O-ethylethylthiophosphonic acid | 7776-66-1

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机硫代磷化合物
• 英文名称: O-ethylethylthiophosphonic acid
• 英文别名: ethyl ethylphosphinothioate；ethyl-phosphonothioic acid O-ethyl ester；(+/-)-Aethyl-thiophosphonsaeure-O-aethylester；Aethyl-thiophosphonsaeure-O-aethylester；racem.-Ethylthiophosphonsaeure-O-ethylester；rac.-Ethylthiophosphonsaeure-O-ethylester；ethoxy-ethyl-hydroxy-sulfanylidene-λ5-phosphane
• CAS: 7776-66-1
• 化学式: C₄H₁₁O₂PS
• 分子量: 154.17
• InChiKey: AIJQQTBLBLBZDI-UHFFFAOYSA-N

物化性质

• 沸点：
  75-76 °C(Press: 0.4 Torr)
• 密度：
  1.0999 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  61.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  O-ethylethylthiophosphonic acid 在 N,N'-二环己基碳二亚胺 作用下， 以 Petroleum ether 为溶剂， 生成 (ethylphosphonic acid ethyl ester)-(ethyl-thiophosphonic acid O-ethyl ester)-anhydride
  参考文献：
  名称：

  Mikolajczyk,M., Chemische Berichte, 1966, vol. 99, p. 2083 - 2090

  摘要：

  DOI：
• 作为产物：
  描述：

  ethyl ethylphosphinate 在 potassium ethoxide 、 sulfur 作用下， 生成 O-ethylethylthiophosphonic acid
  参考文献：
  名称：

  Michalski; Skowronska, Roczniki Chemii, 1956, vol. 30, p. 799,808,810

  摘要：

  DOI：

文献信息

• 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。
• Stereochemistry of nucleophilic substitution reaction at a thiophosphoryl centre—IV
  作者：J. Michalski、M. Mikołajczyk、B. Młotkowska、J. Omelańczuk

  DOI：10.1016/s0040-4020(01)82746-0

  日期：1969.1

  5-dimethyl-1,3,2-dioxaphosphorinan, diethyl phosphorochloridate and O,O-diethyl phosphorochloridothionate respectively. It has been found that alkaline hydrolysis of these anhydrides occurs with full inversion of configuration at the thiophosphoryl centre. The reaction is discussed from the point of view of stereochemistry and the reaction mechanism.

  在旋光的O-乙基乙基膦酸硫代酸（I）与2-氯-2-氧代-5,5-二甲基-1,3,2-二氧杂磷酰氨基己酸酯之间的反应中获得了旋光的焦膦酸酯（II，III和IV），氯代磷酸二乙酯和硫代磷酸氯代O，O-二乙基酯。已经发现这些酸酐的碱水解发生在硫代磷酰基中心的构型完全反转的情况下。从立体化学和反应机理的角度讨论了该反应。
• Synthesis and Structural Analysis of 5-Deoxy-3-<i>O</i>-methyl-5-<i>C</i>-[(<i>R</i>)- and (<i>S</i>)-phenylphosphinothioyl]-α- and β-D-xylopyranoses
  作者：Tadashi Hanaya、Nobuyuki Shigetoh、Hiroshi Yamamoto

  DOI：10.1246/bcsj.61.2499

  日期：1988.7

  compounds were converted into four, separable 1,2,4-tri-O-acetates, the structures and conformations of which were established by spectroscopy. The corresponding per-O-acetyl-5-deoxy-5-C-[(R)- and (S)-phenylphosphinyl] analogues were also prepared and their previously presented structures were revised. Complete 1H NMR (500-MHz) parameters of these two types of compounds are given for a comparative, structural

  5-脱氧-5-碘-1,2-O-异亚丙基-3-O-甲基-α-D-木呋喃糖与苯基硫代膦酸乙酯在 DMF 中 NaH 存在下处理得到 1:1 的 5-脱氧混合物-5-C-[(R)-和(S)-(乙氧基)苯基硫代膦酰基]衍生物。用二氢双（2-甲氧基乙氧基）铝酸钠还原这些 D-呋喃木糖，然后进行酸水解，得到标题化合物，它是第一个在半缩醛环中具有硫代膦酰基的糖类似物。这些化合物被转化为四种可分离的 1,2,4-三-O-乙酸酯，其结构和构象由光谱学确定。还制备了相应的 per-O-acetyl-5-deoxy-5-C-[(R)-和 (S)-phenylphoshinyl] 类似物，并对它们先前提出的结构进行了修改。
• Stereochemistry of nucleophilic displacement reactions at the thiophosphoryl centre—I
  作者：J. Michalski、M. Mikoł;ajczyk

  DOI：10.1016/s0040-4020(01)82285-7

  日期：1966.1

  The reaction of (−)- and (+)-O-ethyl ethylphosphonothioic acid (I) with phosphorus pentachloride has been shown to give optically active O-ethyl ethylphosphonochloridothionate (II) in high yield. For establishing the relative configuration and degree of stereospecificity of (II) use was made of the pyrophosphonothionates, prepared from I and II. The mechanism of the reaction is discussed.

  已经显示出（-）-和（+）-O-乙基乙基膦酰基硫代酸（I）与五氯化磷的反应可以高收率得到光学活性的O-乙基乙基膦酰基氯代硫代酸酯（II）。为了确定（II）的相对构型和立体特异性程度，使用了由I和II制备的焦膦酰硫醚酸酯。讨论了反应机理。
• Reaction of tricoordinate phosphorus compounds with organophosphorus pseudohalogens. 1. Desulfurization and deoxygenation of oxophosphoranesulfenyl chlorides. Scope and mechanism
  作者：E. Krawczyk、J. Mikolajczak、A. Skowronska、J. Michalski

  DOI：10.1021/jo00044a035

  日期：1992.8

  The reaction of oxophosphoranesulfenyl chlorides RR'P(O)SCl 2 with P(III) compounds has been investigated. Its mechanistic features have been elucidated by variable-temperature P-31 NMR spectroscopy and stereochemical changes at P(IV) and P(III) phosphorus centers. These studies show that in all cases phosphonium intermediates containing the sulfur bridge >P(O)-S-P+ less than or similar to Cl- are formed. Depending on electronic and steric factors and reaction conditions, this primary phosphonium salt either decomposes by nucleophilic attack of the chloride counterion on the phosphoryl center (desulfurization pathway) or is transformed into the isomeric phosphonium salt >P(S)-O-P+ less than or similar to Cl-. The latter decomposes by the attack of the chloride anion on the thiophosphoryl center (deoxygenation pathway). P-31 NMR studies fully corroborated the observed stereochemical changes.