THE IODINATION OF 2,4,6-TRIDEUTERIOANISOLE BY IODINE MONOCHLORIDE
THE IODINATION OF 2,4,6-TRIDEUTERIOANISOLE BY IODINE MONOCHLORIDE
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DOI：
10.1021/ja01505a034
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发表时间：
1960-01-01
影响因子：
15
通讯作者：
BERLINER, E
中科院分区：
文献类型：
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作者：
BERLINER, E
本文研究了在含高氯酸和氯离子的水中，一氯化碘与2，4，6-三氘代苯甲醚碘化反应的动力学。该反应的同位素效应约为3.8，与氢离子（0.1 ~ 0.0001 M）和氯离子（0.3 ~ 0.9 M）浓度无关。从H2O到D2 O的变化使反应减慢约30%。实验表明，在很低的氯离子浓度下，同位素效应仍然存在，并得出结论，在各种可能的机理中，以H_2OI ~+作为取代剂的机理更为可能。氯苯胺、2、2，4-二氯苯酚和茴香醚，3的反应符合两种不同的机理，涉及不同的取代剂（方案A和B）。在方案A中，取代剂是H2O I+，它是通过ICl的水解形成的，而在方案B中，它是ICl本身，它与芳香族中间体处于平衡状态。的
The kinetics of iodination of 2, 4, 6-trideuterioanisole by iodine monochloride has been studied in water containing per-chloric acid and chloride ions. Thereaction has an isotope effect of about 3.8, which is independent of the hydrogen ion (0.1 to 0.0001 M) and the chloride ion (0.3 to 0.9 M) concentrations. A change from H20 to D20 slows downthe reaction by about 30%. Experiments were carried out which showed that the isotope effect persists to very low chloride ion concentra-tions, and it is concluded that of the various possible mechanisms, the one which involves H2OI+ as the substituting agent is the more likely.The kinetics of iodination by iodine mono-chloride of fairly reactive compounds, such a.^-chloroaniline, 2 2, 4-dichlorophenol and anisóle, 3 is in agreement with two different mechanisms, involving different substituting agents (Schemes A and B). In Scheme A the substituting agent is H20I+, which is formed by hydrolysis of ICl, and in Scheme B it is I Cl itself, which is in equi-librium with an aromatic intermediate. The