Preparation of Sulfonyl Chlorides by Oxidative Chlorination of Thiols and Disulfides using HNO3/HCl/O2 in a Flow Reactor

被引：1

作者：

Sulzer, Niklas ^{[1
,2
]}

Polterauer, Dominik ^{[1
,2
]}

Hone, Christopher A. ^{[1
,2
]}

Kappe, C. Oliver ^{[1
,2
]}

机构：

[1] Res Ctr Pharmaceut Engn GmbH RCPE, Ctr Continuous Flow Synth & Proc CCLOW, Inffeldgasse 13, A-8010 Graz, Austria

[2] Karl Franzens Univ Graz, Inst Chem, Heinrichstr 28, A-8010 Graz, Austria

来源：

CHEMSUSCHEM | 2024年 / 17卷 / 15期

关键词：

continuous flow; gas-liquid; sulfonyl chloride; oxidative chlorination; HIV-PROTEASE INHIBITORS; SULFONAMIDE DERIVATIVES; SULFINATE DERIVATIVES; LYSINE SULFONAMIDES; CONVENIENT; NAOCL-CENTER-DOT-5H(2)O; CONVERSION; DISCOVERY; PARTNERS; DESIGN;

D O I：

10.1002/cssc.202400292

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A continuous flow metal-free protocol for the synthesis of sulfonyl chlorides from thiols and disulfides in the presence of nitric acid, hydrochloric acid and oxygen was developed. The influence of the reaction parameters was investigated under batch and flow conditions. Online F-19 NMR was successfully implemented to investigate different reaction conditions within a single experiment. The sulfonyl chlorides were isolated (mostly in 70-81 % yield) after performing a simple aqueous washing procedure. In particular, the protocol was successfully operated for >6 hours to convert diphenyl disulfide to its corresponding sulfonyl chloride, achieving a throughput of 3.7 g h(-1). The environmental impact of the protocol was assessed and compared to an existing continuous flow protocol using 1,3-dichloro-5,5-dimethylhydantoin (DCH) as reagent. The process mass intensity (PMI) for the newly-developed flow protocol (15) compared favorably to the DCH flow process (20).

引用

页数：9

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