O,O-二丁基硫代磷酸氢酯 | 10163-62-9

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 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
• 中文名称: O,O-二丁基硫代磷酸氢酯
• 英文名称: O.O-Dibutyl-thiophosphat
• 英文别名: 1-[butoxy(sulfanyl)phosphoryl]oxybutane
• CAS: 10163-62-9
• 化学式: C₈H₁₉O₃PS
• 分子量: 226.277
• InChiKey: CCLBBCBPHBBKKD-UHFFFAOYSA-N

物化性质

• 沸点：
  75-76 °C(Press: 0.008 Torr)
• 密度：
  1.0670 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 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：
  70.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  O,O-二丁基硫代磷酸氢酯 在 磺酰氯 、 苯 作用下， 生成 dibutoxyphosphorylsulfenyl chloride
  参考文献：
  名称：

  Lenard-Borecka; Michalski, Roczniki Chemii, 1957, vol. 31, p. 1167,1172

  摘要：

  DOI：
• 作为产物：
  描述：

  亚磷酸二丁酯 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 三乙胺 作用下， 以 乙醚 为溶剂， 生成 O,O-二丁基硫代磷酸氢酯
  参考文献：
  名称：

  原位形成的邻醌甲基化物的无催化剂硫代磷酸化

  摘要：

  开发了原位形成的邻苯二酚甲基化物 ( o -QM)的金属-、氯化物试剂和无碱硫代磷酸化反应，以合成功能化的硫代磷酸盐。该反应是一个原子经济过程，产生水作为唯一的副产物。(EtO) 2 P(O)SH 作为布朗斯台德酸和亲核硫醇盐分别产生o -QM 中间体和硫代磷酸盐产物。氮杂o -QMs 在催化 TsOH 存在下也成功硫代磷酸化，形成磺胺基硫代磷酸盐。

  DOI：

  10.1039/d2ob02169b

文献信息

• Interrogation of the Substrate Profile and Catalytic Properties of the Phosphotriesterase from <i>Sphingobium</i> sp. Strain TCM1: An Enzyme Capable of Hydrolyzing Organophosphate Flame Retardants and Plasticizers
  作者：Dao Feng Xiang、Andrew N. Bigley、Zhongjie Ren、Haoran Xue、Kenneth G. Hull、Daniel Romo、Frank M. Raushel

  DOI：10.1021/acs.biochem.5b01144

  日期：2015.12.29

  The most familiar organophosphorus compounds are the neurotoxic insecticides and nerve agents. A related group of organophosphorus compounds, the phosphotriester plasticizers and flame retardants, has recently become widely used. Unlike the neurotoxic phosphotriesters, the plasticizers and flame retardants lack an easily hydrolyzable bond. While the hydrolysis of the neurotoxic organophosphates by phosphotriesterase enzymes is well-known, the lack of a labile bond in the flame retardants and plasticizers renders them inert to typical phosphotriesterases. A phosphotriesterase from Sphingobium sp. strain TCM1 (Sb-PTE) has recently been reported to catalyze the hydrolysis of organophosphorus flame retardants. This enzyme has now been expressed in Escherichia coli, and the activity with a wide variety of organophosphorus substrates has been characterized and compared to the activity of the well-known phosphotriesterase from Pseudomonas diminuta (Pd-PTE). Structure prediction suggests that Sb-PTE has a β-propeller fold, and homology modeling has identified a potential mononuclear manganese binding site. Sb-PTE exhibits catalytic activity against typical phosphotriesterase substrates such as paraoxon, but unlike Pd-PTE, Sb-PTE is also able to effectively hydrolyze flame retardants, plasticizers, and industrial solvents. Sb-PTE can hydrolyze both phosphorus–oxygen bonds and phosphorus–sulfur bonds, but not phosphorus–nitrogen bonds. The best substrate for Sb-PTE is the flame retardant triphenyl phosphate with a kcat/Km of 1.7 × 106 M–1 s–1. Quite remarkably, Sb-PTE is also able to hydrolyze phosphotriesters with simple alcohol leaving groups such as tributyl phosphate (kcat/Km = 40 M–1 s–1), suggesting that this enzyme could be useful for the bioremediation of a wide variety of organophosphorus compounds.

  最常见的有机磷化合物是神经毒性杀虫剂和神经毒剂。与其相关的一组有机磷化合物，即磷酰三酯增塑剂和阻燃剂，近来已被广泛使用。与神经毒性磷酰三酯不同，增塑剂和阻燃剂缺乏易于水解的键。尽管磷酰三酯酶对神经毒性有机磷酸盐的水解已为人所熟知，但阻燃剂和增塑剂中缺乏活性键使得它们对典型的磷酰三酯酶不起反应。近期有报道称，来自淡紫拟青霉菌株TCM1（Sb-PTE）的一种磷酰三酯酶能够催化有机磷阻燃剂的水解。这种酶现已在大肠杆菌中表达，其对多种有机磷底物的活性已被鉴定并与其从矮小假单胞菌（Pd-PTE）中提取的活性进行了比较。结构预测表明，Sb-PTE具有β-螺旋桨折叠结构，同源建模揭示了一个潜在的单核锰结合位点。Sb-PTE表现出对如对氧磷等典型磷酰三酯酶底物的催化活性，但与Pd-PTE不同，Sb-PTE还能有效水解阻燃剂、增塑剂和工业溶剂。Sb-PTE能够水解磷氧键和磷硫键，但不是磷氮键。Sb-PTE的最佳底物是阻燃剂三苯基磷酸酯，其kcat/Km值为1.7 × 106 M–1 s–1。非常值得注意的是，Sb-PTE还能够水解具有简单醇离去基团的磷酰三酯，如三丁基磷酸酯（kcat/Km = 40 M–1 s–1），这表明该酶在广泛的有机磷化合物生物修复方面可能非常有用。
• Copper and Photocatalytic Radical Relay Enabling Fluoroalkylphosphorothiolation of Alkenes: Modular Synthesis of Fluorine-Containing <i>S</i>-Alkyl Phosphorothioates and Phosphorodithioates
  作者：Pengbo Zhang、Wenwu Li、Weilong Qu、Zhigang Shu、Yingjun Tao、Jinming Lin、Xia Gao

  DOI：10.1021/acs.orglett.1c03608

  日期：2021.12.3

  A photoredox and copper-catalyzed fluoroalkylphosphorothiolation of activated and unactivated alkenes via a radical relay mechanism is reported. By employing fluoroalkyl halides as radical precursors and P(O)SH or P(S)SH compounds as coupling partners, a wide range of β-monofluoroalkyl-, -difluoroalkyl-, -trifluoromethyl-, or -perfluoroalkyl-substituted S-alkyl phosphorothioates and phosphorodithioates

  报道了通过自由基中继机制光氧化还原和铜催化的活化和未活化烯烃的氟代烷基硫代磷酸化。通过使用氟代烷基卤化物作为自由基前体和 P(O)SH 或 P(S)SH 化合物作为偶联配偶体，可以得到广泛的 β-单氟烷基-、-二氟烷基-、-三氟甲基-或-全氟烷基-取代的S-烷基硫代磷酸酯并且二硫代磷酸酯可以在温和的条件下容易地构建，具有良好的官能团耐受性。此外，这种模块化反应系统可以成功地应用于生物活性分子的后期功能化。
• Photoredox and Copper‐Catalyzed Sulfonylphosphorothiolation of Alkenes toward β‐Sulfonyl Phosphorothioates
  作者：Pengbo Zhang、Wenwu Li、Xianglong Zhu、Ying Li、Xiangmei Zhao、Saige Shi、Fengxiang Zhu、Jinming Lin、Xia Gao

  DOI：10.1002/adsc.202200766

  日期：2022.9.20

  sulfonyl chlorides as radical precursors and (RO)2P(O)SH as coupling partners, a wide range of decorated β-sulfonyl phosphorothioates could be obtained in 37–98% yields with good functional group tolerance. Importantly, this three-component reaction can be conveniently extended to late-stage modification of bioactive molecules and gram-scale synthesis.

  已经开发了烯烃的光氧化还原和铜催化的磺酰基硫代磷酸化。通过使用容易获得的芳基或烷基磺酰氯作为自由基前体和 (RO) 2 P(O)SH 作为偶联伙伴，可以以 37-98% 的收率获得具有良好官能团的各种修饰的 β-磺酰硫代磷酸酯宽容。重要的是，这种三组分反应可以方便地扩展到生物活性分子的后期修饰和克级合成。
• Electrochemically Enabled Dehydrogenative Phosphorothiolation of 2 <i>H</i> ‐Indazoles under Electrolyte‐Free Conditions
  作者：Payel Ghosh、Alakananda Hajra

  DOI：10.1002/adsc.202200932

  日期：2022.12.8

  We have developed an electrochemical method for phosphorothiolation of 2H-indazoles using S-hydrogen phosphorothioates via cross dehydrogenative coupling reaction under metal-free and electrolyte-free conditions. This protocol is compatible with electron donating groups like −Me, −OMe, halogen and elctron withdrawing groups such as −COOEt, affording respective indazolyl phosphorothioates in 62%-91%

  我们开发了一种电化学方法，在无金属和无电解质条件下，通过交叉脱氢偶联反应，使用S -氢硫代磷酸酯对 2 H -吲唑进行硫代磷酸化。该协议与电子捐赠基团如-Me、-OMe、卤素和电子撤回基团如-COOEt 兼容，以 62%-91% 的收率提供相应的吲唑基硫代磷酸酯。综合机理研究表明，反应通过自由基途径进行。
• Direct Synthesis of Benzo[<i>b</i>]fluorenyl Thiophosphates via Tandem Cyclization of Diynols with (RO)₂P(O)SH
  作者：Sha Du、Shimin Jiang、Ruchun Yang、Fengyan Jin、Haiyang Huang、Wan-Fa Tian、Zhao-Zhao Zhou、Xian-Rong Song、Qiang Xiao

  DOI：10.1021/acs.orglett.3c00009

  日期：2023.3.3

  A general and metal-free protocol for the construction of benzo[b]fluorenyl thiophosphates was developed through the cascade cyclization of easily prepared diynols and (RO)2P(O)SH, with water as the only byproduct. The novel transformation involved the allenyl thiophosphate as the key intermediate, followed by Schmittel-type cyclization to achieve the desired products. Notably, (RO)2P(O)SH acted not

  通过简单制备的二炔醇和 (RO) 2 P(O)SH 的级联环化，开发了一种用于构建苯并 [ b ] 芴基硫代磷酸酯的通用且无金属方案，水是唯一的副产物。新的转化以丙二烯硫代磷酸酯为关键中间体，然后进行施密特型环化以获得所需的产物。值得注意的是，(RO) 2 P(O)SH 不仅作为亲核试剂，而且作为启动反应的酸促进剂。