O,O-diethyl N-phenylphosphoramidothioate | 3694-54-0

• 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: O,O-diethyl N-phenylphosphoramidothioate
• 英文别名: phenyl-thiophosphoramidic acid O,O'-diethyl ester；phenyl-amidothiophosphoric acid O,O'-diethyl ester；Phenyl-amidothiophosphorsaeure-O,O'-diaethylester；phenyl-thiophosphoramidic acid diethyl ester；O,O-diethyl phenylphosphoramidothioate；Monothiophosphorsaeure-O.O-diaethylester-anilid；Phosphoramidothioic acid, phenyl-, O,O-diethyl ester；N-diethoxyphosphinothioylaniline
• CAS: 3694-54-0
• 化学式: C₁₀H₁₆NO₂PS
• 分子量: 245.282
• InChiKey: VTOGWEUSGRPLPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  62.6
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  O,O-diethyl N-phenylphosphoramidothioate 在 间氯过氧苯甲酸 作用下， 生成 N-苯基-氨基磷酸二乙酯
  参考文献：
  名称：

  Swinson, Joel; Field Lamar; Heimer, Norman E., Phosphorus and Sulfur and the Related Elements, 1988, vol. 35, p. 159 - 172

  摘要：

  DOI：
• 作为产物：
  描述：

  O,O-二乙基硫代磷酰氯 、 苯胺 以 乙腈 为溶剂， 生成 O,O-diethyl N-phenylphosphoramidothioate
  参考文献：
  名称：

  二甲基和二乙基氯（硫代）磷酸酯苯胺化反应的动力学和机理

  摘要：

  据报道，氘化苯胺亲核试剂（XC 6 H 4 ND 2）的氘动力学同位素效应（KIEs）用于二甲基氯磷酸盐（1），二甲基氯硫代磷酸盐（2），二乙基氯磷酸酯（3）和二乙基氯硫代磷酸酯（4）的反应。乙腈在55.0°C下。将所得到的ķ ħ / ķ d值是0.798-0.979，0.945-1.06，0.714-0.919和1.01-1.10为1，2，3和4， 分别。针对1和3的反应提出了具有显着的背面亲核攻击的协同机制。针对2和4的反应，提出了一种通过氢键键合的四中心过渡态（TS）参与部分正面攻击的协同机制。版权所有©2008 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/poc.1314

文献信息

• 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。
• Process for preparing N-[(phosphinyl)amino]thio- and N-[(phosphinyl)amino]t
  申请人：The Upjohn Company

  公开号：US04201733A1

  公开（公告）日：1980-05-06

  Some new phosphinic acid derivatives of aminothio methylcarbamates have been synthesized and tested as pesticides. The new compounds are active against insects, mites, and nematodes. The N-[(phosphinyl)amino]thio- and N-](phosphinothioyl)amino]thio-methylcarbamates are readily prepared by the general procedure of reacting a phosphinic acid amide with sulfur dichloride so as to obtain the corresponding N-(chlorothio)phosphinic acid amide which reactant will react with a methylcarbamate so as to produce the corresponding object compounds, the N-[(phosphinyl)amino]thio- and N-[(phosphinothioyl)-amino]thio-methylcarbamates of this invention. Various formulations for pesticidal use are described along with appropriate rates of application.

  已合成并测试了一些新的氨硫甲酸酯磷酸衍生物作为杀虫剂。这些新化合物对昆虫、螨和线虫具有活性。N-[(磷氨基)氨基]硫基和N-[(磷硫酰)氨基]硫基甲酸酯可通过将磷酸酰胺与二氯化硫反应的一般程序轻松制备，从而获得相应的N-(氯硫)磷酸酰胺，该反应物将与甲基氨基甲酸酯反应，从而产生本发明的相应化合物，即N-[(磷氨基)氨基]硫基和N-[(磷硫酰)氨基]硫基甲酸酯。描述了用于杀虫剂使用的各种配方以及适当的施用速率。
• N-[(phosphinyl or phosphinothioyl)amino]thio-methylcarbamates and
  申请人：The Upjohn Company

  公开号：US04208409A1

  公开（公告）日：1980-06-17

  Some new phosphinic acid derivatives of aminothio methylcarbamates have been synthesized and tested as pesticides. The new compounds are active against insects, mites, and nematodes. The N-[(phosphinyl)amino]thio- and N-[(phosphinothioyl)amino]thio- methylcarbamates are readily prepared by the general procedure of reacting a phosphinic acid amide with sulfur dichloride so as to obtain the corresponding N-(chlorothio)phosphinic acid amide which reactant will react with a methylcarbamate so as to produce the corresponding object compounds, the N-[(phosphinothioyl)amino]thio- methylcarbamates of this invention. Various formulations for pesticidal use are described along with appropriate rates of application.

  已合成并测试了一些新的氨硫甲酸磷酸酯衍生物作为杀虫剂。这些新化合物对昆虫、螨和线虫具有活性。N-[(磷氨基)硫基]-和N-[(磷硫酰)氨基]硫基甲基氨基甲酸酯可通过将磷酸胺与二氯化硫反应的一般程序制备，从而获得相应的N-(氯硫)磷酸胺，该反应物将与甲基氨基甲酸酯反应，从而产生本发明的相应化合物，即N-[(磷硫酰)氨基]硫基甲基氨基甲酸酯。描述了用于杀虫剂使用的各种配方以及适当的施用速率。
• N-alkylation of amidothiophosphoryl compounds under phase-transfer catalysis conditions. Synthesis and properties of 1,3,2-thiazaphosphacyclanes
  作者：O. I. Artyushin、E. V. Sharova、P. V. Petrovskii、I. L. Odinets

  DOI：10.1007/s11172-009-0032-4

  日期：2009.1

  N (ω-Haloalkyl)amidothiophosphates, N (ω-Haloalkyl)amidothiophosphonates, and N- (ω-Haloalkyl)amidothiophosphinates (Hal = Cl or Br) were obtained in high yields by alkylation of phosphorus(V) acid thioamides with 6h,ω-dihaloalkanes under phase-transfer catalysis (PTC) conditions or through the use of NaH as a base. Thermal rearrangement of N (3-iodopropyl)-or N (4-iodobutyl)amidothiophosphate and N (3-iodopropyl)-or N (4-iodo-butyl)amidothiophosphonate obtained in situ by the Finkelstein reaction provides a convenient route to 2-oxo-1,3,2-thiazaphosphinanes and 2-oxo-1,3,2-thiazaphosphepanes. Reactions of N (ω-Haloalkyl)amidothiophosphinates with NaClO4 in MeCN afforded the first example of stable 1,3,2-thiazaphosphacyclanium salts containing P—C bonds.

  N(ω-卤烷基)氨基硫代磷酸酯、N(ω-卤烷基)氨基硫代磷酸盐和N(ω-卤烷基)氨基硫代磷酸氢盐（Hal = Cl 或 Br）通过在相转移催化（PTC）条件下，或使用NaH作为碱，与6h,ω-二卤烷反应，获得了高收率。N(3-碘丙基)或N(4-碘丁基)氨基硫代磷酸酯和N(3-碘丙基)或N(4-碘丁基)氨基硫代磷酸盐在现场通过Finkelstein反应得到，热重排反应提供了一种便利的合成2-氧代-1,3,2-噻唑膦烷和2-氧代-1,3,2-噻唑膦环的路线。N(ω-卤烷基)氨基硫代磷酸氢盐与MeCN中NaClO4的反应提供了第一个包含P—C键的稳定1,3,2-噻唑膦盐类的实例。