- Aromatic Chlorosulfonylation by Photoredox Catalysis
-
Visible-light photoredox catalysis enables the efficient synthesis of arenesulfonyl chlorides from anilines. The new protocol involves the convenient in situ preparation of arenediazonium salts (from anilines) and the reactive gases SO2and HCl (from aqueous SOCl2). The photocatalytic chlorosulfonylation operates at mild conditions (room temperature, acetonitrile/water) with low catalyst loading. Various functional groups are tolerated (e.g., halides, azides, nitro groups, CF3, SF5, esters, heteroarenes). Theoretical and experimental studies support a photoredox-catalysis mechanism.
- Májek, Michal,Neumeier, Michael,Jacobi von Wangelin, Axel
-
-
Read Online
- Proline-Based Allosteric Inhibitors of Zika and Dengue Virus NS2B/NS3 Proteases
-
The NS2B/NS3 serine proteases of the Zika and Dengue flaviviruses are attractive targets for the development of antiviral drugs. We report the synthesis and evaluation of a new, proline-based compound class that displays allosteric inhibition of both proteases. The structural features relevant for protease binding and inhibition were determined to establish them as new lead compounds for flaviviral inhibitors. Based on our structure-activity relationship studies, the molecules were further optimized, leading to inhibitors with submicromolar IC50 values and improved lipophilic ligand efficiency. The allosteric binding site in the proteases was probed using mutagenesis and covalent modification of the obtained cysteine mutants with maleimides, followed by computational elucidation of the possible binding modes. In infected cells, antiviral activity against Dengue virus serotype 2 using prodrugs of the inhibitors was observed. In summary, a novel inhibitor scaffold targeting an allosteric site shared between flaviviral NS2B/NS3 proteases is presented whose efficacy is demonstrated in vitro and in cellulo.
- Millies, Benedikt,Von Hammerstein, Franziska,Gellert, Andrea,Hammerschmidt, Stefan,Barthels, Fabian,G?ppel, Ulrike,Immerheiser, Melissa,Elgner, Fabian,Jung, Nathalie,Basic, Michael,Kersten, Christian,Kiefer, Werner,Bodem, Jochen,Hildt, Eberhard,Windbergs, Maike,Hellmich, Ute A.,Schirmeister, Tanja
-
-
Read Online
- Preparation method of substituted benzene sulfonyl chloride
-
The invention provides a preparation method of substituted benzene sulfonyl chloride, which comprises the following steps: carrying out diazotization reaction on an aniline compound with a structure as shown in a formula I to obtain fluoboric acid diazonium salt with a structure as shown in a formula II; obtaining substituted benzene sulfonyl chloride with a structure as shown in a formula III from the fluoboric acid diazonium salt with the structure as shown in the formula II; wherein R is selected from any one of ortho-chlorine, bromine, methyl, chloromethyl, bromomethyl, nitro, cyano, acetyl, meta-chlorine, bromine, methyl, chloromethyl, bromomethyl, nitro, cyano, acetyl, para-chlorine, bromine, methyl, chloromethyl, bromomethyl, nitro, cyano and acetyl. The preparation method of the substituted benzene sulfonyl chloride provided by the invention is simple in reaction process, easy to operate, ideal in effect and suitable for industrial production.
- -
-
Paragraph 0055-0058
(2021/05/08)
-
- Facile synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazides
-
A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.
- Chen, Rongxiang,Xu, Shaohong,Shen, Fumin,Xu, Canran,Wang, Kaikai,Wang, Zhanyong,Liu, Lantao
-
-
- Preparation method of dye intermediate 3-(beta-hydroxyethyl sulfonyl) aniline
-
The invention discloses a preparation method of dye intermediate 3-(beta-hydroxyethyl sulfonyl) aniline. The preparation method comprises the following steps: carrying out chlorosulfonation reaction on nitrobenzene and chlorosulfonic acid to obtain m-nitrobenzenesulfonyl chloride; reducing m-nitrobenzenesulfonyl chloride by using sodium pyrosulfite, and regulating the pH value of a reaction solution to 7.4-7.7 in the reaction process; adding sodium chloride after the reaction is finished, and salting out to obtain a reduction product; wherein the molar ratio of sodium pyrosulfite to m-nitrobenzenesulfonyl chloride to sodium chloride is (0.68-0.685): 1: (0.54-0.58); adding ethylene oxide into the reduction product, controlling the PH value to be 7-7.5, and reacting to obtain a condensationproduct; adopting stannous chloride and a Pd/C catalyst for reducing the condensation product to obtain 3-(beta-hydroxyethyl sulfonyl) aniline, wherein the molar ratio of the condensation product to the Pd/C catalyst is (0.45-0.46): 1: 0.0012. The preparation method provided by the invention can effectively inhibit the generation of byproducts in each process link, not only can improve the productquality, but also reduce environmental pollutants, and has a green and environment-friendly effect.
- -
-
Paragraph 0041-0044; 0058-0061; 0075-0078; 0092-0095; 0109
(2020/04/17)
-
- Preparation method of meta-ester and meta-ester (by machine translation)
-
The molar ratio of the reduction product, the ethylene oxide and the sodium phosphate is 7.4 - 7.7; the molar ratio of the reduction product, the ethylene oxide and the sodium phosphate ranges from 0.68 - 0.685: (0.54 - 0.58): 7 - 7.5; the molar ratio Pd / C catalyst in each process link is controlled to 1; the product quality is improved; the environmental pollutants are reduced; and the method has the advantages of environmental protection and environmental protection effects and is obtained by esterification reaction and synthesis of the intermediate ester and Pd / C at PH ranges of (0.52 - 0.63): (0.00.12) 0.0012; and the method comprises the following steps of reducing the product, reducing environmental pollutants and 0.45 - 0.46 reducing environmental pollutants by adding sodium chloride and a Pd/C catalyst to the condensation product after the reaction is complete. (by machine translation)
- -
-
Paragraph 0040-0043; 0058-0061; 0076-0079; 0094-0097
(2020/06/16)
-
- Preparation method of dye intermediate 3-(beta-hydroxyethyl sulfonyl)-nitrobenzene
-
The invention discloses a preparation method of a dye intermediate 3-(beta-hydroxyethyl sulfonyl)-nitrobenzene. The preparation method comprises the following steps: S1, carrying out chlorosulfonationreaction on nitrobenzene and chlorosulfonic acid to obtain m-nitrobenzenesulfonyl chloride; S2, reducing the m-nitrobenzenesulfonyl chloride by using sodium pyrosulfite, and adjusting the pH value ofthe reaction solution to 7.4-7.7 in the reaction process; adding sodium chloride after the reaction is finished, and salting out to obtain a reduction product, wherein the molar ratio of the sodium pyrosulfite to the m-nitrobenzenesulfonyl chloride to the sodium chloride is (0.68-0.685) : 1 : (0.54-0.58); and S3, adding ethylene oxide and sodium phosphate into the reduction product, controlling the pH value to be 7-7.5, and reacting to obtain 3-(beta-hydroxyethyl sulfonyl)-nitrobenzene, wherein the molar ratio of the reduction product to the ethylene oxide to the sodium phosphate is 1: (0.52-0.63): 0.00.12. The preparatio method effectively inhibits the generation of byproducts in each process link, not only improves the product quality, but also reduces environmental pollutants and has agreen and environment-friendly effect.
- -
-
Page/Page column 5-9
(2020/05/14)
-
- Preparation method for symmetric diaryl disulfide
-
The invention discloses a preparation method for symmetric diaryl disulfide. The preparation method comprises the following steps: using aromatic hydrocarbon as shown in a general formula (I) as a rawmaterial and reacting with chlorosulfonic acid to generate aryl chlorosulfonic acid, and reacting with sulfoxide chloride to synthesize aryl sulfonyl chloride as shown in a general formula (II); andpreparing the symmetric diaryl disulfide as shown in a general formula (III) under the action of a reducing agent through a reduction reaction by the aryl sulfonyl chloride as shown in the general formula (II). The disclosed preparation method for the symmetric diaryl disulfide has many advantages of low toxicity of the reaction raw material, short reaction time, cheap reagents and easy acquisition, convenient separation and purification and the like, and has very high application value and industrial production value.
- -
-
Paragraph 0053; 0054; 0055; 0056
(2019/04/17)
-
- 7-substituted-4-aryl coumarins compound, and preparation method and application thereof
-
The invention discloses a 7-substituted-4-aryl coumarins compound, and a preparation method and an application thereof and belongs to the technical field of antitumor drugs. The 7-substituted-4-aryl coumarins compound is acquired in the manner of modifying and remolding 4 and 7 loci of the coumarins. The structural formula is shown in the specification. A pharmacological experiment proves that such a compound has an excellent antitumor activity, can be used for preparing the antitumor drugs, is capable of supplying a new selection for the development and application of the antitumor drugs and further can be applied to the design and optimization of the antitumor drugs. The preparation method of the compound has the advantages of easily acquired raw materials, mild reaction condition, easily realized synthesis method, simple reaction process and operation, low-cost reagents and higher yield.
- -
-
Paragraph 0092; 0093
(2017/08/02)
-
- Janus head type lone pair-π-lone pair and S?F?S interactions in retaining hexafluorobenzene
-
A series of eight tris-arylthiotriazines were synthesized to study the lone pair-π interaction between the triazine ring centroid of these molecules and halogenated solvents. All the eight compounds were characterized using 1H and 13C NMR spectroscopy and single crystal X-ray diffraction techniques. All these compounds show interesting structural properties in the solid state. Unprecedented Janus head type lp?π?lp and S?F?S interactions were observed between one of the tris-arylthiotriazines and hexafluorobenzene.
- Mehrotra, Sonam,Angamuthu, Raja
-
p. 4438 - 4444
(2016/07/06)
-
- Novel lithium and sodium salts of sulfonamides and bis(sulfonyl)imides: Synthesis and electrical conductivity
-
The preparation of new electrolytes for application in lithium or sodium batteries is described. Different salts of lithium and sodium sulfonamide and bis(sulfonyl)imide were prepared in good yields. Ionic conductivity measurements were performed on these salts and conductivities of 0.20 to 0.51 mS cm-1, comparable to those of Li-TFSI, were obtained. The best conductivity was reached for the Li+ salt of a bis(sulfonyl)imide bearing CF3 and 4-FC6H4 groups. This journal is
- Morizur, Vincent,Olivero, Sandra,Desmurs, Jean Roger,Knauth, Philippe,Duach, Elisabet
-
p. 6193 - 6197
(2015/02/19)
-
- Aminoaryl sulphonamide derivatives as functional 5-HT6 ligands
-
The present invention provides aminoaryl sulphonamide derivatives of formula (I), useful in the treatment of a CNS disorder related to or affected by the 5-HT6 receptor. Pharmacological profiles of these components include high affinity binding with 5-HT6 receptors along with good selectivity towards the receptor. The present invention also includes stereoisomers, the salts, methods of preparation and medicine containing the aminoaryl sulphonamide derivatives.
- -
-
Page/Page column 8
(2010/07/08)
-
- Aqueous process chemistry: The preparation of aryl sulfonyl chlorides
-
The use of aqueous acidic conditions for the preparation of arylsulfonyl chlorides from diazonium salts in the presence of copper salts, preferably CuCl, together with thionyl chloride as the sulfur dioxide source, has considerable advantages over recommended literature procedures, whereby reactions are carried out in acetic acid with minimisation of water content of the solvent. The method has been shown to be successful for a wide range of electron-deficient and electron-neutral aryl substrates. The sulfonyl chlorides are protected from hydrolysis by their low solubility in water, which results in their direct precipitation from the reaction mixture in good yields (>70%) and high strength (>98% w/w). The aqueous process, which is additionally safer and more robust, can be readily scaled up and has significant environmental benefits.
- Hogan, Philip J.,Cox, Brian G.
-
experimental part
p. 875 - 879
(2010/04/22)
-
- AMINOALKOXY ARYL SULFONAMIDE COMPOUNDS AND THEIR USE AS 5-HT6 LIGANDS
-
The present invention relates to novel aminoalkoxy arylsulfonamide compounds of the formula (I), their derivatives, their stereoisomers, their pharmaceutically acceptable salts and pharmaceutically acceptable compositions containing them. The present invention also relates to a process for the preparation of above said novel compounds, their derivatives, their stereoisomers, their pharmaceutically acceptable salts and pharmaceutically acceptable compositions containing them. These compounds are useful in the treatment of various disorders that are related to 5-HT6 receptor functions. Specifically, the compounds of this invention are also useful in the treatment of various CNS disorders, hematological disorders, eating disorders, diseases associated with pain, respiratory diseases, genito-urological disorders, cardiovascular diseases and cancer.
- -
-
Page/Page column 20
(2009/01/20)
-
- Isothiazoles as active-site inhibitors of HCV NS5B polymerase
-
Isothiazole analogs were discovered as a novel class of active-site inhibitors of HCV NS5B polymerase. The best compound has an IC50 of 200 nM and EC50 of 100 nM, which is a significant improvement over the starting inhibitor (1). The X-ray complex structure of 1 with HCV NS5B was obtained at a resolution of 2.2 A, revealing that the inhibitor is covalently linked with Cys 366 of the 'primer-grip'. Furthermore, it makes considerable contacts with the C-terminus, β-loop, and more importantly, to the active-site of the enzyme. The uniqueness of this binding mode offers a new insight for the rational design of novel inhibitors for HCV NS5B polymerase.
- Yan, Shunqi,Appleby, Todd,Gunic, Esmir,Shim, Jae Hoon,Tasu, Tania,Kim, Hongwoo,Rong, Frank,Chen, Huaming,Hamatake, Robert,Wu, Jim Z.,Hong, Zhi,Yao, Nanhua
-
-
- AMINOARYL SULPHONAMIDE DERIVATIVES AS FUNCTIONAL 5-HT6 LIGANDS.
-
The present invention provides aminoaryl sulphonamide derivatives of formula (I), useful in the treatment of a CNS disorder related to or affected by the 5-HTg receptor. Pharmacological profile of these compounds includes high affinity binding with 5-HTg receptor along with good selectivity towards the said receptor. The present invention also includes the stereoisomers, the salts, methods of preparation and medicine containing the said aminoaryl sulphonamide derivatives.
- -
-
Page/Page column 17
(2010/11/26)
-
- 5-N-Substituted-2-(substituted benzenesulphonyl) glutamines as antitumor agents. Part II: Synthesis, biological activity and QSAR study
-
Cancer is a major killer disease throughout human history. Thus, cancer becomes a major point of interest in life science. It was proved that cancer is a nitrogen trap and tumor cells are avid glutamine consumers. The non-essential amino acid glutamine, which is a glutamic acid derivative, supplies its amide nitrogen to tumor cells in the biosynthesis of purine and pyrimidine bases of nucleic acids as well as takes part in protein synthesis. Based on these and in continuation of our composite programme of development of new potential anticancer agents through rational drug design, 17 new 5-N-Substituted-2- (substituted benzenesulphonyl) glutamines were selected for synthesis. These compounds as well as 36 earlier synthesized glutamine analogues were screened for antitumor activity using percentage inhibition of tumor cell count as the activity parameter. QSAR study was performed with 53 compounds in order to design leads with increased effectiveness for antitumor activity using both physicochemical and topological parameters. QSAR study showed that steric effect on the aromatic ring is conducive to the activity. n-butyl substitution on aliphatic side chain and atom no 12 is important for antitumor activity of glutamine analogues.
- Samanta, Soma,Srikanth,Banerjee, Suchandra,Debnath, Bikash,Gayen, Shovanlal,Jha, Tarun
-
p. 1413 - 1423
(2007/10/03)
-
- Bispiperidines as antithrombotic agents
-
Novel compounds which are inhibitors of the binding of fibrinogen to the Gp IIb/IIIa platelet receptors, and which can be used therepeutically as antithrombotic agents
- -
-
-
- Process for the preparation of 3-nitrobenzenesulfonyl chloride
-
In a method for preparing 3-nitrobenzene sulphonic acid chloride from nitrobenzene and chlorosulphonic acid, nitrobenzene is reacted with chlorosulphonic acid at approximately 90° to approximately 120° C. and an inorganic acid chloride is then allowed to act on the resultant reaction mixture at approximately 40° to approximately 90° C.
- -
-
-
- Process for the preparation of aromatic sulfonyl chlorides
-
A process for the preparation of aromatic sulfonyl chlorides of the formula I STR1 in which R1, R2 and R3 are identical or different and are hydrogen, fluorine, chlorine, bromine or iodine atoms, alkyl(C1 -C4), acetamido, nitro or carboxyl groups, or R1 and R2 together form an aromatic or heteroaromatic ring having 5 or 6 ring members, which can be substituted by fluorine, chlorine, bromine or iodine atoms, alkyl(C1 -C4), acetamido, nitro or carboxyl groups, by reaction of aromatic compounds of the formula II STR2 in which R1, R2 and R3 have the abovementioned meanings, with chlorosulfonic acid in excess or with chlorosulfonic acid or oleum and thionyl chloride, by reacting in the presence of sulfamic acid as a catalyst.
- -
-
-
- Multiple Structure-Reactivity Relationships for a Menschutkin-type SN2 Reaction
-
The mechanism of nucleophilic displacement was studied by using three variable systems of ρX, ρY and ρZ obtained from the change of substituents X, Y and Z for the reaction of (Z)-substituted benzyl (X)-benzenesulphonates with (Y)-substituted N,N-dimethylanilines in aceton at 35 deg C.The coefficient of the interaction term, ρXY, has a value of 0.21 which means that bond-making and -breaking are concerted in the SN2 transition state.In the range Z = H to p-NO2, in which the SN2 mechanism is predicted to be dominant, the ρZY value is very large, 0.5, which means that the interaction between Z and Y is very large. ρZX is ca. 0.06 which means that the interaction is small between X and Z.In contrast, in the range Z = H to p-Me, in which the SN1 mechanism is dominant, the ρZY value is nearly zero, indicating no interaction between Z and Y.Changes of substituent effect and interaction terms, ρXY, ρYZ and ρZX are useful tools for distinguishing wrong reaction mechanisms.
- Yoh, Soo-Dong,Tsuno, Yuho,Fujio, Mizue,Sawada, Masami,Yukawa, Yasuhide
-
-
- Influence of Pressure on the Menschutkin-Type Reaction of Phenethyl Arenesulfonates with Pyridine
-
Kinetic investigation of β-phenethyl arenesulfonates with pyridine in acetonitrile revealed that the rates of these reactions which were lower than those of the reaction of benzyl benzenesulfonate with pyridine in acetone were increased with raising temperatures and pressures.The activation volumes were comparable to those of benzyl system, but the activation entropies were negatively larger than those of benzyl system.From these phenomena it can be deduced that phenethyl system has more SN2 character in the transition state, comparing with the reaction of benzyl system.With raising pressures the Hammett reaction parameters (ρ) were decreased, indicating that the reaction is probably closer to the tihgt SN2 character at higher pressures.
- Yoh, Soo-Dong,Park, Jong-Hwan,Lee, Kyung-A,Han, In-Sook
-
p. 1149 - 1152
(2007/10/02)
-
- DISSOCIATION OF SUBSTITUTED BENZENESULPHONAMIDES IN WATER, METHANOL AND ETHANOL
-
Thirteen monosubstituted arylsulphonamides (XC6H4SO2NH2) and two 3,4-disubstituted arylsulphonamides (X2C6H3SO2NH2) have been synthetized and their dissociation constants have been measured by potentiometric titration in water, methanol, and ethanol.The Hammett substitution dependences have been calculated for all the media, and changes in the reaction constants due to transition from water to alcohols are discussed in confrontation with analogous dependences of benzoic acids.The reaction constant ρ found in methanol is lower than that in water.The dissociation constants have been treated by the method of the principal components and by multiple linear regression.
- Ludwig, Miroslav,Pytela, Oldrich,Kalfus, Karel,Vecera, Miroslav
-
p. 1182 - 1192
(2007/10/02)
-
- KINETICS OF THE TRANSFORMATIONS OF AROMATIC SULFO DERIVATIVES TO ACID HALIDES IN CHLORO- AND FLUOROSULFONIC ACID MEDIA
-
The pseudofirst-order rate constants for the formation of the corresponding sulfonic acid halides (keff) from sulfo derivatives with the general formula RC6H4SO3X, where X = NH2, Cl, F, and R = H, p-Cl, p-NO2, and m-NO2, were measured by GLC in fluorosulfonic and chlorosulfonic acids.The effect of substituents in the benzene ring on the rate of the transformations of the sulfo derivatives into the halides is similar to the previously investigated effect of substituents on the rate of solvolysis of substituted benzenesulfonyl halides in 100percent sulfuric acid (ρ -4).Com parison of the ratios of the keff values for the transformations of the sulfonamides in chlorosulfonic and fluorosulfonic acids and also the sulfonyl fluorides in 100percent sulfuric acid and chlorosulfonic acid with the ratios of the acidities of the respective media shows that these reactions have acid-catalytic character.The sulfonyl chlorides and sulfonamides in 100percent sulfuric acid are solvolyzed to a significant degree with the participation of H2S2O7.
- Ivanov, S. N.,Gnedin, B. G.
-
p. 1909 - 1914
(2007/10/02)
-
- Process for preparing amides by reaction in presence of molecular sieve
-
There is provided a process for preparing amides which comprises reacting an amine, or an amide, and an acid halide, or anhydride, in suitable molecular proportions, in an inert organic diluent, in the presence of an effective amount of a molecular sieve, until the reaction is completed, separating the molecular sieve, and recovering the amide from the organic mother liquor.
- -
-
-