中国科学院上海有机化学研究所机构知识库
Advanced  
SIOC OpenIR  > 分析化学研究室  > 期刊论文
学科主题: 分析化学
题名: Sulfonamide bond cleavage in benzenesulfonamides and rearrangement of the resulting p-aminophenylsulfonyl cations: application to a 2-pyrimidinyloxybenzylaminobenzenesulfonamide herbicide
其他题名: 质谱学研究气相中2-羟基苄基-N-嘧啶胺衍生物的逆-Michael类型裂解反应
作者: Wang HY(王昊阳) ; Zhang X(张祥) ; Guo YL(郭寅龙) ; Lv L(吕龙)
通讯作者: 郭寅龙 ; 吕龙
刊名: Rapid Commun. Mass Spectrom.
发表日期: 2005-01-01
卷: 19, 期:12, 页:1696-1702
收录类别: SCI
部门归属: 上海有机化学研究所
英文摘要: The gas-phase fragmentation/rearrangement reactions of compound 1, [2-(4,6-dimethoxypyrimidin-2-yloxy)-benzyl]-[4-(piperidine-l-sulfonyl)ph enyl]amine, have been examined by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The analyses reveal that under sustained off-resonance irradiation collision-induced dissociation (SORI-CID) conditions in the FTICR cell, protonated 1 undergoes two competitive pathways initiated by different protonation positions. The first pathway is initiated by protonation on the amino group and yields only one fragment ion due to loss of the entire benzenesulfonamide moiety. In the second pathway, protonation of the sulfonamide group leads to cleavage of a sulfonamide bond with loss of the neutral piperidine, followed by loss of SO via a sulfonyl cation rearrangement. An intrarnolecular SNAr mechanism is proposed to rationalize the rearrangement of the p-aminophenylsulfonyl cation and the resulting SO loss. To test the generality of this process, SORI-CID spectra of protonated sulfamethoxazole and of the p-aminophenylsulfonyl cation (SBN) were obtained. For the SBN ion, SORI-CID experiments as well as density functional theory (B3LYP) calculations show that rearrangement, assigned as a SNAr reaction of the sulfonyl cation group, can account for the observed SO loss process. Candidate transition state structures were optimized at the B3LYP/6-31+G (d, p) level of theory using the Gaussian98 molecular modeling package. The computational results show that the barrier for SO loss from SBN is much lower than that for SO2 loss, which satisfactorily rationalizes the SORT-CID experimental results for SBN. Moreover, it is proposed that a fragment ion at m/z 196 in the MS/MS spectrum of protonated 1 is formed via the ion resulting from SO loss via a second intramolecular SNAr mechanism. Copyright (c) 2005 John Wiley & Sons, Ltd.
语种: 英语
相关网址: 查看原文
WOS记录号: WOS:000229846800015
Citation statistics:
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/19894
Appears in Collections:分析化学研究室_期刊论文

Files in This Item: Download All
File Name/ File Size Content Type Version Access License
2005150.pdf(920KB)----开放获取--View Download

Recommended Citation:
Wang HY,Zhang X,Guo YL,et al. Sulfonamide bond cleavage in benzenesulfonamides and rearrangement of the resulting p-aminophenylsulfonyl cations: application to a 2-pyrimidinyloxybenzylaminobenzenesulfonamide herbicide[J]. Rapid Commun. Mass Spectrom.,2005,19(12):1696-1702.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[王昊阳]'s Articles
[张祥]'s Articles
[郭寅龙]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[王昊阳]‘s Articles
[张祥]‘s Articles
[郭寅龙]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
文件名: 2005150.pdf
格式: Adobe PDF
此文件暂不支持浏览
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace