1-(2-oxido-1,3,2-dioxaphospholan-2-yl)pyridin-1-ium chloride | 1360820-36-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: 1-(2-oxido-1,3,2-dioxaphospholan-2-yl)pyridin-1-ium chloride
• CAS: 1360820-36-5
• 化学式: C₇H₉NO₃P*Cl
• 分子量: 221.58
• InChiKey: MPUINESXYNVPJM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -2.02
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  39.41
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  吡啶 、 2-氯-2-氧-1,3,2-二氧磷杂环戊烷 以 乙腈 为溶剂， 生成 1-(2-oxido-1,3,2-dioxaphospholan-2-yl)pyridin-1-ium chloride
  参考文献：
  名称：

  Kinetics and Mechanism of the Pyridinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  摘要：

  在乙腈中，以动力学方法研究了1,2-苯二基膦氯化物（1c）与X-吡啶的亲核取代反应，反应温度为-25.0°C。对于亲核试剂中取代基X的变化，自由能相关性呈现出双相向上凹，且在X=3-Ph处有一个断裂点。1c的吡啶解离速率是它的非环状类似物（1a：苯基乙基氯膦酸酯）的2.70×10^5倍，这是由于与1a相比，1c的活化熵（ΔS≠=+26 eu）为正值，而1a的活化熵为负值（ΔS≠=-24 eu），尽管1c的活化焓（ΔH≠=20.5 kcal mol^-1）比1a的（ΔH≠=12.7 kcal mol^-1）更不利。巨大的活化焓和正值的活化熵归因于过渡态（TS）的立体拥挤以及TS中溶剂结构的破坏。基于与弱碱性吡啶相比，强碱性吡啶的选择性参数（ρX=-1.99和βX=0.41）大于弱碱性吡啶的（ρX=-0.42和βX=0.07），提出了一个协同机制，涉及亲核攻击方向从强碱性吡啶的前侧攻击到弱碱性吡啶的后侧攻击的改变。

  DOI：

  10.5012/bkcs.2012.33.1.270

文献信息

• Kinetics and Mechanism of the Pyridinolysis of (2R,4R,5S)-(+)-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-Sulfide in Acetonitrile
  作者：Hasi Rani Barai、Hai-Whang Lee

  DOI：10.5012/bkcs.2012.33.3.1047

  日期：2012.3.20

  The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide with X-pyridines are investigated kinetically in acetonitrile at $5.0^\circ}C$. The free energy relationships for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ac. Unusual positive $\rho_X$ (= +4.73) and negative $\beta}_X$ (= -0.75) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_ISOKINETIC}=39.3^\circ}C$. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater magnitudes of selectivity parameters ($\rho_X$ = -6.15 and $\beta}_X$ = 1.11) with the strongly basic pyridines compared to those ($\rho_X$ = 4.73 and $\beta}_X$ = -0.75) with the weakly basic pyridines.

  在乙腈中于$5.0^\circ}C$条件下，研究了(2R,4R,5S)-(+)-2-氯-3,4-二甲基-5-苯基-1,3,2-氧氮磷杂环己烷-2-硫酮与X-吡啶衍生物的亲核取代反应动力学。核试剂中取代基X的变化的自由能关系表现出双相向上凹，并在X=3-乙酰基处有断裂点。对于弱碱性吡啶，得到了异常的正值$\rho_X$（=+4.73）和负值$\beta}_X$（=-0.75），并通过等温关系和等温温度$t_ISOKINETIC}=39.3^\circ}C$进行了合理化解释。基于与强碱性吡啶（$\rho_X$=-6.15和$\beta}_X$=1.11）相比，弱碱性吡啶的选择性参数（$\rho_X$=4.73和$\beta}_X$=-0.75）更大的数值，提出了一种协同机理，涉及从强碱性吡啶的前侧攻击到弱碱性吡啶的后侧攻击的亲核攻击方向的改变。
• Kinetics and Mechanism of the Pyridinolysis of Ethylene Phosphorochloridate in Acetonitrile
  作者：Hasi Rani Barai、Hai-Whang Lee

  DOI：10.5012/bkcs.2011.32.12.4347

  日期：2011.12.20

  The nucleophilic substitution reactions of ethylene phosphorochloridate (2) with X-pyridines are investigated kinetically in acetonitrile at $-20.0^\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. Unusual positive $\rho}_X$ (= +2.49) and negative $\beta}_X$ (= -0.41) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_ISOKINETIC}=6.6^\circ}C$. The pyridinolysis rate of 2 with a cyclic five-membered ring is forty thousand times faster than its acyclic counterpart (3: diethyl chlorophosphate) because of great positive value of the entropy of activation of 2 ($\Delta}S^\neq}$ = +49.2 eu) compared to negative value of 3 ($\Delta}S^\neq}$ = -44.1 eu) over considerably unfavorable enthalpy of activation of 2 ($\Delta}H^\neq}=28.4\;kcal\;mol^-1}$) compared to 3 ($\Delta}H^\neq}=6.3\;kcal\;mol^-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed.

  在<$TEX}$>$-20.0^\circ}C$的乙腈中，研究了乙烯磷氯酸酯（2）与X-吡啶的亲核取代反应的动力学。亲核试剂中取代基X变化的自由能关联表现为二次相走势，且在X = 3-苯处出现了转折点。对于弱碱性吡啶，获得了异常的正<$\rho}_X$（= +2.49）和负<$\beta}_X$（= -0.41）值，并通过同动力学关系解释，得到的同动力学温度为<$TEX}$>$t_ISOKINETIC} = 6.6^\circ}C$。2与一个五元环的吡啶醇反应的速率比其无环对应物（3：二乙基氯磷酸酯）快四万倍，这归因于2的活化熵值的大正值（<$\Delta}S^\neq}$ = +49.2 eu），与3的负值（<$\Delta}S^\neq}$ = -44.1 eu）相比，在2的活化焓（<$\Delta}H^\neq}=28.4\;kcal\;mol^-1}$）相较于3（<$\Delta}H^\neq}=6.3\;kcal\;mol^-1}$）的显著不利下。大的焓和正的活化熵归因于立体拥挤的过渡态（TS）和在过渡态中溶剂结构的破坏。提出了一种协同机制，涉及从强碱性吡啶的前侧攻击向弱碱性吡啶的后侧攻击的亲核攻击方向的变化。