ethyl (Z)-2-carbomethoxyethenesulfinate | 216007-92-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (Z)-2-carbomethoxyethenesulfinate
• 英文别名: methyl (Z)-3-ethoxysulfinylprop-2-enoate
• CAS: 216007-92-0
• 化学式: C₆H₁₀O₄S
• 分子量: 178.209
• InChiKey: UQOFOSRBFCBMKG-PLNGDYQASA-N

物化性质

• 沸点：
  264.5±42.0 °C(Predicted)
• 密度：
  1.268±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  71.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (Z)-2-carbomethoxyethenesulfinate 在 碘 、 silver trifluoroacetate 、 zinc dibromide 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 (1S,2S,3S,6S,7R,9R)-2-Iodo-5-oxo-4-oxa-tricyclo[4.2.1.0^3,7]nonane-9-sulfinic acid (S)-ethyl ester
  参考文献：
  名称：

  2-羧甲氧基乙烯亚磺酸乙酯与环戊二烯的狄尔斯-阿尔德环加成。路易斯酸的增强和竞争性立体差分化碘内酯化和碘磺化反应的加合物鉴定。

  摘要：

  为了确定它们在Diels-Alder反应中的反应性，将（Z）-2-碳甲氧基乙烯亚磺酸乙酯（1）和（E）-2-碳甲氧基乙烯亚磺酸乙酯（2）分别进行环戊二烯（约3当量）处理。热反应在不到4小时内进行，而路易斯酸增强的反应则显着加快并显示出更高的选择性。特别地，BF（3）.Et（2）O介导的环加成1以大约90％的收率得到了syn / endo环加合物3a作为主要的非对映异构体。2的反应在合成上不太有用。通过结合X射线晶体结构测定以及通过将化合物暴露于亲电子碘试剂来建立环加合物的结构。每个环加合物都与羧酸酯或亚磺酸酯进行碘环化反应，分别参与多环内酯或磺胺的形成。碘环化反应可以进一步阐明环加合物的结构。

  DOI：

  10.1021/jo991082g
• 作为产物：
  描述：

  乙醇 、 (Z)-2-carbomethoxyethenesulfinyl chloride 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 ethyl (Z)-2-carbomethoxyethenesulfinate
  参考文献：
  名称：

  1-Alkenesulfinyl Chlorides:  Synthesis, Characterization, and Some Substitution Reactions

  摘要：

  A number of 1-alkenyl sulfoxides bearing either a diphenylmethyl (DPM) or a p-methoxybenzyl (PMB) group have been prepared and exposed to the chlorine surrogate SO2Cl2. Through an oxidative fragmentation reaction, a new family of sulfur acid derivatives, 1-alkenesulfinyl chlorides, is generated. They can be characterized by IR spectroscopy before chemical capture with an alcohol. Ethenesulfinyl chloride (2a) and 1-propenesulfinyl chloride (2b), obtained from their corresponding DPM precursor, can be distilled at reduced pressure to afford ca. 90% pure material. NMR chemical shift comparison of various 1-alkenesulfinyl-containing compounds is made. 1-Alkenesulfinylmethyl phenyl(alkyl) ketones (6) can be prepared directly from sulfinyl chlorides 2 although decomposition and/or isomerization is sometimes extensive during purification.

  DOI：

  10.1021/jo980970t

文献信息

• Evaluation of ethyl 2-carbomethoxyethenesulfinates as 2-hydroxymethyl enethiol equivalents in the Diels–Alder reaction
  作者：Robert J. Faragher、Dino Alberico、Adrian L. Schwan

  DOI：10.1016/j.tet.2004.11.050

  日期：2005.1

  Z- and E-ethyl 2-carbomethoxyethenesulfinates 1 and 2 hold the potential to be enethiol equivalents by way of Diels-Alder cycloaddition chemistry followed by reduction. To pursue this, both dieneophiles were subjected to thermal and Lewis acid mediated [4 + 2] cycloadditions with a number of dienes. Yields of cycloadduct ranged from 34 to 94%, with cycloadditions of the aromatic dienes proceeding in moderate yields, presumably due to the reversibility of the reactions. Many cycloadducts were obtained as a mixture of sulfur epimers, but these isomers were unified in the subsequent reduction step. Using either LAH or DIBAL, the cycloadducts were reduced providing P-mercapto (or sulfanyl) carbinols in 32-97%. The sequence of two reactions places sulfur and hydroxy functional groups in set relative stereochemistry within a 6-membered ring. (C) 2004 Elsevier Ltd. All rights reserved.
• 1-Alkenesulfinyl Chlorides:  Synthesis, Characterization, and Some Substitution Reactions
  作者：Adrian L. Schwan、Rick R. Strickler、Yvonne Lear、Mark L. Kalin、Tanya E. Rietveld、Ting-Jian Xiang、Denis Brillon

  DOI：10.1021/jo980970t

  日期：1998.10.1

  A number of 1-alkenyl sulfoxides bearing either a diphenylmethyl (DPM) or a p-methoxybenzyl (PMB) group have been prepared and exposed to the chlorine surrogate SO2Cl2. Through an oxidative fragmentation reaction, a new family of sulfur acid derivatives, 1-alkenesulfinyl chlorides, is generated. They can be characterized by IR spectroscopy before chemical capture with an alcohol. Ethenesulfinyl chloride (2a) and 1-propenesulfinyl chloride (2b), obtained from their corresponding DPM precursor, can be distilled at reduced pressure to afford ca. 90% pure material. NMR chemical shift comparison of various 1-alkenesulfinyl-containing compounds is made. 1-Alkenesulfinylmethyl phenyl(alkyl) ketones (6) can be prepared directly from sulfinyl chlorides 2 although decomposition and/or isomerization is sometimes extensive during purification.
• Diels−Alder Cycloadditions of Ethyl 2-Carbomethoxyethenesulfinates with Cyclopentadiene. Lewis Acid Enhancement and Adduct Identification with the Assistance of Competitive Stereodifferentiating Iodolactonization and Iodosultinization Reactions
  作者：Yvonne Lear、Adrian L. Schwan

  DOI：10.1021/jo991082g

  日期：1999.10.1

  subjected to cyclopentadiene (ca. 3 equiv) in order to determine their reactivity in Diels-Alder reactions. Thermal reactions proceeded in less than 4 h, while Lewis Acid enhanced reactions were substantially faster and demonstrated greater selectivity. In particular, the BF(3).Et(2)O-mediated cycloaddition of 1 gave syn/endo cycloadduct 3a as a major diastereomer in about 90% yield. The reactions of 2 were

  为了确定它们在Diels-Alder反应中的反应性，将（Z）-2-碳甲氧基乙烯亚磺酸乙酯（1）和（E）-2-碳甲氧基乙烯亚磺酸乙酯（2）分别进行环戊二烯（约3当量）处理。热反应在不到4小时内进行，而路易斯酸增强的反应则显着加快并显示出更高的选择性。特别地，BF（3）.Et（2）O介导的环加成1以大约90％的收率得到了syn / endo环加合物3a作为主要的非对映异构体。2的反应在合成上不太有用。通过结合X射线晶体结构测定以及通过将化合物暴露于亲电子碘试剂来建立环加合物的结构。每个环加合物都与羧酸酯或亚磺酸酯进行碘环化反应，分别参与多环内酯或磺胺的形成。碘环化反应可以进一步阐明环加合物的结构。