- 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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- AEROBIC OXIDATIVE SYNTHESIS OF SULFONAMIDE USING Cu CATALYST
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The present invention relates to a method for oxidative synthesis of sulfonamides using copper catalysts. , Oxygen (O) is used. 2 The oxidative synthesis of sulfonamides (1) comprises reacting a 2 th or sulfonyl hydrazide primary amine with a sulfonyl hydrazide (sulfonamide) with a copper catalyst on a solvent under the conditions in which the sulphonamide is fed. The oxidation coupling of the present invention showed extensive substrate ranges in an amine comprising a 2 primary amine, 1 primary amine and amine hydrochloride salt. It is worth notable that non-reactive aliphatic sulfonyl hydrazides in previously reported anaerobic systems can be used for the aerobic oxidation coupling of the present invention. The oxidation coupling of the present invention has been more effective on large scale.
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Paragraph 0033-0037; 0039-0054; 0119-0120
(2021/04/06)
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- Using Small Molecules to Enhance P450 OleT Enzyme Activity in Situ
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Cytochrome P450 OleT is a fatty acid decarboxylase that catalyzes the production of olefins with biofuel and synthetic applications. However, the relatively sluggish catalytic efficiency of the enzyme limits its applications. Here, we report the application of a novel class of benzene containing small molecules to improve the OleT activity. The UV-Vis spectroscopy study and molecular docking results confirmed the high proximity of the small molecules to the heme group of OleT. Up to 6-fold increase of product yield has been achieved in the small molecule-modulated enzymatic reactions. Our work thus sheds the light to the application of small molecules to increase the OleT catalytic efficiency, which could be potentially used for future olefin productions.
- Zhang, Libo,Ma, Dumei,Yin, Yingwu,Wang, Qian
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supporting information
p. 8940 - 8945
(2021/05/28)
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- Cyanide-Mediated Synthesis of Sulfones and Sulfonamides from Vinyl Sulfones
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We report a facile synthesis of sulfones, β-keto sulfones, and sulfonamides from vinyl sulfones via an addition-elimination sequence where in situ generation of nucleophilic sulfinate ion is mediated by cyanide. The use vinyl sulfones renders high selectivity for S -alkylation to produce sulfones in high yields. In the presence of N -bromosuccinimide, primary and secondary amines underwent sulfonamide formation. A preliminary mechanistic study showed the formation of acrylonitrile as an innocent byproduct, without interfering with the desired reaction pathway while generating a sulfinate nucleophile.
- Lee, Ji-Woong,Roy, Tamal
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p. 455 - 458
(2020/03/13)
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- Solid-phase synthesis method of N-butylbenzenesulfonamide
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The invention discloses a solid-phase synthesis method of N-butylbenzenesulfonamide, which comprises the following steps: (1) feeding reaction, namely, carrying out a solvent-free solid-phase reactionon benzenesulfonyl chloride, an n-butylamine raw material and an inorganic alkaline compound; (2) suction filtration, namely, separating and washing the reacted solid by using an organic solvent, andcombining organic phases; and (3) distillation and purification, namely, carrying out reduced pressure distillation and purification on the combined organic phase under vacuum, and collecting 150-160DEG C/0.5mmHg of distillate to obtain the N-butylbenzenesulfonamide. Benzenesulfonyl chloride, the n-butylamine raw material and the inorganic alkaline compound are subjected to a solvent-free solid-phase reaction to synthesize N-butylbenzenesulfonamide, the method has the advantages of simple process, mild reaction conditions, high synthesis rate, safety and environmental protection, and the obtained N-butylbenzenesulfonamide has the advantages of high yield, high purity and good quality and has a wide market prospect.
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-
Paragraph 0021-0035
(2020/04/17)
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- Liganding Functional Tyrosine Sites on Proteins Using Sulfur-Triazole Exchange Chemistry
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Tuning reactivity of sulfur electrophiles is key for advancing click chemistry and chemical probe discovery. To date, activation of the sulfur electrophile for protein modification has been ascribed principally to stabilization of a fluoride leaving group (LG) in covalent reactions of sulfonyl fluorides and arylfluorosulfates. We recently introduced sulfur-triazole exchange (SuTEx) chemistry to demonstrate the triazole as an effective LG for activating nucleophilic substitution reactions on tyrosine sites of proteins. Here, we probed tunability of SuTEx for fragment-based ligand discovery by modifying the adduct group (AG) and LG with functional groups of differing electron-donating and -withdrawing properties. We discovered the sulfur electrophile is highly sensitive to the position of modification (AG versus LG), which enabled both coarse and fine adjustments in solution and proteome activity. We applied these reactivity principles to identify a large fraction of tyrosine sites (～30%) on proteins (～44%) that can be liganded across >1500 probe-modified sites quantified by chemical proteomics. Our proteomic studies identified noncatalytic tyrosine and phosphotyrosine sites that can be liganded by SuTEx fragments with site specificity in lysates and live cells to disrupt protein function. Collectively, we describe SuTEx as a versatile covalent chemistry with broad applications for chemical proteomics and protein ligand discovery.
- Brulet, Jeffrey W.,Borne, Adam L.,Yuan, Kun,Libby, Adam H.,Hsu, Ku-Lung
-
supporting information
p. 8270 - 8280
(2020/05/25)
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- Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols
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Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.
- Laudadio, Gabriele,Barmpoutsis, Efstathios,Schotten, Christiane,Struik, Lisa,Govaerts, Sebastian,Browne, Duncan L.,No?l, Timothy
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supporting information
(2019/04/16)
-
- Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols
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Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.
- Laudadio, Gabriele,Barmpoutsis, Efstathios,Schotten, Christiane,Struik, Lisa,Govaerts, Sebastian,Browne, Duncan L.,No?l, Timothy
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supporting information
p. 5664 - 5668
(2019/04/17)
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- Cu-catalyzed aerobic oxidative synthesis of sulfonamides from sulfonyl hydrazides and amines
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An environmentally friendly route for sulfonamides has been developed. The oxidative coupling of sulfonyl hydrazides and amines was catalyzed by CuBr2 to produce various sulfonamides with the water and nitrogen gas as byproducts. Preliminary experiments revealed that the sulfonyl radical is likely to be involved in the reaction mechanism.
- Chung, Sohyun,Kim, Jinho
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p. 792 - 795
(2019/02/16)
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- Synthesis method for N-butyl benzsulfamide
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The invention discloses a synthesis method for N-butyl benzsulfamide. The synthesis method comprises the following steps: by taking sodium hydroxide, phenyl sulfonyl chloride, n-butylamine, sodium metaaluminate, phosphoric acid, dipentaerythritol, ammonium polyphosphate and tetraethoxysilane as primary raw materials, carrying out contact of phenyl sulfonyl chloride and excessive n-butylamine and an alkaline reagent under the action of a porous catalyst; then removing water and excessive amine in an organic phase; and separating butyl benzsulfamide. The reaction yield is further improved by means of an ultrasonic assisted reaction, and the follow-up separation and purification processes are simplified, thereby providing a novel method for industrial production of a plasticizer N-butyl benzsulfamide.
- -
-
Paragraph 0007; 0009-0028
(2019/03/08)
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- Efficient synthesis, spectroscopic characterization and DFT based studies of novel 1-amide 4-sulfonamide-1,2,3-triazole derivatives
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In the present study, for the first time 1-amide 4-sulfonamide-1,2,3-triazole scaffolds were synthesized by using an azide-alkyne Huisgen cycloaddition reaction. The target products were obtained in moderate to good yields (45–75%) by using catalytic CuI and green system H2O/EtOH. The easy availability of the inexpensive starting materials, avoiding isolation and handling of hazardous organic azides and mild reaction conditions make this method a valuable tool for generating functionalized 1,2,3-triazole derivatives. The unambiguous characterization of synthesized compounds was accomplished by using various spectroscopic techniques such as 1H NMR, 13C NMR, and FT-IR. The information regarding optimized geometry, were obtained by applying DFT/B3LYP-6-31G(d) method. The electrophilicity index, 1H and 13C chemical shift values, lithium and sodium ion affinities of the desired product 3b have been also calculated by the mentioned method. As a whole, the calculated results were found in close agreement to that of experimental data. The studies revealed that the compound 3b possesses good Li+ and Na+ affinity and cation π interaction plays a vital role in the complexation of 3b. For the first time, nucleus–independent chemical shift index was used to confirm the cation π interaction of 3b.
- Bonyad, Sarvenaz Rouhi,Mirjafary, Zohreh,Saeidian, Hamid,Rouhani, Morteza
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p. 164 - 170
(2019/07/18)
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- MANUFACTURING METHOD OF COMPOUND HAVING SULFONYL GROUP
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The present invention relates to a method for manufacturing a compound having a sulfonyl group, which includes a step for reacting thiosulfonates in a solvent comprising nucleophilic bases with an electrophilic agent. Accordingly, the present invention can manufacture the compound having the sulfonyl group with a variety of structures with high efficiency and high yield through more simplified processes than conventional methods.COPYRIGHT KIPO 2018
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Paragraph 0187; 0188; 0190-0193
(2018/10/03)
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- A Route to O-Aminosulfonates and Sulfonamides through Insertion of Sulfur Dioxide and Hydrogen Atom Transfer
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A three-component reaction of aryldiazonium tetrafluoroborates, the 1,4-diazabicyclo[2.2.2]octane?bis(sulfur dioxide) adduct [DABCO?(SO2)2] and hydroxylamines under catalyst-free and additive-free conditions has been developed, providing aryl O-aminosulfonates in good yields. Sulfonamides could also be obtained via a one-pot process through the reaction of aryldiazonium tetrafluoroborates, DABCO?(SO2)2 and amines in the presence of N-hydroxybenzotriazole. A mechanism involving the insertion of sulfur dioxide and hydrogen atom transfer is proposed and supported by theoretical calculations. (Figure presented.).
- Liu, Tong,Zheng, Danqing,Li, Zhenhua,Wu, Jie
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supporting information
p. 2653 - 2659
(2017/08/16)
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- Synthesis of Sulfones and Sulfonamides via Sulfinate Anions: Revisiting the Utility of Thiosulfonates
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Simple and high-yielding strategies for the production of a variety of sulfones and sulfonamides, using thiosulfonates synthesized by copper-catalyzed aerobic dimerization, are reported. Although thiosulfonates are an old class of compound, practical methods for their synthesis and utilization have not been rigorously developed. In this study, we revisit the reactions of easily accessible thiosulfonates to form sulfinate anions. Because of the similar reactivity of thiosulfonates and metal sulfinates derived from toxic SO2, thiosulfinates are proposed to be stable, nontoxic alternatives to metal sulfinate salts.
- Shyam, Pranab K.,Jang, Hye-Young
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p. 1761 - 1767
(2017/02/10)
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- (Dicyclopentadiene) platinum(II) dichloride: An efficient catalyst for the hydrosilylation reaction between alkenes and triethoxysilane
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(Dicyclopentadiene) platinum(II) dichloride was found to be an efficient hydrosilylation catalyst (homogeneous) upon a wide variety of functionalized alkenes and alkenes terminated with chemical moieties (diphenyl amino-, N-carbazol- and N-isoindoline-1,3-dione-). It is noteworthy that the hydrosilylation of aminated alkenes with triethoxysilane exhibited the yield of over 70% and the selectivity (γ-isomer/β-isomer) of more than 3/1. Due to steric hindrance lowering Markovnikov probability, the alkenes with big terminal moieties (diphenyl amino-, N-carbazol- and N-isoindoline-1,3-dione-) presented the high ratio of anti-Markovnikov isomers. The strategy of the hydrosilylation of the protected diamino chelating alkene was developed.
- Wu, Huarui,Zheng, Chaoyue,Chen, Naiwu,Zhu, Jie,Gao, Deqing
-
supporting information
p. 1576 - 1578
(2017/04/03)
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- Efficient synthesis of novel 1,3-diyne-based sulfonamides using CuCl2/Et3N as a robust catalytic system
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An efficient and practical synthesis of 1,3-diyne-based sulfonamides using CuCl2/Et3N as a catalytic system is disclosed. Mild reaction conditions, atom-economy and high yields (50–91%) make this method an attractive option for the preparation of 1,3-diyne-based sulfonamide derivatives.
- Mirjafary, Zohreh,Sadighian, Hamed,Piri, Samira,Saeidian, Hamid
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p. 188 - 194
(2017/03/07)
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- Metal-free direct construction of sulfonamides via iodine- mediated coupling reaction of sodium sulfinates and amines at room temperature
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A simple, practical, and metal-free protocol has been developed for the synthesis of sulfonamides from sodium sulfinates and various amines through an iodine-mediated SN bond formation reaction at room temperature. This green reaction is cost-effective, operationally straightforward, and especially proceeds under very mild conditions to afford the target products in good to excellent yields (up to 98%).
- Wei, Wei,Liu, Chunli,Yang, Daoshan,Wen, Jiangwei,You, Jinmao,Wang, Hua
-
supporting information
p. 987 - 992
(2015/03/30)
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- Palladium-Catalyzed Regio- and Chemoselective Reactions of 2-Bromobenzyl Bromides: Expanding the Scope for the Synthesis of Biaryls Fused to a Seven-Membered Sultam
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Speedy access to biaryls fused to seven-membered sultams was achieved by starting from readily accessible N-alkylbenzenesulfonamides and 2-bromobenzyl bromides. The protocol features a domino reaction and proceeds through an N-benzylation followed by an intramolecular direct C-H arylation that occurs ortho to the sulfonamide group. A palladium-catalyzed domino reaction of N-alkylbenzenesulfonamides and 2-bromobenzyl bromides gives biaryls fused to a seven-membered sultam. This approach employs readily accessible substrates and provides speedy access to fused-ring compounds.
- Laha, Joydev K.,Sharma, Shubhra,Dayal, Neetu
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p. 7885 - 7891
(2015/12/24)
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- Synthesis of nitromethyl-substituted oxindole derivatives via a desulfonylation cascade
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A cascade reaction giving nitromethyl-substituted oxindole derivatives was developed. The reaction used NaNO2 as the nitro source and potassium peroxydisulfate as an oxidant. This reaction proceeded via a radical mechanism involving substitution-desulfonlylation-cyclization steps in one pot and afforded good yields under mild conditions without using toxic metal catalysts. The resultant nitromethyl-substituted oxindole derivatives are convenient and valuable structures for different derivative syntheses.
- Niu, Ben,Xie, Ping,Bian, Zhaogang,Zhao, Wannian,Zhang, Min,Zhou, Yang,Feng, Lei,Pittman, Charles U.,Zhou, Aihua
-
supporting information
p. 635 - 638
(2015/03/14)
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- TiCl4-mediated direct N-alkylation of sulfonamides with inactive ethers
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A TiCl4-mediated intermolecular or intramolecular direct N-alkylation reaction of sulfonamides with inactive ethers as alkylating agents was successfully achieved. This method provides a novel approach towards N-alkyl sulfonamides from inactive ethers via an easy workup procedure. Georg Thieme Verlag Stuttgart · New York.
- Chen, Jiayan,Dang, Ling,Li, Qiang,Ye, Yong,Fu, Shaomin,Zeng, Wei
-
supporting information; experimental part
p. 595 - 600
(2012/03/27)
-
- Ionic liquid-supported synthesis of sulfonamides and carboxamides
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An ionic liquid-supported aldehyde was designed and converted to ionic liquid-supported secondary aryl amines through reductive amination. The reaction of ionic liquid-supported aryl amines with sulfonyl chlorides and acid chlorides, respectively, followed by cleavage using trifluoroacetic acid (TFA) afforded sulfonamides and caboxamides. To introduce additional diversity in the synthesis of sulfonamides and caboxamides, ionic liquid-supported iodosubstituted aryl amine was synthesized using the same strategy, and underwent Suzuki coupling reaction, followed by reaction with a methanesulfonyl chloride to generate the corresponding biaryl sulfonamide. The advantages of the protocol over solid-phase synthesis are homogeneous reaction medium, high loading, easy separation of products, and characterization of intermediates.
- Muthayala, Manoj Kumar,Chhikara, Bhupender S.,Parang, Keykavous,Kumar, Anil
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experimental part
p. 60 - 65
(2012/02/04)
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- Synthesis and applications of Fe3O4- diisopropylaminoacetamide as a versatile and reusable magnetic nanoparticle supported N,N-diisopropylethylamine equivalent
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A magnetic nanoparticle supported N,N-diisopropylaminoacetamide (Fe 3O4-DIPA) was developed for application as a magnetic recoverable, and reusable N,N-diisopropylethylamine equivalent. The Fe 3O4 nanoparticles were coated with a silica layer using the sol-gel method, followed by surface modification with 3- aminopropyltriethoxysilane. Subsequent acylation with chloroacetyl chloride and chlorine displacement with diisopropylamine afforded Fe3O 4-DIPA in 90% yield with a loading of 0.96 mmol/g. The applicability of Fe3O4-DIPA was demonstrated in the synthesis of amine derivatives cv sulfonation, acylation, and N-alkylation reactions. The desired products were obtained in excellent yields and purities after scavenging the residual starting amines by treatment with silica-supported dichlorotriazine. Fe3O4-DIPA was readily recovered by separation using a magnet and could be reused several times without significant loss of reactivity.
- Rattanaburi, Parintip,Khumraksa, Bannarak,Pattarawarapan, Mookda
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supporting information; experimental part
p. 2689 - 2693
(2012/07/17)
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- One-pot synthesis of sulfonamides from methyl sulfinates using ultrasound
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Room temperature ultrasonic irradiation of neat mixtures of methyl sulfinates and primary or secondary amines (1.5 equiv) produced sulfinamides, which on m-CPBA oxidation (in dichloromethane) were converted into the corresponding sulfonamides. The two steps can be accomplished in one pot, in good overall yields, when using secondary amines, but primary amines give better sulfonamide yields when the peracid oxidation is effected on the purified sulfinamide. This constitutes a mild, efficient, and potentially scalable route to sulfonamides, which obviates the use of water sensitive, often lachrymatory sulfonyl chlorides and large reagent excesses.
- García Ruano, José L.,Parra, Alejandro,Marzo, Leyre,Yuste, Francisco,Mastranzo, Virginia M.
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experimental part
p. 2905 - 2910
(2011/05/05)
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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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- Synthesis and application of a microgel-supported acylating reagent by coupled ring-opening metathesis polymerization and activators Re-Generated by electron transfer for atom transfer radical polymerization
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A novel microgel-supported acylating reagent (MGAR) was prepared by combining ring-opening metathesis polymerization (ROMP) and Activators Re-Generated by Electron Transfer for Atom Transfer Radical Polymerization (ARGET ATRP): (1) synthesis of an ATRP macroinitiator 3 by living ROMP of oxanorbornene-based activated ester 1, derived from Af-hydroxysuccinimide, using the Grubbs initiator RuCl2(PCy3)2(=CHPh) and (Z)-but-2-ene-l,4-diyl bis(2-bromopropanoate) (BDBP) as a terminating agent; (2) synthesis of MGAR 4 by ARGET ATRP of styrene (S) and divinylbenzene (DVB) using the prepared macroinitiator 3, a CuCI2ZMe6TREN (tris[2-(dimethylamino)ethyl]amine) catalyst system, a Sn(Oct)2 [tin(II)2ethylhexanoate] reducing agent. The synthesized microgels 4 exhibit excellent acyl (acetyl, benzoyl, phenylsulfonyl) transfer properties for primary and secondary amines (n-BuNH2, Et2NH, morpholine, etc.) under mild conditions (25 °C, 13.5-14 h) affording N-acylamines with high yield (95.6-100%) and purity (94.1-96.0%).
- Li, Hong,Pang, Zi-Bo,Jiao, Zhi-Feng,Lin, Fei
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experimental part
p. 255 - 259
(2010/09/03)
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- 2-Aryl propionamides via 1,4-aryl radical migration from N-arylsulfonyl-2-bromopropionamides
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Reaction of N-alkyl-N-arylsulfonyl-2-halo-propionamides with pentamethyldiethylenetriamine and either CuBr or CuCl leads to 2-aryl propionamides via initial radical generation, 1,4-aryl migration with loss of SO2 and reduction of the intermedia
- Clark, Andrew J.,Coles, Stuart R.,Collis, Alana,Fullaway, David R.,Murphy, Nicholas P.,Wilson, Paul
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scheme or table
p. 6311 - 6314
(2010/01/18)
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- A practical and efficient method for the preparation of sulfonamides utilizing Cl3CCN/PPh3
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Cl3CCN in combination with PPh3 proved to be a highly reactive reagent for the conversion of sulfonic acids to the corresponding sulfonyl chlorides in refluxing CH2Cl2. Upon reaction with amines, the corresponding sulfonamides were obtained in good to excellent yields.
- Chantarasriwong, Oraphin,Jang, Doo Ok,Chavasiri, Warinthorn
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p. 7489 - 7492
(2007/10/03)
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- Benzenesulfonyl chloride with primary and secondary amines in aqueous media - Unexpected high conversions to sulfonamides at high pH
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We have determined pH-yield profiles under pseudo-first-order conditions of the reactions of benzenesulfonyl chloride with a set of primary and secondary water-soluble alkylamines, and have found with certain amines, such as dibutylamine, a profile taking the form of a sigmoid pH-yield curve with relatively high yields of the sulfonamide persisting with increasing basicity up to and including 1.0 mol/L sodium hydroxide. This behaviour is quantitatively accounted for by invoking, in addition to the usual second-order reaction of the sulfonyl chloride with the amine, two third-order terms (i) one first-order in sulfonyl chloride, amine and hydroxide anion, and (H) another first-order in sulfonyl chloride and second-order in the amine. The importance of the third-order terms correlates approximately with the total number of alkyl carbon atoms in the amine, and this in turn is regarded as related to the hydrophobic character of the amine. Experiments to test this picture included: (i) observation of a bell-shaped curve with bis(2-methoxyethyl)amine, (H) in the reaction of dibutylamine in THF-H2O (1:1), and also (iii) in the reaction of dibutylamine in 1.0 mol/L tetrabutylammonium bromide, and (iv) increase in the contributions of the third-order terms in 1.0 mol/L aqueous sodium chloride. Preparative reactions with dibutylamine, 1-octylamine, and hexamethylenimine in 1.0 mol/L aqueous sodium hydroxide with a 5% excess of benzenesulfonyl chloride gave, respectively, 94%, 98%, and 97% yields of the corresponding sulfonamides.
- King, James F.,Gill, Manjinder S.,Ciubotaru, Petru
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p. 1525 - 1535
(2007/10/03)
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- Acetophenone-based linker for solid phase synthesis of secondary amides and sulfonamides on the multipin(TM) support
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A new and simple linker has been developed for synthesis of secondary amides and sulfonamides. This application is based on the reductive amination reaction between the acetophenone subunit of the linker and a wide range of primary amines including aliphatic and aromatic amines. Cleavage is effected under mild acidic conditions (20% TFA/DCM) to release the products in good yield and purity.
- Bui, Chinh T.,Bray, Andrew M.,Ercole, Francesca,Pham, Yen,Rasoul, Firas A.,Maeji, N. Joe
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p. 3471 - 3474
(2007/10/03)
-
- Experimental and Computational Evidence for the Formation of Iminopersulfinic Acids
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An experimental and computational study of the reactions of singlet oxygen with N-substituted sulfenamides is reported. Intermediates capable of epoxidizing norbornene were observed during the photooxidations of three sulfenamides. These results are used to argue for formation of iminopersulfinic acids. The structural integrity of two iminopersulfinic acids was supported by their successful location at the MP2/6-31G* level of theory. Furthermore, the inability to locate computationally significant persulfinimide precursors suggests that the iminopersulfinic acids form by enelike reactions involving near-simultaneous addition of singlet oxygen to sulfur and hydrogen abstraction.
- Clennan, Edward L.,Chen, Ming-Fang,Greer, Alexander,Jensen, Frank
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p. 3397 - 3402
(2007/10/03)
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- Preparation of arylsulfonamides
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A process improvement for the preparation of arylsulfonamides that avoids the multistep arylsulfonyl chloride refining operation presently used and, in one step, neutralizes and removes all the acidic by-products of chlorosulfonation simultaneously with arylsulfonamide formation which comprises the steps of (a) reacting an aryl hydrocarbon with chlorosulfonic acid to form a crude chlorosulfonation reaction product, (b) combining in an aqueous media said crude reaction product and a source of ammonia to form an amidation reaction mixture, (c) maintaining the temperature of the amidation reaction mixture at between about 40° C. and 70° C. and the pH at above about 7 with stirring for a period of time sufficient to form an amidation reaction product containing an arylsulfonamide, and optionally (d) separating the resulting arylsulfonamide from the amidation reaction product.
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