- 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
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- Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst
-
Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one—light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
- Antonietti, Markus,Guldi, Dirk M.,Markushyna, Yevheniia,Savateev, Aleksandr,Schü?lbauer, Christoph M.,Ullrich, Tobias
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supporting information
p. 20543 - 20550
(2021/08/12)
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- Synthesis, biological evaluation, and enzyme assay of some 5-N-substituted-2-N-(arylsulphonyl)-L(+)glutamines as potential anticancer agents
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Thirty 5-N-substituted-2-N-(arylsulphonyl)-L(+)glutamines were synthesized and evaluated biologically for their anticancer activities. The best active compound of this series showed 92.92% inhibition of tumor weight against Ehrlich Ascites Carcinoma cells. The most active compound was proved to be a competitive inhibitor of glutaminase in the enzyme assay. The best active compound may be a starting point to generate 'lead' for further exploration.
- Jha, Tarun,Samanta, Soma,Halder, Amit Kumar,Adhikari, Nilanjan,Abdul Amin,Sanyal, Arpita,Mukherjee, Tanmoy
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p. 1259 - 1264
(2020/12/04)
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- Preparation method for symmetric diaryl disulfide
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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 0048; 0049; 0050; 0051
(2019/04/17)
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- Synthesis of Air-stable, Odorless Thiophenol Surrogates via Ni-Catalyzed C?S Cross-Coupling
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Thiophenols are versatile synthetic intermediates whose practical appeal is marred by their air sensitivity, toxicity and extreme malodor. Herein we report an efficient catalytic method for the preparation of S-aryl isothiouronium salts, and demonstrate that these air-stable, odorless solids serve as user-friendly sources of thiophenols in synthesis. Diverse isothiouronium salts featuring synthetically useful functionality are readily accessible by nickel-catalyzed C?S cross-coupling of (hetero)aryl iodides and thiourea. Convenient, chromatography-free isolation of these salts is achieved by precipitation, allowing the methodology to be applied directly to large scales. Thiophenols are liberated from the corresponding isothiouronium salts upon treatment with a weak base, enabling an in situ release/S-functionalization strategy that entirely negates the need to isolate, purify or manipulate these noxious reagents.
- Magné, Valentin,Ball, Liam T.
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p. 8903 - 8910
(2019/06/17)
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- High yielding protocol for direct conversion of thiols to sulfonyl chlorides and sulfonamides
-
In this paper, a new method for oxidative chlorination of thiols to sulfonyl chlorides and sulfonamides using H2O2 in the presence of TMSCl is reported. The excellent yields, short reaction times, excellent efficiencies, low costs, and easy separation of products are the most important advantages of this method.
- Sohrabnezhad, Samira,Bahrami, Kiumars,Hakimpoor, Farahman
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p. 256 - 264
(2019/02/06)
-
- Design, synthesis and biological evaluation of novel phenylsulfonylurea derivatives as PI3K/mTOR dual inhibitors
-
Five series of novel phenylsulfonylurea derivatives, 19a–d, 20a–d, 21a–d, 22a–d and 23a–d, bearing 4-phenylaminoquinoline scaffold were designed, synthesized and their IC50 values against four cancer cell lines (HepG-2, A549, PC-3 and MCF-7) were evaluated. Most compounds showed moderate cytotoxicity activity against the cancer cell lines. Structure–activity relationships (SARs) and pharmacological results indicated that introduction of 4-aminoquinoline scaffold and phenylsulfonylurea scaffold were beneficial for anti-tumor activity. Moreover, para-methoxyl substitution of 4-anilino moiety and para-halogen substitution of phenylsulfonylurea have different impacts on different series of compounds. Furthermore, the micromolecule group substitution in the 6-position of the quinoline ring have a slight impact on the cellular activity of the target compounds.
- Zhao, Bingbing,Lei, Fei,Wang, Caolin,Zhang, Binliang,Yang, Zunhua,Li, Wei,Zhu, Wufu,Xu, Shan
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-
- Possible anticancer agents: synthesis, pharmacological activity, and molecular modeling studies on some 5-N -Substituted-2-N-(substituted benzenesulphonyl)-L(+)Glutamines
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On the basis of our earlier work, fortyone 5-N-substituted-2N-(substituted benzenesulphonyl)-L(+)glutamines were synthesized and screened for cancer cell inhibitory activity. The best active compounds showed 91% tumor cell inhibition, whereas other three compounds showed more than 80% inhibition. Two-dimensional quantitative structure–activity relationship modeling and three-dimensional quantitative structure–activity relationship k-nearest neighbor molecular field analysis studies were done to get an insight into structural requirements toward further improved anticancer activity. Considering the fact that these compounds are competitive inhibitors of glutaminase, a molecular docking study followed by molecular dynamic simulation analysis were performed. The work may help to develop new anticancer agents.
- Jha, Tarun,Basu, Soumya,Halder, Amit Kumar,Adhikari, Nilanjan,Samanta, Soma
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p. 1437 - 1458
(2017/06/05)
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- Aromatic Chlorosulfonylation by Photoredox Catalysis
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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
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p. 151 - 155
(2017/01/17)
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- Sulfonyl halide synthesis by thiol oxyhalogenation using NBS/NCS – iPrOH
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A rapid and facile method provides a general route to sulfonyl bromides/chlorides by the oxidation of thiols using NXS – ROH (X?=?Br,Cl, R?=?iPr) as an oxyhalogenation reagent. Control experiments suggest that the alcohol component is the source of oxygen. The proposed method enable the access to structurally diverse sulfonyl bromides and chlorides including challenging examples, inaccessible by other synthetic methods.
- Silva-Cuevas, Carolina,Perez-Arrieta, Carlos,Polindara-García, Luis A.,Lujan-Montelongo, J. Armando
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supporting information
p. 2244 - 2247
(2017/05/16)
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- Conversion of thiols into sulfonyl halogenides under aerobic and metal-free conditions
-
An environmentally benign, metal-free synthesis of sulfonyl chlorides and bromides from thiols in the presence of ammonium nitrate, an aqueous solution of HCl and HBr and oxygen as a terminal oxidant was developed. The reactivity of various substituted thiophenols, benzylic-, aliphatic- and heteroaromatic thiols was examined. Ammonium nitrate served as a source of nitrogen oxides (NO/NO2), which are the crucial players in a redox-catalytic cycle. Sulfonyl chlorides and bromides were isolated without extraction and "filtered" over a short pad of silica gel; the use of solvents was greatly reduced in comparison with traditional isolation and purification. A "one-pot" protocol for the conversion of thiol into sulfonamide is also demonstrated. Scale-up experiments on the preparation of sulfonyl chloride and bromide are shown. A possible reaction pathway is discussed.
- Jereb, Marjan,Hribernik, Luka
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supporting information
p. 2286 - 2295
(2017/07/24)
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- Aminoxidation of Arenethiols to N-Chloro-N-sulfonyl Sulfinamides
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A simple and efficient method to synthesize N-chloro-N-sulfonylsulfinamides by the direct aminoxidation of arenethiols under aqueous and mild conditions is disclosed, geminally installing the oxo and amino groups on the sulfur atom of arenethiols. The products have been primarily developed as sulfinylation reagents to convert Grignard reagents into sulfoxides, and as amination reagents to convert secondary amines into hydrazine derivatives.
- Yang, Zhanhui,Xu, Wei,Wu, Qiuyue,Xu, Jiaxi
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p. 3051 - 3057
(2016/04/26)
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- COMPOUNDS AS CRTH2 ANTAGONIST AND USES THEREOF
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The compounds of Formula (I) which can be used as CRTH2 receptor antagonists are provided. The compounds of Formula (I) can be used in the treatment and prevention of asthma, allergic rhinitis and atopic dermatitis, as well as other diseases mediated by prostaglandin D2 (PGD2) at the CRTH2 receptor.
- -
-
Paragraph 00409
(2016/04/20)
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- 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
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p. 6193 - 6197
(2015/02/19)
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- Oxyhalogenation of thiols and disulfides into sulfonyl chlorides/bromides using oxone-KX (X = Cl or Br) in water
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A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides by oxyhalogenation of thiols and disulfides with oxone-KX (X = Cl or Br) using water as the solvent is described. This journal is the Partner Organisations 2014.
- Madabhushi, Sridhar,Jillella, Raveendra,Sriramoju, Vinodkumar,Singh, Rajpal
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supporting information
p. 3125 - 3131
(2014/06/10)
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- One-pot tandem reactions for direct conversion of thiols and disulfides to sulfonic esters, and Paal-Knorr synthesis of pyrrole derivatives catalyzed by TCCA
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A convenient synthesis of sulfonic esters from thiols and disulfides is described. In situ preparation of sulfonyl chlorides from thiols is accomplished by oxidation with trichloroisocyanuric acid (TCCA), tetra-butylammonium chloride (t-Bu4NCl), and water. The sulfonyl chlorides are then further allowed to react with phenol derivatives in the same reaction vessel. Also, a facile synthesis of N-substituted pyrroles by the reaction of hexane-2,5-dione with primary amines has been accomplished using TCCA as a catalyst under mild condition with excellent yields.
- Hemmati, Saba,Mojtahedi, Mohammad Majid,Abaee, Mohammad Saeed,Vafajoo, Zahra,Saremi, Shokufe Ghahri,Noroozi, Mohammad,Sedrpoushan, Alireza,Ataee, Meral
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p. 347 - 357
(2013/09/23)
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- Molecular design and synthesis of HCV inhibitors based on thiazolone scaffold
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A series of thiazolone derivatives was designed and synthesized as potential HCV NS5B allosteric polymerase inhibitors at the allosteric site thumb II. Their antiviral activity was evaluated and molecular modeling was utilized to give further envision on their probable binding modes in the allosteric binding site. Among the tested molecules, compound 9b displayed sub-micromolar inhibitory activity with an EC50 of 0.79 μM indicating excellent potency profile. It also showed good safety profile (CC50 ≥ 75 μM and SI ≥ 94.3).
- Al-Ansary, Ghada H.,Ismail, Mohamed A.H.,Abou El Ella, Dalal A.,Eid, Sameh,Abouzid, Khaled A.M.
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-
- Synthesis of aryl sulfonamides via palladium-catalyzed chlorosulfonylation of arylboronic acids
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A palladium-catalyzed method for the preparation of sulfonamides is described. The process exhibits significant functional group tolerance and allows for the preparation of a number of arylsulfonyl chlorides and sulfonamides under mild conditions.
- Debergh, J. Robb,Niljianskul, Nootaree,Buchwald, Stephen L.
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supporting information
p. 10638 - 10641
(2013/08/23)
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- One-pot tandem reactions for direct conversion of thiols and disulfides to sulfonic esters, alcohols to bis(indolyl)methanes and synthesis of pyrroles catalyzed by N-chloro reagents
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A convenient synthesis of sulfonic esters from thiols and disulfides has been described. In situ preparation of sulfonyl chlorides from thiols is accomplished by oxidation with Chloramin-T, tetra-butylammonium chloride (t-Bu4NCl) and water. The sulfonyl chlorides are then further allowed to react with phenol derivatives in the same reaction vessel. Also, a facile synthesis of bis(indolyl)methanes from alcohols using TCCA/KBr/wet-SiO2, and N-substituted pyrroles by reaction of hexane-2,5-dione with primary amines has been accomplished under mild condition with excellent yields.
- Veisi, Hojat,Ataee, Meral,Fatolahi, Leila,Lotfi, Shahram
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p. 111 - 117
(2013/07/26)
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- Synthesis of sulfonyl chlorides and sulfonic acids in SDS micelles
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H2O2/POCl3 is found to be a reactive reagent system that can be used in sodium dodecyl sulfate (SDS) micellar solution in aqueous media for the direct oxidative chlorination of thiol and di-sulfide derivatives to give the desired sulfonyl chlorides. The oxidation of thiols and disulfides to sulfonic acids with this system is also reported. In most cases, these reactions are highly selective, simple, and clean, affording products in excellent yields and high purity. Georg Thieme Verlag Stuttgart · New York.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Abbasi, Jamshid
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experimental part
p. 316 - 322
(2012/03/26)
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- Trichloroisocyanuric acid (TCCA) and N-chlorosuccinimide (NCS) as efficient reagents for the direct oxidative conversion of thiols and disulfides to sulfonyl chlorides
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Trichloroisocyanuric acid (TCCA) and N-chlorosuccinimide (NCS) were found to be mild and efficient reagents for the direct oxidative conversion of sulfur compounds to the corresponding arenesulfonyl chlorides in good-to-excellent yields through the oxidative chlorination. The overall process is simple and practical, and it provides convenient access to a variety of aryl or heteroarylsulfonyl chlorides. The mild reaction conditions and the broad substrate scope render this method attractive and complementary to existing syntheses of aryl or heteroarylsulfonyl chlorides. Copyright
- Veisi, Hojat,Sedrpoushan, Alireza,Hemmati, Saba,Kordestani, Davood
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experimental part
p. 769 - 775
(2012/06/30)
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- Synthesis of sulfonyl chlorides and thiosulfonates from H2O 2-TiCl4
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A new method is described for the oxidative chlorination of thiols to sulfonyl chlorides using titanium tetrachloride in combination with the oxidant hydrogen peroxide. Direct conversion of thiols into their corresponding thiosulfonates is also reported. Good to excellent yields, short reaction times, high efficiencies, cost-effectiveness, and, facile isolation of the desired products make the present methodology a practical alternative.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Khaledian, Donya
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experimental part
p. 354 - 358
(2012/01/19)
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- Synthesis of sulfonamides and sulfonic esters via reaction of amines and phenols with thiols using H2O2-POCl3 system
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Phosphorus oxychloride efficiently promoted the synthesis of sulfonamides and sulfonic esters from thiols with hydrogen peroxide in the presence of Amberlite IRA-400 (OH-). This method has been applied to a variety of substrates including nucleophilic and sterically hindered amines, and also phenols with excellent yields of sulfonamides and sulfonic esters. In most cases these reactions are highly selective, simple, and clean, affording products in excellent yields and high purity.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Abbasi, Jamshid
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supporting information; experimental part
p. 5095 - 5101
(2012/07/28)
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- TAPC-promoted synthesis of sulfonyl chlorides from sulfonic acids
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A novel and efficient method is described for the preparation of sulfonyl chlorides from sulfonic acids using TAPC as chlorinating agent. Mild reaction conditions, shorter reaction times, high efficiencies, cost-effectiveness, and facile isolation of the desired products make the present methodology a practical alternative and will provide a valuable synthetic tool for various pharmaceutical applications. Georg Thieme Verlag Stuttgart · New York.
- Bahrami, Kiumars
-
experimental part
p. 2671 - 2674
(2011/12/04)
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- Poly(N,N'-Dichloro-N-ethyl-benzene-1,3-disulfonamide) and N,N,N',N'-Tetrachlorobenzene-1,3-disulfonamide as efficient reagents to direct oxidative conversion of thiols and disulfide to sulfonyl chlorides
-
Poly(N,N'-Dichloro-N-ethyl-benzene-1,3-disulfonamide) (PCBS) and N,N,N',N'-Tetrachlorobenzene-1,3- disulfonamide (TCBDA) were found to be a mild and efficient reagent for the direct oxidative conversion of sulfur compounds to the corresponding arenesulfonyl chlorides in good to excellent yields through the oxidative chlorination. The overall process is simple, practical, and it provides convenient access to a variety of aryl or heteroarylsulfonyl chlorides. The mild reaction conditions and the broad substrate scope render this method attractive, and complementary to existing syntheses of aryl or heteroarylsulfonyl chlorides.
- Veisi, Hojat,Ghorbani-Vaghei, Ramin,Mahmoodi, Jafar
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experimental part
p. 3692 - 3695
(2012/01/11)
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- A simple and highly effective oxidative chlorination protocol for the preparation of arenesulfonyl chlorides
-
2,4-Dichloro-5,5-dimethylhydantoin (DCDMH) was found to be a mild and efficient reagent for the direct oxidative conversion of sulfur compounds to the corresponding arenesulfonyl chlorides in good to excellent yields through oxidative chlorination. The method is suitable for many types of sulfur substrates (thiols, disulfides, and benzylic sulfides). The overall process is simple, practical, and it provides convenient access to a variety of aryl or heteroarylsulfonyl chlorides. The mild reaction conditions and the broad substrate scope render this method attractive and complementary to existing syntheses of aryl or heteroarylsulfonyl chlorides.
- Pu, Yu-Ming,Christesen, Alan,Ku, Yi-Yin
-
supporting information; experimental part
p. 418 - 421
(2010/03/04)
-
- A novel, practical synthesis of sulfonyl chlorides from thiol and disulfide derivatives
-
Hydrogen peroxide, in the presence of zirconium tetrachloride, is a very efficient reagent for the direct oxidative conversion of thiol and disulfide derivatives into the corresponding sulfonyl chlorides with high purity through oxidative chlorination. Excellent yields, very short reaction times, mild reaction conditions, and the avoidance of harsh reagents are the main advantages of this method.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Soheilizad, Mehdi
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experimental part
p. 2773 - 2776
(2010/02/28)
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- Direct conversion of thiols to sulfonyl chlorides and sulfonamides
-
(Chemical Equation Presented) H2O2 in combination with SOCl2 proved to be a highly reactive reagent for the direct oxidative conversion of thiol derivatives to the corresponding sulfonyl chlorides with high purity through oxidative chlorination. Upon reaction with amines, the corresponding sulfonamides were obtained in excellent yields and in very short reaction times.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Soheilizad, Mehdi
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supporting information; experimental part
p. 9287 - 9291
(2010/03/04)
-
- Chlorotrimethylsilane-nitrate salts as oxidants: Direct oxidative conversion of thiols and disulfides to sulfonyl chlorides
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(Chemical Equation Presented) A mixture of nitrate salt and chlorotrimethylsilane is found to be a mild and efficient reagent for the direct oxidative conversion of thiols (1) and disulfides (2) to the corresponding sulfonyl chlorides (3) in excellent yields through oxidative chlorination. Sulfides and sulfoxides were also found to undergo oxidation to sulfones under similar reaction conditions. In most cases these reactions are highly selective, simple, and clean, affording products in high yield and purity.
- Prakash, G. K. Surya,Mathew, Thomas,Panja, Chiradeep,Olah, George A.
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p. 5847 - 5850
(2008/02/09)
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- Phenylenediamine urotensin-II receptor antagonists and CCR-9 antagonists
-
The present invention relates to urotensin II receptor antagonists, CCR-9 antagonists, pharmaceutical compositions containing them and their use.
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-
- Polymer electrolyte and process for producing the same
-
A polymer electrolyte having, in a main chain, a structural unit represented by the following formula (1):-[Ar1-(SO2-N-(X+)-SO2-Ar2)m-SO2-N-(X+)-SO2-Ar1-O]- wherein Ar1 and Ar2 independently represent a divalent aromatic groups, m represents an integer of 0 to 3, and X+ represents an ion selected from hydrogen ion, an alkali metal ion and ammonium ion, which is excellent in proton conductivity, thermal resistance and strength. The polymer electrolyte is soluble in solvents and has excellent film forming property and recycling efficiency.
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- Bispiperidines as antithrombotic agents
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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
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- Benzocyclobutenones and polymers derived therefrom
-
The invention disclosed relates to novel functionalized benzocyclobutenones of structural formula I STR1 wherein R is NH2, reactive NH2 derivatives including acids, acid chlorides, amides and diazonium salts, OH, CN, NO2, H, I, F Br, Cl, mercapto and deuterium. Also disclosed are polymer compositions comprising thermal reaction products of the benzocyclobutenones of formula I and either a polyol or a polyamine.
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-
- Effects of medium and substituents on dissociation of 4,4′-disubstituted bis(benzenesulfon)imides
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Ten 4,4′-disubstituted bis(arenesulfon)imides of the general formula XC6H4SO2NHSO2C6H 4X have been synthesized and their structures confirmed by their 1H NMR spectra. Elemental analyses are presented for the compounds not yet described. The dissociation constants of these model substances have been measured potentiometrically in pyridine, dimethylformamide, methanol, ethanol, propylene carbonate, acetone, acetonitrile, 1,2-dichloroethane and tetramethylene sulfone. The pKHA values obtained have been correlated with three sets of the Hammett substituent constants and the results have been used to discuss the solvent and substituent effects on the dissociation of the compounds studied. Sulfonimides with electron-acceptor substituents behave as rather strong acids in some solvents (pyridine, dimethylformamide, methanol and ethanol), whereas normal substituent dependences are found in other solvents. The experimental data have also been interpreted with the help of the statistical methods based on latent variables. From the calculations it follows that only the first principal component, which correlates well with the substituent constant sets adopted, is statistically significant in describing the substituent effect on the acid-base process studied.
- Ludwig, Miroslav,Stverka, Pavel
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p. 1205 - 1214
(2007/10/03)
-
- Wasserloesliche Phosphane. II. Ein neuer Syntheseweg fuer wasserloesliche sekundaere und tertiaere Phosphane mit sulfonierten aromatischen Resten - Kristallstruktur von P(p-C6H4-SO3K)3*KCl*0.5H2O
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Water soluble tertiary phosphanes 2, 7, 10-17 with sulfonated aromatic substituents p-C6H4-SO3K and 2,4-C6H3(SO3K)2 can be obtained in good yields by nucleophilic aromatic substitution of fluorine in p-F-C6H4-SO3K (1) or F-C6H3-2,4-(SO3K)2 (5) with PH3 or primary and secondary phosphanes in the superbasic medium dimethyl sulfoxide (DMSO)/KOH(solid).The first water-soluble secondary phosphane HP2 (6) having sulfonated aromatic substituents can be obtained if 5 is reacted under similar conditions with PH3.Highly sulfonated phosphanes (7-9) with remarkable solubilities in water are formed upon reaction of 6 with F-C6H5, n-BuBr or C6H5-CH2-Br, respectively, in the superbasic medium.The resulting compounds have been identified by their 1H, 13C and 31P NMR spectra.X-Ray structural analysis of P(p-C6H4-SO3K)3*KCl*0.5H2O shows C3 symmetry for the trianion of 2 with the P-C-P bond angles (103.5(2)o) and P-C bond lengths (1.843(4) Angstroem) being almost identical to those in Ph3P.Key words: Phosphine; Catalysis; Nuclear magnetic resonance; Water soluble phosphine; Phase transfer; Hydroformylation
- Herd, Oliver,Hessler, Antonella,Langhans, Klaus P.,Stelzer, Othmar,Sheldrick, William S.,Weferling, Norbert
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-
- Convenient One-Pot Synthesis of Sulfonyl Chlorides from Thiols Using Sulfuryl Chloride and Metal Nitrate
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Various sulfonyl chlorides were obtained in excellent yields by the reaction of alkyl and aryl thiols with sulfuryl chloride in the presence of metal nitrate under mild condition in aprotic solvents such as acetonitrile and N,N-dimethylformamide.
- Park, Young Jun,Shin, Hyun Ho,Kim, Yong Hae
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p. 1483 - 1486
(2007/10/02)
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- Quinolinoxy phenylsulphonamides
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New phenylsulphonamide of the formula in which STR1 R1 represents a pyridyl, quinolyl or isoquinolyl radical which is unsubstituted or substituted by halogen, alkyl, cycloalkyl, alkoxy, cyano, nitro, halogenoalkyl, halogenoalkoxy, alkoxycarbonyl or alkylsulphonyl, R2 represents hydrogen, cyano, nitro, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or alkoxycarbonyl, R3 represents an aryl radical which is unsubstituted or monosubstituted, disubstituted or trisubstituted by halogen, halogenoalkyl, halogenoalkoxy, alkyl, alkoxy, alkylthio, alkylsulphonyl, cyano, nitro or alkoxycarbonyl, the substituents being identical or different, or represents pentafluorophenyl or represents a straight-chain, branched or cyclic alkyl which is unsubstituted or substituted by halogen, aryl, aryloxy, cyano, alkoxycarbonyl, alkoxy, alkylthio or trifluoromethyl, and X represents an --O--, --A--B-- or --B--A-- group where A denotes --O--, STR2 and B denotes --CH2 -- or STR3 where R1 does not represent a pyridyl radical when x represents an --O-- group, and salts thereof are prepared by reacting appropriate amines with sulphonyl halides. The substituted phenylsulphonamides can be employed as active compounds for inhibiting enzymatic reactions and for inhibiting thrombocyte aggregations.
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- A KINETIC STUDY OF THE FRIEDEL-CRAFTS REACTION OF NAPHTHALENE WITH PARA- SUBSTITUTED BENZENESULPHONYL CHLORIDES: THE EFFECT OF THE SUBSTITUENT
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The kinetics of the Friedel-Crafts reaction of naphthalene with para-substituted benzenesulphonyl chlorides have been investigated.The rate constants for equations (i) (formation of the sulphonyl cation) and (ii) (sulphone formation) were determined separately.The effect of the para-substituents on k1 was XC6H4SO2Cl + AlCl3 XC6H4SO2+*AlCl4- , XC6H4SO24*AlCl4- + C10H8 XC6H4SO2C10H7*AlCl3 + HCl well expressed by Yukawa-Tsuno equation, log(k1X/K1H)= ρ1(Δ?R(+))> where ρ1= -2.7 and γ1= 0.4.On the other hand, the effect of the para-substituents on k3(=k1k2/k-1) was expressed by the Brown-Okamoto equation, log(k3X/k3H)= ρ3?+ where ρ3= -2.8.Thus, the electron-donating para-substituents gave the greater reaction rates.We concluded that the sulphonyl cation gives large negative ρ values as a result of its high reactivity, and that its low selectivity for α-attack is due to a steric effect.These kinetic results have been rationalised in terms of bifunctional acid-base catalysis in phenylsulphonnylation.
- Yoshii, Yoshihiro,Ito, Akiyoshi,Hirashima, Tsuneaki,Shinkai, Seiji,Manabe, Osamu
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p. 777 - 782
(2007/10/02)
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- DISSOCIATION OF SUBSTITUTED BENZENESULPHONAMIDES IN WATER, METHANOL AND ETHANOL
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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
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p. 1182 - 1192
(2007/10/02)
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