Department of Chemistry, Portland State University, Portland, Oregon 97207-0751, USA.
J Org Chem. 2010 Jun 18;75(12):4292-5. doi: 10.1021/jo100276m.
Pyridine derivatives and dichloromethane (DCM) are commonly used together in a variety of different applications. However, DCM slowly reacts with pyridine and a variety of other representative pyridine derivatives to form methylenebispyridinium dichloride compounds under ambient conditions. The proposed mechanism (two consecutive S(N)2 reactions) was studied by evaluating the kinetics of the reaction between 4-(dimethylamino)pyridine and DCM. The second-order rate constants for the first (k(1)) and second (k(2)) substitutions were found to be 2.56(+/-0.06) x 10(-8) and 4.29(+/-0.01) x 10(-4) M(-1) s(-1), respectively. Because the second substitution is so much faster than the first, the monosubstitution product could not be isolated or detected during the reaction; it was synthesized independently in order to observe its kinetics.
吡啶衍生物和二氯甲烷(DCM)在各种不同的应用中通常一起使用。然而,在环境条件下,DCM 会缓慢地与吡啶和各种其他代表性的吡啶衍生物反应,形成亚甲基双吡啶二氯化物化合物。通过评估 4-(二甲氨基)吡啶与 DCM 之间的反应动力学,研究了该反应的机理(两个连续的 S(N)2 反应)。发现第一个取代(k(1))和第二个取代(k(2))的二级速率常数分别为 2.56(+/-0.06) x 10(-8) 和 4.29(+/-0.01) x 10(-4) M(-1) s(-1)。由于第二个取代反应比第一个取代反应快得多,因此在反应过程中无法分离或检测到单取代产物;为了观察其动力学,它是独立合成的。