dibutyl chlorothiophosphate | 2524-07-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机硫代磷酸及其衍生物
• 英文名称: dibutyl chlorothiophosphate
• 英文别名: Thiophosphorsaeure-O.O-dibutylester-chlorid；Dibutylchlorthiophosphat；Thiophosphorsaeure-dibutylester-chlorid；Phosphorochloridothioic acid, dibutyl ester；dibutoxy-chloro-sulfanylidene-λ5-phosphane
• CAS: 2524-07-4
• 化学式: C₈H₁₈ClO₂PS
• 分子量: 244.722
• InChiKey: YQNUVUVGKIVWNY-UHFFFAOYSA-N

物化性质

• 沸点：
  95-98 °C(Press: 2 Torr)
• 密度：
  1.0695 g/cm3(Temp: 00 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  13
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  dibutyl chlorothiophosphate 在 sodium hydrogensulfide 、 乙醇 作用下， 生成 O,O-dibutyldithiophosphoric acid
  参考文献：
  名称：

  Basic Research and Implications for Practice in Family Science: A Content Analysis and Status Report for U.S. Ethnic Groups

  摘要：

  Articles published in prominent family science journals over a 14‐year period were analyzed for their attention to U.S. ethnic groups. Articles were analyzed in terms of their ethnic population of interest, topic of study, type of implication for applied professionals, funding source, and sample characteristics. A number of findings indicate an increasing sensitivity and dedication to research focusing on these groups; however, fewer than 16% of the articles were found to focus on U.S. ethnic populations, and only one fourth of these offered specific recommendations to practicing family science professionals. This analysis of the family science literature provides a baseline against which future efforts in basic and applied research can be measured.

  DOI：

  10.1111/j.1741-3729.2002.00015.x
• 作为产物：
  描述：

  O,O-dibutyldithiophosphoric acid 在 氯 作用下， 生成 dibutyl chlorothiophosphate
  参考文献：
  名称：

  Method of preparing dialkyl chlorothiophosphates

  摘要：

  公开号：

  US02692893A1

文献信息

• Synthesis and Cholinesterase Inhibitory Activity of N-Phosphorylated/ N-Tiophosphorylated Tacrine
  作者：Maja Przybyłowska、Iwona Inkielewicz-Stepniak、Szymon Kowalski、Krystyna Dzierzbicka、Sebastian Demkowicz、Mateusz Daśko

  DOI：10.2174/1573406415666190716115524

  日期：2020.11.6

  agents. Methods: 9-Chlorotacrine was treated with propane-1,3-diamine in the presence of sodium iodide to yield N1-(1,2,3,4-tetrahydroacridin-9-yl)propane-1,3-diamine 6. Finally, it was treated with corresponding acid ester or thioester to give phosphorus or thiophosphorus tacrine derivative 7-14. All of the obtained final structures were characterized by 1H NMR, 13C NMR, 31P NMR and MS. Results: The

  背景：阿尔茨海默氏病（AD）是进行性和不可逆的神经退行性疾病。当前的药物疗法不能停止疾病的进展并且只能改善认知功能。因此，正在寻找新的药物来减缓疾病的发展。 目的：设计，合成新型的磷和硫代磷他克林衍生物7-14，并研究它们的生物学活性和分子模型，作为一种潜在的新型抗阿尔茨海默氏病（AD）药物。 方法：在碘化钠存在下，用丙烷-1,3-二胺处理9-氯代高辛，得到N1-（1,2,3,4-四氢ac啶-9-基）丙烷-1,3-二胺6。最后，用相应的酸酯或硫代酯处理，得到磷或硫代磷他克林衍生物7-14。通过1 H NMR，13 C NMR，31 P NMR和MS表征所有获得的最终结构。 结果：对接研究的结果表明，新设计的磷和硫代磷他克林类似物在理论上具有AChE和BChE结合能力。动力学研究表明，该系列中的8和12被证明是比他克林更有效的电鳗AChE（eeAChE）和人类（hAChE）抑制剂，其中8种和
• Reaction of oxophosphoranesulphenyl chlorides with phosphorus trichloride
  作者：J. Omelańczuk、P. Kielbasiński、J. Michalski、J. Mikołajczak、M. Mikołajczyk、A. Skowrońska

  DOI：10.1016/0040-4020(75)80295-x

  日期：1975.1

  phosphorus trichloride has been found to give thiophosphoryl chlorides, and phosphoryl oxychloride—the products of the exclusive deoxygenation of sulphenyl chloride. Optically active phosphonochloridothionates and phosphorochloridothionates in a high state of optical purity have been obtained with inversion of configuration from optically active sulphenyl chlorides and phosphorus trichloride. It has been

  已经发现无环的氧代磷酰氨基磺酰氯与三氯化磷的反应生成了硫代磷酰氯和磷酰氯，这是亚硫酰氯的唯一脱氧产物。通过旋光性的亚硫酰氯和三氯化磷的构型的反转，已经获得了具有高光学纯度的旋光性膦酰氯硫代酸酯和磷酰氯硫代酸酯。然而，已经表明，当用三氯化磷处理时，环状氧代磷酸金磺酰苯氯会同时脱硫和脱氧。使用顺式和反式-2-氯硫代-4-甲基-1，3，2-二氧杂磷酰胺基-2-酮的异构体已经证明，脱氧伴随着转化，而脱硫发生并保留在磷上。讨论了标题反应的机理。
• 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 Anilinolyses of Ethyl Methyl, Ethyl Propyl and Diisopropyl Chlorothiophosphates in Acetonitrile
  作者：Hasi Rani Barai、Md. Ehtesham Ul Hoque、Hai Whang Lee

  DOI：10.5012/bkcs.2013.34.12.3811

  日期：2013.12.20

  methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at . A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; ) are secondary inverse () with 2, primary normal and secondary inverse () with 4, and primary normal () with 7. The

  甲基乙基 (2)、乙基丙基 (4) 和二异丙基 (7) 氯硫代磷酸酯与取代的苯胺和氘代苯胺的亲核取代反应在乙腈中进行了动力学研究。基于选择性参数提出了一种协同机制。氘动力学同位素效应 (DKIEs;) 是 2 的次级逆 ()、4 的初级正态和次级逆 () 以及 7 的初级正态 ()。初级正态和次级逆 DKIE 通过涉及氢键的正面攻击合理化，四中心型过渡态和涉及直列型过渡态的背面攻击，分别。基于反应性、两个配体的空间效应、硫代效应、反应机理、DKIE 和活化参数检测了十种氯代硫代磷酸酯的苯胺水解。
• Kinetics and Mechanism of Anilinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile
  作者：Hasi Rani Barai、Hai Whang Lee

  DOI：10.5012/bkcs.2014.35.9.2797

  日期：2014.9.20

  Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^\circ}C$. A concerted mechanism is proposed for 8 based on the negative $\rho}_XY}$ (= -0.23) value, while a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed for 10 based on the positive $\rho}_XY}$ (= +0.68) value. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are 0.89-1.28 and 0.62-1.20 with 8 and 10, respectively. Primary normal and secondary inverse DKIEs are rationalized by a frontside attack involving hydrogen bonded, four-center-type transition state and backside attack involving in-line-type transition state, respectively.

  在乙腈中于$55.0^\circ}C$下，研究了Y-芳基甲基（8）和Y-芳基丙基（10）氯硫磷酸盐与取代苯胺和氘代苯胺的亲核取代反应动力学。基于负值的$\rho}_XY}$（=-0.23），为8提出了协同机理，而基于正值的$\rho}_XY}$（=+0.68），为10提出了带有速率限制中间体离去基团的分步机理。氘的同位素效应（DKIEs; $k_H/k_D$）分别为8的0.89-1.28和10的0.62-1.20。通过涉及氢键的四中心型过渡态的前侧攻击和涉及直线型过渡态的后侧攻击，分别合理化了初级正常和次级反向的DKIEs。