- Novel catalyst based on mono- and di-vanadium substituted Keggin polyoxometalate incorporated in poly(acrylic acid-co-acrylamide) polymer for the oxidation of sulfides
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Composite materials based on [PVxW12-xO40](3+x)? with x = 1 or 2 (PVW and PV2W respectively), included in poly(acrylic acid-co-acrylamide) gel (PAACA), were synthesized. The samples were characterized by different techniques such as FT-IR, 31P MAS-NMR, 51V-NMR, XRD, DTA-TGA, UV–vis DRS, and the acidic properties were estimated by means of potentiometric titration with n-butylamine. Samples containing 10, 20 and 30% (w/w) of polyoxotungstovanadate (POTV) were prepared by inclusion of the POTV in the polymer during its synthesis. According to Fourier transform infra-red and magic angle spinning-nuclear magnetic resonance studies, the predominat anion present in the samples is [PVxW12-xO40](3+x)?, and there is no evidence of its decomposition during the synthesis of hybrid materials and the drying step. According to XRD results, these anions are greatly dispersed in the PAACA or present as amorphous phases. UV–vis DRS data reveal that the samples synthesized using POTV with two vanadium atoms (PAACA-PV2W) exhibit lower values of absorption edge energy than those prepared using PVW (PAACA-PVW), which correlates with a higher oxidizing capacity. The potentiometric titration shows strong acid sites of the hybrid materials, and their number increases with the number of vanadium atoms and with the amount of POTV incorporated in the PAACA grid. The hybrid materials prepared by inclusion of POTV during the polymer synthesis exhibit appropriate physicochemical features to catalyze the oxidation of diphenyl sulfide (DPS) to its sulfone employing acetonitrile as solvent H2O2 as a green oxidant. The samples with 30% w/w of POVT, which show higher catalytic performance, are suitable for the DPS oxidation and can be reused without remarkable drop of their catalytic activity. Furthermore, they show high activity as a catalyst in the oxidation reaction of 4,4′-diamino diphenyl sulfide to the corresponding sulfone (dapsone) used for malaria treatment.
- Frenzel, Romina A.,Romanelli, Gustavo P.,Pizzio, Luis R.
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Read Online
- Regioselective C-H Thioarylation of Electron-Rich Arenes by Iron(III) Triflimide Catalysis
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A mild and regioselective method for the preparation of unsymmetrical biaryl sulfides using iron(III) catalysis is described. Activation of N-(arylthio)succinimides using the powerful Lewis acid iron(III) triflimide allowed the efficient thiolation of a range of arenes, including anisoles, phenols, acetanilides, and N-heterocycles. The method was applicable for the late-stage thiolation of tyrosine and tryptophan derivatives and was used as the key step for the synthesis of pharmaceutically relevant biaryl sulfur-containing compounds such as the antibiotic dapsone and the antidepressant vortioxetine. Kinetic studies revealed that while N-(arylthio)succinimides bearing electron-deficient arenes underwent thioarylation catalyzed entirely by iron(III) triflimide, N-(arylthio)succinimides with electron-rich arenes displayed an autocatalytic mechanism promoted by the Lewis basic product.
- Dodds, Amy C.,Sutherland, Andrew
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p. 5922 - 5932
(2021/05/04)
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- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
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supporting information
p. 8691 - 8695
(2021/10/22)
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- NEW CYCLOADDUCT PRECURSORS OF DIHALODIPHENYLSULFONES AND PREPARATIONS THEREOF
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The invention relates to new compounds of formula (I) wherein X represents a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine, which are useful for the preparation of 4,4'dihalodiphenylsulfones of formula (III) wherein X is as defined above.
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Page/Page column 21
(2019/02/25)
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- C-S coupling with nitro group as leaving group via simple inorganic salt catalysis
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An efficient and practical synthetic protocol to synthesize nonsymmetrical aryl thioethers by nucleophilic aromatic substitution (SNAr) reaction of nitroarenes by thiols with potassium phosphate as the catalyst is described. Various moderate to strong electron-withdrawing functional groups are tolerated by the system to provide thioethers in a good to excellent yields. We also showed that the present method allows access to 3 drug examples in a short reaction time. Finally, mechanistic studies suggest that the reaction may form the classic Meisenheimer complex through a two-step addition-elimination mechanism.
- Xuan, Maojie,Lu, Chunlei,Lin, Bo-Lin
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- Palladium-catalyzed one-step synthesis of symmetrical diaryl sulfones from aryl halides and a sulfur dioxide surrogate
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A convenient method for the one-step synthesis of symmetrical diaryl sulfones from aryl halides has been developed. A keystone of the method is the use of K2S2O5, which can be easily and safely handled, as a sulfur dioxide surrogate. The palladium catalyst bearing P(t-Bu)3 as a ligand enables formation of the desired sulfones without significant formation of byproducts.
- Tanaka, Hiromichi,Konishi, Hideyuki,Manabe, Kei
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supporting information
p. 760 - 763
(2019/08/02)
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- Copper complex catalyst and preparation method thereof as well as 4,4 ’ - application of copper complex catalyst in synthesis of diaminodiphenyl sulfone (by machine translation)
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The invention belongs to the technical field of, organic synthesis, and particularly relates to a copper complex catalyst and a preparation method thereof 4,4 ’ - as well as a structural. formula of the copper complex catalyst in catalysis: synthesis of diaminediphenyl sulphone. The preparation method of: the 5 - copper complex catalyst according to the invention has, the advantages that. the copper, complex catalyst, is simple in, synthesis 5 °C step, and 2-4 the, yield of the copper, complex 4,4 ’ - catalyst in the application of the copper complex catalyst in the catalytic synthesis of the diaminodiphenyl sulfone 4,4 ’ - is higher than that of the copper. complex catalyst, 84 - 92%. (by machine translation)
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Paragraph 0019; 0053-0060
(2019/12/31)
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- Preparation method of diaminodiphenyl sulfone
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The invention relates to drug synthesis methods, particularly to a preparation method of diaminodiphenyl sulfone. The method comprises taking a formula-n compound as the raw material, adding in solvent, performing oxidizing reaction under the condition of hydrogen peroxide and catalysts to obtain a formula-III compound, hydrolyzing the formula-III compound under alkali conditions and then regulating pH to obtain formula-I diaminodiphenyl sulfone. The preparation method of the diaminodiphenyl sulfone is simple, high in safety, low in price and simple in acquisition of applied catalysts, recyclable in the solvent, environmentally friendly and high in quality of prepared products. When detected by national standards, the content of single impurity and the content of total impurities of the prepared diaminodiphenyl sulfone can be lower than 0.1%.
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Paragraph 0040-0041; 0042-0043; 0044-0045
(2018/08/28)
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- Synthesis method for dapsone
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The invention belongs to the field of medical chemistry, and discloses a preparation method for dapsone, wherein the method comprises the following steps: with chlorobenzene as a raw material and sulfuric acid as a solvent, carrying out a dehydration reaction to obtain dichlorodiphenyl sulfone, and then adding an ammoniation reagent into the reaction system, to prepare dapsone. The dilute sulphuric acid is used as the solvent, no any ligand, no protection with inert gas or no separation is required, sodium hydrosulfite is added as a reducing agent, and dapsone can be prepared. The method can obviously improve the yield and quality of dapsone.
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Paragraph 0011
(2017/08/05)
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- PROCESS FOR THE SYNTHESIS OF DAPSONE AND ITS INTERMEDIATES
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A process for the synthesis of Dapsone and intermediates thereof are described.
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Page/Page column 11
(2016/03/08)
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- Carbon-supported metal-modified lacunary tungstosilicic polyoxometallates used as catalysts in the selective oxidation of sulfides
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Lacunary tungstosilicic polyoxometallates modified with transition metal ions [SiW11O39M(H2O)]6-, where M = Mn2+, Fe2+, Co2+or Cu2+, were synthesized and supported on activated carbon to obtain the SiW11MC catalysts. The samples were characterized by FT-IR, XRD, N2 adsorption-desorption measurements, and the acidic properties were determined using the isopropanol dehydration test reaction. The activity and selectivity of the catalysts were evaluated in the selective oxidation of a series of sulfides to sulfoxides or sulfone. The reaction was carried out in acetonitrile as solvent using H2O2 35% p/V as a clean oxidant. The conversion values decreased in the following order: SiW11MnC > SiW11FeC > SiW11CuC > SiW11CoC. The catalysts were reused without appreciable loss of their catalytic activity. It was found that the activity of the catalysts decreases in parallel with the increment in the reduction temperature values. The most easily reducible catalyst displayed the highest conversion values. We found a convenient and selective procedure for oxidizing sulfides to sulfoxides or sulfones using aqueous hydrogen peroxide and a catalytic amount of lacunary tungstosilicic polyoxometallates supported on carbon at low temperatures (20-50 °C) in a reasonably short reaction time
- Frenzel, Romina,Sathicq, ángel G.,Blanco, Mirta N.,Romanelli, Gustavo P.,Pizzio, Luis R.
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- The synthesis of diarylsulfones with simple arenes and K2S2O8 through double C-S bond formation
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An unprecedented double C-S bond formation method has been developed to prepare both symmetric and unsymmetric diarylsulfones with simple arenes in a single step. This represents the first example that K2S2O8 can be employed as a highly effective sulfonating agent to synthesize diarylsulfones. The reaction demonstrates excellent reactivity, good functional group tolerance and high yields.
- Yang, Yiqing,Chen, Zhang,Rao, Yu
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p. 15037 - 15040
(2014/12/11)
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- SOLUBLE PHARMACEUTICAL FORMS OF N,N'-DIAMINODIPHENYL SULPHONE FOR OPTIMUM USE IN THE TREATMENT OF VARIOUS DISEASES
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The present invention aims to demonstrate that a soluble pharmaceutical formulation can be prepared of N,N'-Diaminodiphenyl sulfone which is useful in the development of an ideal drug for use against cerebral infarction, epilepsy, traumatic spinal cord injury, cranio-encephalic trauma, leprosy, Pneumocystis carinii infections and any condition which requires rapid and complete absorption of the compound. A s a representative example of this application, the dissolution of N,N'-Diamino-diphenyl sulfone was evaluated as a neuroprotector in a model of acute cerebral infarction in rats. In this study, N,N'-Diamino-diphenyl sulfone showed significant prevention of brain damage, without presenting adverse effects in animals. It is also shown that the soluble pharmaceutical formulations prepared in this manner produce peak blood levels 30 minutes from oral administration and immediately via the intravenous route.
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- Functionalized Photoreactive Compounds
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The present invention concerns functionalized photoreactive compounds of formula (I), that are particularly useful in materials for the alignment of liquid crystals. Due to the adjunction of an electron withdrawing group to specific molecular systems bearing an unsaturation directly attached to two unsaturated ring systems, exceptionally high photosensitivities, excellent alignment properties as well as good mechanical robustness could be achieved in materials comprising said functionalized photoreactive compounds of the invention.
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- PROCESS FOR SYNTHESIS OF 4-4'-DIAMINO-DIPHENYL-SULFONE
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A new process for the preparation and purification of 4-4'-diamino-diphenyl-sulfone (dapsone) is described. The process described is a three step process comprising a condensation reaction with the synthesis of a thioeter intermediate and then steps of oxidation and reduction in suitable conditions in order to obtain a product with good yield and purity.
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Page/Page column 9
(2008/06/13)
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- Chemoselective reduction of azides with sodium sulfide hydrate under solvent free conditions
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Sodium sulfide hydrate has been employed for an efficient reduction of a variety of azides to the primary amines in good-to-excellent yields under solvent-free system and without perturbing many active functionalities such as ether, carbonyl, sulfonyl, and nitro.
- Kazemi, Foad,Kiasat, Ali Reza,Sayyahi, Sohyl
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p. 1813 - 1817
(2007/10/03)
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- Process for the preparation of organic compounds containing a sulfinyl or sulfonyl group in the presence of epsilon-phthalimidoperhexanoic acid
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A process for the oxidation of thioethers to sulfoxides or sulfones or for the oxidation of sulfoxides to sulfones by treatment of thioethers or sulfoxides with an oxidizing amount of ε-phthalimidoperhexanoic acid is particularly useful for the preparation of compounds of industrial interest, in particular pharmaceuticals for human or veterinary use.
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- Process for the preparation of organic compounds containing a sulfinyl or sulfonyl group
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A process for the oxidation of thioethers to sulfoxides or sulfones or for the oxidation of sulfoxides to sulfones by treatment of thioethers or sulfoxides with an oxidizing amount of ε-phthalimidoperhexanoic acid is particularly useful for the preparation of compounds of industrial interest, in particular pharmaceuticals for human or veterinary use.
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- NADH cytochrome b5 reductase and cytochrome b5 catalyze the microsomal reduction of xenobiotic hydroxylamines and amidoximes in humans
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Hydroxylamine metabolites, implicated in dose-dependent and idiosyncratic toxicity from arylamine drugs, and amidoximes, used as pro-drugs, are metabolized by an as yet incompletely characterized NADH-dependent microsomal reductase system. We hypothesized that NADH cytochrome b5 reductase and cytochrome b5 were responsible for this enzymatic activity in humans. Purified human soluble NADH cytochrome b5 reductase and cytochrome b5 expressed in Escherichia coli, efficiently catalyzed the reduction of sulfamethoxazole hydroxylamine, dapsone hydroxylamine, and benzamidoxime, with apparent Km values similar to those found in human liver microsomes and specific activities (Vmax) 74 to 235 times higher than in microsomes. Minimal activity was seen with either protein alone, and microsomal protein did not enhance activity other than additively. All three reduction activities were significantly correlated with immunoreactivity for cytochrome b5 in individual human liver microsomes. In addition, polyclonal antibodies to both NADH cytochrome b5 reductase and cytochrome b5 significantly inhibited reduction activity for sulfamethoxazole hydroxylamine. Finally, fibroblasts from a patient with type II hereditary methemoglobinemia (deficient in NADH cytochrome b5 reductase) showed virtually no activity for hydroxylamine reduction, compared with normal fibroblasts. These results indicate a novel direct role for NADH cytochrome b5 reductase and cytochrome b5 in xenobiotic metabolism and suggest that pharmacogenetic variability in either of these proteins may effect drug reduction capacity.
- Kurian, Joseph R.,Bajad, Sunil U.,Miller, Jackie L.,Chin, Nathaniel A.,Trepanier, Lauren A.
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p. 1171 - 1178
(2007/10/03)
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- Synthesis of deuterated 4, 4′-diaminodiphenylsulfone (Dapsone) and related analogs
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A general scheme tor the synthesis ot 4,4′-diaminodiphenylsulfone-d5 (Dapsone) from aniline-d5 is described. The method may have general application and the preparation of the related analogs, 4,4′-dimethylaminodiphenyl sulfone from aniline-d5 and 4,4′-dimethoxydiphenyl sulfone from phenol-d5, is also described. Copyright
- Gannett, Peter M.,Johnson II, Edward M.,Grimes, Michael A.,Myers, Alan L.,Deavers III, Robert E.,Tracy, Timothy S.
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p. 107 - 114
(2007/10/03)
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- Thermoplastic resin composition and a method of molding the same
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This invention provides a thermoplastic resin composition comprising a thermoplastic resin and 0.1 to 100 parts by weight, per 100 parts by weight of the thermoplastic resin, of an imide compound prepared, e.g., by dehydration condensation of 1,2,3,4-butanetetracarboxylic acid or a monoanhydride or a dianhydride thereof with a primary amine, and a method of molding the resin composition.
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- Studies on 2,3,N,N'-substituted 4,4'-diaminodiphenylsulfones as potential antimalarial agents
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A series of new 4,4'-diaminodiphenylsulfones substituted at 2 and 3 position and also at primary amino group of the phenyl rings have been synthesised and evaluated for their antimalarial activity against Plasmodium berghei infection in mice. Some of these compounds were active and showed complete inhibition of parasitaemia which included 7a1-7a4, 7b3, 7b4 and 16a at 1 mg/kg i.p. for 4 days and 16a, at 0.3 mg/kg for 4 days. Some compounds tested for their synthetase inhibitory action in cell-free system isolated from P. berghei (7b1, 7b2 and 8b2) were found to be more active than diaminodiphenylsulphone. The difference in order of activity between these in vivo and in vitro tests may be due to differences in their pharmacokinetic properties.
- Saxena,Saxena,Raina,Chandra,Sen,Anand,Seydel,Wiese
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p. 1081 - 1084
(2007/10/02)
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- Bis-(maleamic acid) derivatives of triamines
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The compositions described herein comprise polyimides having bis-maleimide terminal groups and having the formula: STR1 wherein Q is a trivalent aromatic radical, Ar is a divalent aromatic radical, Ar" is a tetravalent aromatic radical and n has a value of 0-20. Derivatives may be made of these compounds by homopolymerization, copolymerization with other copolymerizable materials and by reaction with Diels-Alder reactable materials.
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- Silicone containing bis-thioether aromatic amines
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A silicone containing bis-thioether aromatic amine has a chemical structure wherein an aromatic nucleus at each end of the chemical radical is chemically bonded to the remainder of the chemical radical by either sulfur, sulfoxide or sulfone.
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