obtenus aprés administration, d'isoniazide (P<0.001). Chez les inactivateurs lents par contre, la différence des taux sanguins des deux médicaments n'atteint pas le taux de signification (0.10>P>0.05). En un grupo de 20 individuos. 10 inactivadores rápidos y 10 inactivadores lentos, se compararon los niveles sanguineos alcanzados despues de administrar isoniazida, y su derivado methanesulfonato (methaniazida). Ambas drogas se administraron oralmente, a la dosis de 5 mg./kg. calculadas en isoniazida; se obtuvieron muestras de sangre a las tres, seis y nueve horas y se empleó el método de difusión vertical usando el Mycobacterium tuberculosis H37Rv como germen testigo. El análisis estadístico de los datos mostró que en los inactivadores rápidos el nivel sanguíneo alcanzado despues de administrar methaniazida era significativamente más elevado que cuando se daba isoniazida (P<0.001). En los inactivadores lentos la diferencia de los niveles sanguineos obtenida con las dos drogas no fué estadísticamente significativa (0.10.>P>0.05).

Proton resonance spectra of heterocycles. Part V. 4(1H)-cinnolone and substituted 4-cinnolones

The literature n.m.r. assignment for 4-cinnolones is revised. The spectra of substituted 4-cinnolones are used to confirm the gross structures of 4-cinnolones and to investigate the tautomerism of some sulphonic acid derivatives. The effect of substituents on chemical shifts and coupling constants in the cinnolone series is discussed.

Photochemical reactions of azo compounds. XIII. Photochemical reaction of 11H-Dibenzo[c,f]-[1,2]-diazepine under acidic conditions

11H-Dibenzo[c,f]-[1,2]-diazepine is converted into a mixture of dibenzo[c,f]-[1,2]-diazepin-11-one, 2,2?-diaminobenzophenone, and 2,2?- diaminodiphenylmethane when irradiated in weakly acidic ethanol. Irradiation of the same compound in concentrated sulphuric acid appears to give only a sulphonic acid derivative of diaminobenzophenone. No photochemical reaction occurs in neutral ethanol or in benzene.

Butadiene sulphone chemistry. Part IV. Evidence for the structures of some butadiene sulphone derivatives from proton magnetic resonance measurements

Proton magnetic resonance data are given for some butadiene sulphone derivatives described earlier. The results support the earlier deductions.

The chemotherapy of schistosomiasis. VII. 2-Methyl- and 2-(substituted methyl)-4-aminophenyl ethers.

Chloromethylation of p-nitrophenol or its alkyl ethers gave reactive 2-chloromethyl intermediates which have been converted into 2-hydroxymethyl-(VII), 2-mercaptomethyl-(II), or 2-aminomethyl-4-nitrophenyl ethers (X), and various acyl, alkyl, aryl, and sulphone derivatives. The amines (VIII) obtained on reduction have been studied as schistosomicides.

Benzoate displacements on sulphonate esters of some 1,2- O-isopropylidenepentofuranoses

The benzoate displacement of sulphonate derivatives of several 1,2- O-isopropylidenepentofuranoses has been studied. Displacement occurs readily with 5-sulphonates, more slowly with endo-3-sulphonates, and not at all with exo-3-sulphonates. Neighbouring-group participation from 5-benzoate groups does not assist in the displacement of the 3-sulphonates.

Über die chemische Konstitution der mit Divinylsulfon vernetzten Cellulose. 12. Mitteilung über textilchemische Untersuchungen

AbstractCotton and viscose fibres treated with divinyl sulphone under alkaline conditions were degraded in sulphuric acid. By column chromatography degradation products have been identified which contain two glucose units on mono‐ and dimeric sulphone derivatives, i.e. glucose ethers of 2,2′‐dihydroxyethylsulphone and of 2,2′‐bis‐(hydroxyethylsulphonyl)‐diethylether. This is the first direct chemical proof of the existence of cross‐linkages in cellulose treated with bifunctional reagents.

Preparation of aryl difluoromethyl ether, thioether and sulphone derivatives. Electronic properties of the difluoromethoxy, -methylthio and -methylsulphonyl substituents.

Preparation of aryl difluoromethyl ether, thioether and sulphone derivatives. Electronic properties of the difluoromethoxy, -methylthio and -methylsulphonyl substituents.

THE METHYL 2-O- (BENZYLTHIO)CARBONYL DERIVATIVE AS A PRECURSOR TO PARTIAL ESTERS OF METHYL α-D-GLUCOPYRANOSIDE

The utility of the thiocarbonyl group for blocking the C2 hydroxyl in methyl glucosides has been demonstrated. Methyl 2-O-(benzylthio)carbonyl-α-D-glucopyranoside has been synthesized in good yield and its structure proved. Use of this 2-O-thiocarbonyl derivative in conjunction with acid-labile blocking groups has permitted the first syntheses of the following esters of methyl α-D-glucopyranoside: 3-O-benzoyl-, 3,4-di-O-benzoyl-, and 3,4,6-tri-O-benzoyl-, and the crystalline 2-O-(p-toluene)sulphonate derivative of each.