ethyl phenyl chlorophosphate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl phenyl chlorophosphate
• 英文别名: ethyl phenyl phosphorochloridate；O-phenyl O-ethyl chlorophosphate；[chloro(ethoxy)phosphoryl]oxybenzene
• 化学式: C₈H₁₀ClO₃P
• 分子量: 220.592
• InChiKey: LCXRVPWGRALHAD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl phenyl chlorophosphate 在 水 作用下， 生成 ethyl phenyl hydrogen phosphate
  参考文献：
  名称：

  Morel, Bulletin de la Societe Chimique de France, 1899, vol. <3> 21, p. 493

  摘要：

  DOI：
• 作为产物：
  描述：

  (chloroselanyl)diethoxy(phenoxy)phosphonium chloride 生成 ethyl phenyl chlorophosphate
  参考文献：
  名称：

  Reaction products of selenophosphorus acid esters with sulfuryl chloride

  摘要：

  DOI：

  10.1007/bf00921509

文献信息

• Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorothiophosphate in Acetonitrile
  作者：Md. Ehtesham Ul Hoque、Hai-Whang Lee

  DOI：10.5012/bkcs.2012.33.3.843

  日期：2012.3.20

  The nucleophilic substitution reactions of dibutyl chlorothiophosphate (4S) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs;$k_H/k_D$) are primary normal ($k_H/k_D$ = 1.10-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of the chlorothiophosphates are discussed. The anilinolyses of P=S systems are compared with those of their P=O counterparts on the basis of the reactivities, thio effects, selectivity parameters, and DKIEs.

  丁基氯硫酯（4S）与取代苯胺（$XC_6H_4NH_2$）和重氘取代苯胺（$XC_6H_4ND_2$）的亲核取代反应在<越南>$55.0^\circ}C$的乙腈中进行了动力学研究。获得的氘动力学同位素效应（DKIEs；$k_H/k_D$）为一级正常型（$k_H/k_D$ = 1.10-1.35）。根据一级正常DKIEs和选择性参数，提出了一种以前侧亲核攻击为主的协同机制。提出了氢键结合的四中心型过渡态。讨论了两种配体对氯硫磷酸酯苯胺水解速率的立体效应。在反应性、硫效应、选择性参数和DKIEs的基础上，比较了P=S系统的苯胺水解与其P=O对应物的苯胺水解。
• Kinetics and mechanism of the aminolysis of aryl ethyl chloro and chlorothio phosphates with anilines
  作者：Md. Ehtesham Ul Hoque、Nilay Kumar Dey、Chan Kyung Kim、Bon-Su Lee、Hai Whang Lee

  DOI：10.1039/b713167d

  日期：——

  acetonitrile at 55.0 degrees C are studied kinetically and theoretically. Kinetic results yield the primary kinetic isotope effects (k(H)/k(D) = 1.07-1.80 and 1.06-1.27 for 1 and 2, respectively) with deuterated aniline (XC(6)H(4)ND(2)) nucleophiles, and the cross-interaction constants rho(XY) = -0.60 and -0.28 for and , respectively. A concerted mechanism involving a partial frontside attack through a hydrogen-bonded

  动力学和理论上研究了乙基Y-苯基氯（1）和氯硫代（2）磷酸酯与X-苯胺在乙腈中在55.0摄氏度下的反应。动力学结果产生了氘代苯胺（XC（6）H（4）ND（2）的主要动力学同位素效应（1和2的k（H）/ k（D）分别为1.07-1.80和1.06-1.27）亲核试剂，以及的交叉相互作用常数rho（XY）= -0.60和-0.28。提出了一种通过氢键，四中心型过渡态参与部分正面攻击的协同机制。大的rho（X）（rho（nuc）= -3.1至-3.4）和beta（X）（beta（nuc）= 1.1-1.2）值似乎是带有离去基团的磷酸盐和硫代磷酸盐的苯胺分解的特征。由于苯胺亲核试剂相对较大，
• Kinetics and Mechanism of the Anilinolysis of Ethylene Phosphorochloridate in Acetonitrile
  作者：Hasi Rani Barai、Hai-Whang Lee

  DOI：10.5012/bkcs.2011.32.12.4185

  日期：2011.12.20

  The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines () and deuterated anilines () are investigated kinetically in acetonitrile at . The anilinolysis rate of 1c involving a cyclic five-membered ring is four thousand times faster than its acyclic counterpart (1a: diethyl chlorophosphate) because of great positive value of the entropy of activation of

  在乙腈中于 2000 年 2 月对氯代磷酸乙烯酯 (1c) 与取代苯胺 () 和氘代苯胺 () 的亲核取代反应进行了动力学研究。涉及环状五元环的 1c 的苯胺分解速率比其非环状对应物（1a：氯磷酸二乙酯）快 4000 倍，因为 1c 的活化熵的正值（与 1a 的负值（）相比相当大）与 1a () 相比，1c () 的活化焓不利。大的活化焓和正熵归因于空间拥挤的过渡态 (TS) 和 TS 中的溶剂结构破坏。对于取代基 X，自由能相关性表现出向上的双相凹X-苯胺的变化在 X = 3-Me 处具有断点。氘动力学同位素效应是弱碱性苯胺的二次逆（> 1），并且分别通过从主要背面攻击到主要正面攻击的 TS 变化合理化。提出了一种协同机制，并且主要的正常氘动力学同位素效应由氢键、四中心型 TS 证实。
• Kinetics and Mechanism of the Pyridinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile
  作者：Hasi Rani Barai、Hai-Whang Lee

  DOI：10.5012/bkcs.2012.33.1.270

  日期：2012.1.20

  The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1c) with X-pyridines are investigated kinetically in acetonitrile at $-25.0^\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 1c with a cyclic five-membered ring is $2.70\times}10^5$ times faster than its acyclic counterpart (1a: phenyl ethyl chlorophosphate) because of great positive value of the entropy of activation of 1c ($\Delta}S^\neq}$ = +26 eu) compared to negative value of 1a ($\Delta}S^\neq}$= -24 eu) over considerably unfavorable enthalpy of activation of 1c ($\Delta}H^\neq}=20.5kcal\;mol^-1}$) compared to 1a ($\Delta}H^\neq}=12.7kcal\;mol^-1}$). 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 on the basis of greater selectivity parameters ($\rho}_X$ = -1.99 and $\beta}_X$ = 0.41) with the strongly basic pyridines compared to those ($\rho}_X$ = -0.42 and $\beta}_X$ = 0.07) with the weakly basic pyridines.

  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。
• Kinetics and Mechanism of the Anilinolysis of Aryl Ethyl Isothiocyanophosphates in Acetonitrile
  作者：Hasi Rani Barai、Keshab Kumar Adhikary、Hai Whang Lee

  DOI：10.5012/bkcs.2013.34.6.1829

  日期：2013.6.20

  Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at . The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines

  Y-芳基乙基异硫氰基磷酸酯与取代的X-苯胺和氘代X-苯胺的亲核取代反应在乙腈中进行了动力学研究。亲核试剂中与 X 的自由能关系表现出双相向下凹入，在 X = H 处具有断点。基于强碱性苯胺的限速键形成和弱碱性苯胺的限速键断裂的逐步机制被提出分别为负值和正值。氘动力学同位素效应 (DKIEs;) 逐渐从强碱性苯胺的初级正态、苯胺的初级正态和次级逆向转变为弱碱性苯胺的次级逆向。初级正态和次级反向 DKIE 通过涉及氢键的正面攻击合理化，