HYDROLYSIS AND ALKYLATING REACTIVITY OF AROMATIC NITROGEN MUSTARDS
HYDROLYSIS AND ALKYLATING REACTIVITY OF AROMATIC NITROGEN MUSTARDS
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DOI：
10.1039/p29910001933
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发表时间：
1991-12-01
期刊：
影响因子：
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通讯作者：
MCLENNAN, DJ
中科院分区：
文献类型：
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作者：
OCONNOR, CJ;DENNY, WA;MCLENNAN, DJ
使用 HPLC 技术获得了一系列芳香族氮芥 Ar-X-C6H4-N(CH2CH2Cl)2 (X = O、CH2、CONH、S、CO 和 SO2) 在缓冲的丙酮水溶液混合物中水解的速率常数，该技术可以评估连续反应中两种氯的水解置换的速率常数。 水解具有一般碱催化成分，并伴有外部氯离子返回。 氮丙啶鎓离子中间体涉及至少一种途径。 芥子气还烷基化亲核试剂硫脲和 4-(4-硝基苯甲基)-吡啶 (NBP)，并且再次涉及氮丙啶鎓离子中间体，因为动力学行为排除了直接的 S(N)2 途径。
Rate constants for the hydrolysis of a series of aromatic nitrogen mustards Ar-X-C6H4-N(CH2CH2Cl)2 (X = O, CH2, CONH, S, CO and SO2) in buffered aqueous acetone mixtures have been obtained using an HPLC technique which allows evaluation of the rate constants for hydrolytic displacement of both chlorines in consecutive reactions. Hydrolysis has a general-base-catalysed component and is accompanied by external chloride ion return. An aziridinium ion intermediate is implicated in at least one pathway. The mustards also alkylate the nucleophiles thiourea and 4-(4-nitrobenzyl)-pyridine (NBP) and again the aziridinium ion intermediate is involved since the kinetic behaviour rules out a direct S(N)2 pathway.