- RING-SIZE EFFECTS ON THE IONIZATION POTENTIALS OF N-SUBSTITUTED AZACYCLOALKANES
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The ionization potential of the Ione-pair electrons of nitrogen has been determined for N-methyl- and N-tosyl-azacycloalkanes by means of gas-phase u.v. photoelectron spectroscopy.The cyclic compounds examined contain small, common, medium, and large-membered rings.The ionization potentials are affected by conformational features and, in particular, by the strain present in the ring.More precisely, the IPs reflect changes of hybridization of the nitrogen Ione pair upon varying the ring size, whereby a lower or higher energy is required for the ionization process of the cyclic compounds relative to a series of open-chain alkyl amines taken as reference.Steric inhibition of resonance by the N-tosyl substituent takes place in the case of the strained small rings.
- Cauletti, Carla,Di Vona, Maria Luisa,Gargano, Patrizia,Grandinetti, Felice,Galli, Carlo,Lilloci, Claudio
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- Synthesis of Ferrocenesulfonyl Chloride: Key Intermediate toward Ferrocenesulfonamides
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Ferrocenesulfonyl chloride is the key intermediate in the synthesis of ferrocenesulfonamides, a family of underexplored derivatives. A one-pot synthesis of this compound, able to easily deliver multigram quantities of product, is reported. An original protocol for the synthesis of ferrocenesulfonamides is described along with highlighting the reactivity difference between arene and ferrocenesulfonyl chlorides. Finally, an example of diastereoselective deprotolithiation of chiral ferrocenesulfonamides is described.
- Erb, William,Wen, Min,Roisnel, Thierry,Mongin, Florence
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- NUCLEAR MAGNETIC RESONANCE AND X-RAY DIFFRACTION STUDIES ON SOME SUBSTITUTED BENZENESULPHONAMIDES
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Solid-state 13C c.p.-m.a.s. and solution 13C, 15N, and 17O n.m.r. spectra were measured for toluene-p-sulphonamide, N-methyltoluene-p-sulphonamide, NN-dimethyltoluene-p-sulphonamide, p-chlorobenzenesulphonamide, and NN-simethyl-p-chlorobenzenesulphonamide.The 13C c.p.-m.a.s. n.m.r. resonance lines of the carbon atoms bonded to nitrogen show characteristic line broadening with sligthly asymmetric doublet petterns.Some differences are evident in the 13C shielding of the carbon atoms between the solid-state and solution-state spectra.In the solution spectra the 15N and 17O chemical shifts increase in conformity with the polarity order of the amides.The n.m.r. relaxation times of the methyl groups of the compounds were measured as well.The crystal structures of N-methyltoluene-p-sulphonamide and NN-dimethyltoluene-p-sulphonamide were determined by single-crystal X-ray diffraction technique and refined to final R values of 0.056 and 0.044, respectively.Except for some baely significant differences, the bond lengths and angles are similar in the two compounds.The most striking difference is the value of the C-C-S-N torsion angle.
- Haekkinen, Anna-Marija,Ruostesuo, Pirko,Kivekaes, Raikko
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Read Online
- A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
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A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
- Huang, Binbin,Guo, Lin,Xia, Wujiong
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p. 2095 - 2103
(2021/03/26)
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- Debenzylative Sulfonylation of Tertiary Benzylamines Promoted by Visible Light
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An efficient, general, inexpensive, and environmentally friendly photosynthesis of sulfonamides via visible light promoted debenzylative sulfonylation of tertiary benzylamines is described. Compared to the traditional S?N coupling reactions, which are promoted by oxidative C?N bond cleavage of symmetrical tertiary alkylamines, this strategy provides a selective C?N bond cleavage protocol and avoids the use of transition-metal, explosive oxidants, and ligands.
- Fu, Ying,Wu, Qing-Kui,Du, Zhengyin
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supporting information
p. 1896 - 1900
(2021/04/06)
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- Synthesis method of aryl tertiary sulfonamide compounds promoted by visible light
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The invention provides a synthesis method of aryl tertiary sulfonamide compounds promoted by visible light. In a non-protonic solvent, N-benzyl tertiary amine and arylsulfonyl chloride are used as rawmaterials, under the conditions of photosensitizer catalysis and illumination, a reaction is carried out for 1-4h at room temperature, and then separation and purification are carried out to obtain the product. The synthesis method of the aryl tertiary sulfonamide compound provided by the invention has the advantages of mild reaction conditions, simplicity and convenience in operation, short reaction time, no need of any transition metal catalysis and environmental friendliness.
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Paragraph 0017-0018
(2021/01/25)
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- Controlled synthesis of N, N-dimethylarylsulfonamide derivatives as nematicidal agents
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Gramine can be intelligently and efficiently supplied with N, N-dimethylamino group and then reacted with the corresponding sulfonyl chlorides to synthesize N, N-dimethylarylsulfonamides. We herein designed and controlled synthesis of N, N-dimethylarylsulfonamide derivatives, and first reported the results of the nematicidal activity of 15 title compounds 3a-o against Meloidogyne incongnita in vitro, respectively. Among all of the title derivatives, compounds 3a, 3c, 3k, and 3o exhibited potent nematicidal activity with median lethal concentration (LC50) values ranging from 0.22 to 0.26 mg/L. Most noteworthy, N, N-dimethyl-4-methoxyphenylsulfonamide (3c) and N, N-dimethyl-8-quinolinesulfonamide (3o) showed the best promising and pronounced nematicidal activity, with LC50 values of 0.2381 and 0.2259 mg/L, respectively.
- Chen, Gen-Qiang,Xia, Yan-Fei,Yang, Jin-Ming,Che, Zhi-Ping,Sun, Di,Li, Shen,Tian, Yue-E,Liu, Sheng-Ming,Jiang, Jia,Lin, Xiao-Min
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p. 1197 - 1206
(2019/12/03)
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- Preparation method of N,N-dimethylsulfamide derivatives
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The invention discloses a preparation method of N,N-dimethylsulfamide derivatives and belongs to the technical field of synthesis of medical compounds. The preparation method comprises the following steps: reacting gramine, a reactant with sulfonyl chloride groups and an alkaline substance with any one of solvents such as CH2Cl2, CH3COCH3 and CH3CN at a temperature of minus 15 DEG C to 80 DEG C for 24-48 hours so as to obtain the product, wherein the molar ratio of the gramine to the reactant to the alkaline substance is (1.0-2.0):(1.2-4.0):(1.5-6.0). The N,N-dimethylsulfamide derivatives can be simply and efficiently prepared withlow cost, and the yield is up to 70-98%.
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Paragraph 0066-0070; 0164
(2019/10/01)
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- Minisci-Photoredox-Mediated α-Heteroarylation of N-Protected Secondary Amines: Remarkable Selectivity of Azetidines
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The development of a general, mild, and functional-group-tolerant direct functionalization of N-heteroarenes by C-H functionalization with N-protected amines, including azetidines under Minisci-mediated photoredox conditions, is reported. A broad scope of substituted azetidines, including spirocyclic derivatives, and heterocycles were explored. This reaction enables the production of sp3-rich complex druglike structures in one step from unactivated feedstock amines and heterocycles.
- Bosset, Cyril,Beucher, Hélène,Bretel, Guillaume,Pasquier, Elisabeth,Queguiner, Laurence,Henry, Cyril,Vos, Ann,Edwards, James P.,Meerpoel, Lieven,Berthelot, Didier
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supporting information
p. 6003 - 6006
(2018/10/05)
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- Potassium tert-butoxide-mediated metal-free synthesis of sulfonamides from sodium sulfinates and N,N-disubstituted formamides
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By using formamides as amine sources, a novel and efficient KO-t-Bu mediated amination of sodium sulfinates has been developed. The reaction utilizes readily available starting materials under metal-free conditions, thus providing an alternative and attractive route to sulfonamides.
- Bao, Xiaodong,Rong, Xiaona,Liu, Zhiguo,Gu, Yugui,Liang, Guang,Xia, Qinqin
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supporting information
p. 2853 - 2858
(2018/06/25)
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- Charge-Transfer Complex Promoted Regiospecific C?N Bond Cleavage of Vicinal Tertiary Diamines
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A catalyst-free, charge-transfer complex promoted coupling of sulfonyl chlorides with vicinal tertiary diamines to generate sulfonamides is presented. Mechanistic studies showed that these reactions are proceeded via charge transfer of vicinal tertiary diamines to sulfonyl chlorides, forming the unstable sulfonyl quaternary ammonium like complexes which induced the regiospecific intramolecular C?N bond cleavage of vicinal tertiary diamines. (Figure presented.).
- Fu, Ying,Xu, Qin-Shan,Shi, Chun-Zhao,Du, Zhengyin,Xiao, Caiqin
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supporting information
p. 3502 - 3506
(2018/09/14)
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- Catalyst-free synthesis of 4-acyl-NH-1,2,3-triazoles by water-mediated cycloaddition reactions of enaminones and tosyl azide
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The synthesis of 4-acyl-NH-1,2,3-triazoles has been accomplished with high efficiency through the cycloaddition reactions between N,N-dimethylenaminones and tosyl azide. This method is featured with extraordinary sustainability by employing water as the s
- Yang, Lu,Wu, Yuwei,Yang, Yiming,Wen, Chengping,Wan, Jie-Ping
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supporting information
p. 2348 - 2353
(2018/09/14)
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- Aryl sulfonamide tertiary amine compound synthesizing method
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The invention provides an aryl sulfonamide tertiary amine compound synthesizing method. According to the method, in an anhydrous aprotic solvent and under nitrogen protection, acryl sulfonyl chlorideand di-tertiary amine react for 1 to 12 hours according to a molar ratio of (1 to 1) to (1 to 20) under the condition of 50 to 150 DEG C, and the aryl sulfonamide tertiary amine compound can be obtained by purification. According to the method disclosed by the invention, the acryl sulfonyl chloride and the di-tertiary amine can directly generate C-S bond formation in the aprotic solvent and generate C-N bond breakage at the same time. According to the one-step aryl sulfonamide synthesizing method, raw materials are easy to obtain, a synthesizing technology is simple, operation is convenient, cost is low, and yield is high.
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Paragraph 0014
(2018/05/16)
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- An approach to C-N activation: Coupling of arenesulfonyl hydrazides and arenesulfonyl chlorides with: Tert -amines via a metal-, oxidant- and halogen-free anodic oxidation
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tert-Amines were harnessed to afford arenesulfonyl hydrazides and arenesulfonyl chlorides via a metal-, oxidant- and halogen-free electrochemical oxidative coupling in an undivided cell at RT. This environmentally benign approach afforded a wide spectrum of sulfonamides in satisfactory yields using cheap and renewable Pencil Graphite Electrodes (PGEs).
- Sheykhan,Khani,Abbasnia,Shaabanzadeh,Joafshan
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supporting information
p. 5940 - 5948
(2017/12/26)
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- Preparation method for sulfonamide compound
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The invention discloses a preparation method for a sulfonamide compound. The preparation method comprises the following steps: with NIS as an oxidizing agent and potassium tert-butoxide as a base, reacting formamide with sodium arylsulfinate in an organic solvent, and carrying out post-treatment after the reaction is completed so as to obtain the sulfonamide compound. The preparation method uses formamide and sodium arylsulfinate as substrates for synthesis of the sulfonamide compound; the raw materials for the reaction are cheap and easily available; and the preparation method is simple.
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Paragraph 0026; 0027; 0028; 0029; 0030; 0031; 0032-0082
(2017/12/14)
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- Electrochemical synthesis of sulfonamides from arenesulfonohydrazides or sodium p-methylbenzenesulfinate and amines
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An efficient electrochemical synthesis of sulfonamides (yields 56–98%) from arenesulfonohydrazides or sodium p-methylbenzenesulfinate and amines was performed in an undivided cell with graphite anode and iron cathode in MeCN–H2O medium using halides as redox mediators and supporting electrolytes.
- Terent'ev, Alexander O.,Mulina, Olga M.,Pirgach, Dmitry A.,Syroeshkin, Mikhail A.,Glinushkin, Alexey P.,Nikishin, Gennady I.
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p. 538 - 539
(2016/12/02)
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- I2/TBHP Mediated C-N and C-H Bond Cleavage of Tertiary Amines toward Selective Synthesis of Sulfonamides and β-Arylsulfonyl Enamines: The Solvent Effect on Reaction
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A novel method toward synthesis of sulfonamides and β-arylsulfonyl enamines has been developed via I2/TBHP mediated C-N and C-H bond cleavage of tertiary amines, which features highly selective formation of two different target products depending on the reaction solvent. The experimental results reveal that H2O as the solvent could effectively achieve the C-N bond cleavage to produce sulfonamides due to H2O participating in the reaction process where H2O plays a dual role. Differing from H2O, organic solvents (such as dimethyl sulfoxide) could promote the C-H bond cleavage of tertiary amines to yield β-arylsulfonyl enamines.
- Lai, Junyi,Chang, Liming,Yuan, Gaoqing
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supporting information
p. 3194 - 3197
(2016/07/14)
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- Synthesis of sulfonamides: Via copper-catalyzed oxidative C-N bond cleavage of tertiary amines
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A copper-catalyzed coupling reaction of sulfonyl chlorides with tertiary amines via the oxidative C-N bond cleavage of tertiary amines was developed. Sulfonamides were synthesized using this strategy in moderate to good yields. The reaction was applicable to various tertiary amines, as well as sulfonyl chlorides.
- Ji, Jing,Liu, Zhengyi,Liu, Ping,Sun, Peipei
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p. 7018 - 7023
(2016/07/30)
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- NH4I-Catalyzed Synthesis of Sulfonamides from Arylsufonylhydrazides and Amines
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A novel and efficient approach to sulfonamides has been developed. Using TBHP as the oxidant and NH4I (20 mol%) as the catalyst, arylsulfonyl hydrazides reacted with amines to provide sulfonamides in moderate to good yields. Possible reaction pathway for the formation of the products was also discussed in this paper. Sulfonimides were synthesized through the oxidation coupling of arylsufonylhydrazides and amines by TBHP/NH4I system in moderate to good yields.
- Yu, Hui,Zhang, Yonghao
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supporting information
p. 359 - 362
(2016/04/26)
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- Metal-free oxidative coupling of amines with sodium sulfinates: A mild access to sulfonamides
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A practical and mild procedure for the preparation of sulfonamides through TBAI-catalyzed oxidative coupling of amines with sodium sulfinates using TBHP as an oxidant was presented. A variety of amines and sodium sulfinates could go through the transformation, without impacting the hydroxyl group. This journal is
- Zhao, Jinwu,Xu, Jingxiu,Chen, Jiaxi,Wang, Xiaoqin,He, Minghua
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p. 64698 - 64701
(2015/04/27)
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- Copper-mediated S-N formation via an oxygen-activated radical process: A new synthesis method for sulfonamides
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Copper-mediated direct S-N formation using readily available starting materials via an oxygen-activated radical process has been developed. This method provides a novel and direct approach for synthesis of sulfonamides under air conditions. the Partner Organisations 2014.
- Huang, Xin,Wang, Jichao,Ni, Zhangqin,Wang, Sichang,Pan, Yuanjiang
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supporting information
p. 4582 - 4584
(2014/05/06)
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- Copper-catalyzed sulfonamides formation from sodium sulfinates and amines
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A new and convenient method for the construction of sulfonamides via a copper-catalyzed oxidative coupling between sodium sulfinates and amines with 1 atm O2 or DMSO as the oxidant was described. This method provides efficient and robust synthesis of functional sulfonamides in good yields and excellent chemoselectivity. And detailed mechanistic studies showed that this transformation may go through a single electron transfer (SET) pathway.
- Tang, Xiaodong,Huang, Liangbin,Qi, Chaorong,Wu, Xia,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 6102 - 6104
(2013/07/11)
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- Electrochemical synthesis of amides: Direct transformation of methyl ketones with formamides
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A direct transformation from methyl ketones to secondary or tertiary amides has been developed through a novel electrochemical approach and a wide scope of formamides could be utilized as the amide sources. This transformation was promoted by in situ generated iodine through electrolysis of sodium iodide under mild, metal-free conditions. This electrochemical procedure could avoid the use of stoichiometric iodine and afforded the target products in good to excellent yields.
- Huang, Haolai,Yuan, Gaoqing,Li, Xianwei,Jiang, Huanfeng
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supporting information
p. 7156 - 7159
(2013/12/04)
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- Oxidative addition of a strained C-C bond onto electron-rich rhodium(I) at room temperature
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The C-C bond of cyclobutanones undergoes oxidative addition to a T-shape rhodium(I) complex possessing a PBP pincer ligand at room temperature. The remarkable propensity of the rhodium complex for oxidative addition is attributed to the highly electron-donating nature of the boron ligand as well as the unsaturation on the rhodium center.
- Masuda, Yusuke,Hasegawa, Maki,Yamashita, Makoto,Nozaki, Kyoko,Ishida, Naoki,Murakami, Masahiro
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supporting information
p. 7142 - 7145
(2013/06/27)
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- CsF-Celite as an efficient heterogeneous catalyst for sulfonylation and desulfonylation of heteroatoms
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CsF-Celite is found to be as an efficient reusable catalyst for sulfonylation and desulfonylation of heteroatoms. Sulfonamides and N-acylsulfonamides deprotect efficiently in the presence of CsF-Celite under solvent free conditions to give the free amines or amides in good to excellent yields.
- Tamaddon, Fatemeh,Nasiri, Alireza,Farokhi, Somayeh
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experimental part
p. 1477 - 1482
(2012/06/18)
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- One-Pot synthesis of sulfonamides from primary and secondary amine derived sulfonate salts using cyanuric chloride
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A convenient, mild and efficient one-pot synthesis of new sulfonamides is described. The reaction of primary or secondary amine derived sulfonate salts in the presence of cyanuric chloride, triethylamine as base, and anhydrous acetonitrile as solvent at room temperature gives the corresponding sulfonamides in good to excellent yields. Georg Thieme Verlag Stuttgart.
- Rad, Mohammad Navid Soltani,Khalafi-Nezhad, Ali,Asrari, Zeinab,Behrouz, Somayeh,Amini, Zohreh,Behrouz, Marzieh
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experimental part
p. 3983 - 3988
(2010/03/26)
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- Gold-catalyzed substitution reaction with ortho-alkynylbenzoic acid alkyl ester as an efficient alkylating agent
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ortho-Alkynylbenzoic acid alkyl esters behave as alkylating agents in combination with gold catalysts. The reaction with alcohols occurs smoothly in the presence of catalytic amounts of Ph3PAuCl and AgOTf under mild conditions to produce the corresponding ether products in high yields. The protocol is also useful for Friedel-Crafts alkylation and N-alkylation of sulfonamides. The reaction likely proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack of nucleophiles, such as alcohols, aromatic compounds, and sulfonamides.
- Aikawa, Haruo,Tago, Sakie,Umetsu, Kazuteru,Haginiwa, Naomichi,Asao, Naoki
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experimental part
p. 1774 - 1784
(2009/06/20)
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- Microwave-assisted efficient methylation of alkyl and arenesulfonamides with trimethylsulfoxonium iodide and KOH
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A solvent-free synthesis of N-methyl and N,N-dimethylsulfonamides has been achieved by treating the primary and secondary sulfonamides with Me3S+OI- and KOH under microwave irradiation on alumina support. Copyright Taylor & Francis Group, LLC.
- Malik, Sarika,Nadir, Upender K.,Pandey, Pramod S.
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p. 3074 - 3081
(2008/12/22)
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- ACYLUREA CONNECTED AND SULFONYLUREA CONNECTED HYDROXAMATES
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The present invention relates to hydroxamate compounds which are inhibitors of histone deacetylase. More particularly, the present invention relates to acylurea/sulfonylurea containing compounds and methods for their preparation. These compounds may be useful as medicaments for the treatment of proliferative disorders as well as other diseases involving, relating to or associated with enzymes having histone deacetylase activities.
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Page/Page column 60-61
(2010/02/11)
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- NOVEL BENSOPHENONE DERIVATIVES OR SALTS THEREOF
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A benzophenone derivative represented by the following formula: whereinR1 represents, for example, an optionally substituted heterocyclic group, or a substituted phenyl group; Z represents, for example, an alkylene group; R2 represents, for example, a carboxyl group optionally protected with alkyl;R3 represents, for example, an optionally protected hydroxyl group; R4 represents, for example, an optionally substituted cycloalkyloxy group; and R5 represents, for example, a hydrogen atom, ???or a salt thereof has anti-arthritic activity, inhibits bone destruction caused by arthritis, and provides high safety and excellent pharmacokinetics and thus is useful as therapeutic agent for arthritis. These compounds have inhibitory effect on AP-1 activity and are useful as preventive or therapeutic agent for diseases in which excessive expression of AP-1 is involved.
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- PROCESS FOR MAKING SUBSTITUTED ARYL SULFONAMIDES USING AN INDIUM BASED CATALYST SYSTEM
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A process for making substituted aryl sulfonamides by sulfamoylation of an activated aromatic compound using an indium compound as a catalyst.
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- Catalytic arylation of sulfamoyl chlorides: A practical synthesis of sulfonamides
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Commercially available indium(III) triflate is shown to be an efficient catalyst for the sulfamoylation of aromatics.
- Frost, Christopher G.,Hartley, Joseph P.,Griffin, David
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p. 1928 - 1930
(2007/10/03)
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- Synthesis and characterization of β-O-Tosyldehydroserine as a precursor of dehydroamino acids
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β-O-Tosyldehydroserine 3 is prepared directly by the oxidation of the corresponding serine derivative 1 with dimethyl sulfoxide which is activated by p-toluenesulfonyl chloride. The enol tosylate 3 retains reactivities characteristic of aldehydes like those expected for the corresponding dehydroserine derivative 2. A typical reaction of 3 includes substitution of the tosyl group with nucleophiles such as primary and secondary amines, leading to other dehydroamino acids.
- Nakazawa, Takashi,Suzuki, Tomiko,Ishii, Masako
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p. 8951 - 8954
(2007/10/03)
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- BENZENESULPHONAMIDE DERIVATIVES
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The invention concerns benzenesulphonamide derivatives of the formula I wherein R1 is (1-4C)alkyl, (3-4C)alkenyl or (3-4C)alkynyl; R2 and R3 together form ?A2?X2?A3? which defines a ring having 5 or 6 ring atoms, wherein A2 and A3 each is (1-3C)alkylene and X2 is oxy, thio, sulphinyl or sulphonyl; A1 is a direct link to X1 or is (1-3C)alkylene; X1 is oxy, thio or imino; Ar is optionally substituted phenylene; R4 is (1-4C)alkyl, fluoro-(2-4C)alkyl or optionally substituted phenyl or a heterocyclic moiety; R5 is hydrogen or (1-4C)alkyl; and R6 is hydrogen, halogeno, trifluoromethyl, (1-4C)alkyl or (1-4C)alkoxy; or a pharmaceutically-acceptable salt thereof; processes for their manufacture; pharmaceutical compositions containing them and their use as 5-lipoxygenase inhibitors
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- ACTIVATING EFFECT OF THE IMINIUM GROUP IN AROMATIC NUCLEOPHILIC SUBSTITUTION OF AN ALKOXY GROUP AND HALOGEN ATOMS BY THE ACTION OF NITROGEN BASES
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The characteristics of aromatic nucleophilic substitution with activation by the iminium group in the iminium derivatives of p-alkoxy- and p-halogenobenzaldehydes were investigated.They are determined by the concurrent addition of the nucleophilic agents at the C=N multiple bond.The activating effect of the iminium group depends on the nature of the leaving group, the solvent, the substituent in the benzene ring, and the nature and concentration of the protonating agent.The action of heat on p-methoxybenzylidenemethylamine with a tenfold excess of methylamine hydrochloride in a 30percent alcohol solution of methylamine at 150 deg C for 40 h leads to substitutioon of the methoxymethylamino group with a yield of 90percent.
- Blokhin, A.V.,Bundel, Yu. G.,Terenin, V.I.,Kurtz, A.L.
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p. 2116 - 2123
(2007/10/02)
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- Pseudomolecular Rearrangement of O-Ethyl N-Methyl Toluene-4-sulphonimidate to N-Ethyl-N-methyltoluene-4-sulphonamide and its Relevance to the Nucleophilic Properties of Neutral Sulphonamides
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Kinetic studies are reported for the pseudo-molecular rearrangement of O-ethyl N-methyl toluene-4-sulphonimidate to N-ethyl-N-methyltoluene-4-sulphonamide in organic solvents at 34-100 deg C.Without catalysts, the rearrangement follows the equation rate = krearr 2, which is indicative of an intermolecular SN2 transalkylation via an ion-pair intermediate: it is accompained by concurrent E2 elimination to N-methyltoluene-4-sulphonamide.The rearrangement is catalysed by electrophilic reagents such as alkyl halides, ZnI2, and HBr where rate = k2 .For alkyl halides, a two-step mechanism via an ionic intermediate applies in which formation of the intermediate by an SN2 reaction between the substrate and alkyl halide is rate limiting.Other catalysts effect rearrangement by forming alkyl halides in an initial rapid reaction with the substrate.The results are discussed in relation to the ambident nucleophilic properties of sulphonamides.It is suggested that, like carboxylic acid amides and phosphinylamides, alkylation occurs most readily at the O-atom of neutral sulphonamides to give a sulphonimidate (kinetic product), which then rearranges in the presence of electrophilic catalysts to give an N-substituted sulphonamide (thermodynamic product).Rearrangement is normally too fast for the isolation of O-alkyl sulphonimidates, but O-aryl analogues can be obtained.
- Challis, Brian C.,Iley, James N.
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p. 699 - 704
(2007/10/02)
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- Chemistry of Organic Chloramines. Formation of Arenesulfonamides by Derivatization of Organic Chloramines with Sodium Arenesulfinates
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Organic chloramines react rapidly with sodium benzenesulfinate or sodium toluenesulfinate to form arenesulfonamides.Derivatization was carried out by three different methods, one involving derivatization of pure chloramines and two involving derivatization of the chloramines generated in situ by reaction of the amine with sodium hypochlorite.Seventeen arenesulfonamides whose amine precursors included primary and secondary aliphatic amines, aromatic amines, and amino acids were synthesized in poor to excellent yields depending on the method used.Effects of structure,stability, and water solubility of the chloramine precursors are discussed.Benzenesulfonyl chloride can be isolated from the reaction of 10-4 M N-chloropiperidine with sodium benzenesulfinate.Competing hydrolysis of the sulfonyl chloride accounts for low yields of sulfonamide for dilute solutions of chloramine.
- Scully, Frank E.,Bowdring, Katherine
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p. 5077 - 5081
(2007/10/02)
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- Cycloaddition Reactions of Heterocumulenes, XXIII.- Nitrogen-Containing Five-Membered Heterocycles from Carbodiimides or Ketenimines with 3-Dimethylamino-2H-azirines
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Depending on the substituents, carbodiimides 1 effect 1,2 or 1,3 ring-opening of aminoazirines 2; alkyl(sulfonyl)carbodiimides 1b-d can enter into the cycloaddition via either C=N bond.Thus, starting from diphenylcarbodiimide (1a) or the sulfonylcarbodiimides 1c, d, the zwitterions 5 are formed by cleavage of C=N in 2; the reduction, hydrolysis, thiolysis, or aminolysis of which yields imidazolidines 7-9, 15.With methyl iodide, 5a, b are alkylated non-specifically either at the endo- or exo-cyclic nitrogen of the anion moiety.In the reactions of 1c and d with 2 1,2-competes with 1,3-bond cleavage and leads to acrylamidines 17d-g as well as imidazolines 18d, 19c.For mesyl(methyl)carbodiimide (1b), 1,2 ring-opening is observed exclusively affording 17a-c besides 19a, b.Similarly, in the cycloaddition of ketenimines 23a, b with azirine 2b only 1,2-bond cleavage can be detected to give pyrrolines 26a, b and imidazole derivatives 28, respectively.
- Schaumann, Ernst,Grabley, Susanne
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p. 290 - 305
(2007/10/02)
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- Die Hydrolyse von 6exo-substituierten 2exo- und 2endo-Norbornylestern der p-Toluolsulfonsaeure
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Hydrolysis of the 6exo-substituted 2exo- and 2endo-norbornyl p-toluenesulfonates 1b-l and 2b-l, respectively, in 70percent dioxane led to different amounts of the following products: Unrearranged 2exo-norbornanols 3 and norbornenes 5, accompained in somes cases by small amounts of the rearranged Rendo-epimers 4 and 6 and by nortricyclenes 7.When the 6exo-substituent was a nucleophile group as in 1e-l and 2e-l, various amounts of tricyclic products were also formed by endo-cyclozation.These results show that the 2exo- and 2endo-esters 1 and 2, respectively, react by way of different intermediates.In cases where the 6exo-substituent was an n-electron donor, as in 1m-r and 2m-r, quantitative fragmentation to (3-cyclopentenyl)acetaldehyde (13) occurred.
- Fischer, Walter,Grob, Cyril A.,Sprecher, Georg von,Waldner, Adrian
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p. 928 - 937
(2007/10/02)
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