2-Prop-2-enylpent-4-eneselenothioic acid S-butyl ester | 173281-64-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫基化合物
• 英文名称: 2-Prop-2-enylpent-4-eneselenothioic acid S-butyl ester
• 英文别名: 1-Butylsulfanyl-2-prop-2-enylpent-4-ene-1-selone
• CAS: 173281-64-6
• 化学式: C₁₂H₂₀SSe
• 分子量: 275.317
• InChiKey: XYJOUQBCOJVADQ-UHFFFAOYSA-N

物化性质

• 沸点：
  324.7±52.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  14
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-Prop-2-enylpent-4-eneselenothioic acid S-butyl ester 在 cadmium(II) acetate 、 三乙胺 作用下， 以 甲醇 为溶剂， 生成 Bis[1-(butylthio)-2-prop-2-enylpenta-1,4-dienyl] diselenide
  参考文献：
  名称：

  Cadmium Acetate Mediated Cenversion of Selenothioic AcidS-Alkyl Esters to Selenophenes and Ketene Selenothioacetals

  摘要：

  硒硫酸S-烷基酯与Et3N和Cd(OAc)2·2H2O反应生成了对称取代的硒吡啶，而在烷基卤化物存在下进行类似反应则在中等产率下获得了烯酮硒硫醇醚。

  DOI：

  10.1246/cl.1996.877
• 作为产物：
  描述：

  Bis[1-(butylthio)-2-prop-2-enylpenta-1,4-dienyl] diselenide 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.08h， 以83%的产率得到2-Prop-2-enylpent-4-eneselenothioic acid S-butyl ester
  参考文献：
  名称：

  硒代硫辛酸S酯与三价磷化合物的反应：α-磷酰基烷基硫化物和烷基硒化物的新合成方法

  摘要：

  硒原子的挤出使硒代硫代酸S-酯1与亚磷酸三烷基酯的反应顺利进行，从而以高至高收率得到α-磷酰基硫化物2。类似的反应更容易发生二甲基苯基膦酸酯 和 甲基二苯基次膦酸酯，虽然烯酮硒代乙缩醛3也作为副产物以增加的产率形成。二硒酸的用途酯类 1f和1g给出α-磷酰基硒化物2m和2n。该产品在其产品中表现出特征性的化学位移和偶联常数31 P NMR光谱。通过X射线分子结构分析确认了α-磷酰基硒化物2n的结构。与之反应三苯膦 导致氧化二聚 酯 1d得到高产率的二乙烯基二硒化物4。催化量的三苯膦 也可以有效地形成 二乙烯基二硒化物 4。反应可能始于三苯膦 在硒代羰基的碳原子上 酯 1D。还讨论了导致α-磷酰基硫化物2的反应途径的细节。与薄荷基二苯基次膦酸酯12的反应表明，该反应可能是通过对三价磷化合物的硒原子上带有烷氧基的三价磷化合物进行初始亲核攻击而进行的。酯类 1。中介叶立德 14的反应也得到了支持酯

  DOI：

  10.1039/a909469e

文献信息

• Highly Efficient Generation of Ammonium Eneselenolates, Their Reactions and Electronic Properties
  作者：Toshiaki Murai、Shuuya Hayakawa、Shinzi Kato

  DOI：10.1246/cl.2000.368

  日期：2000.4

  The ammonium eneselenolates generated from selenothioic acid S-esters and ammonium fluoride were reacted with carbon electrophiles to furnish ketene selenothioacetals with high stereoselectivities. The spectroscopic properties of the ammonium eneselenolates have suggested that the electrons on the selenium atom efficiently delocalize on the carbon-carbon double bond.

  从硒硫酸S酯和氟化铵生成的铵盐烯硒醇盐与碳亲电试剂反应，生成了高立体选择性的酮烯硒硫醚。铵盐烯硒醇盐的光谱性质表明，硒原子上的电子能够有效地在碳-碳双键上进行去局域化。
• Reactions of Selenothioic Acid<i>S</i>-Esters and Diselenoic Acid Esters with Trialkyl Phosphites Leading to<i>α</i>-Phosphoryl Sulfides and Selenides
  作者：Toshiaki Murai、Chiyoko Izumi、Shinzi Kato

  DOI：10.1246/cl.1999.105

  日期：1999.2

  The reaction of selenothioic acid S-esters with trialkyl phosphites proceeded smoothly to afford α-phosphoryl sulfides as a major product in good to high yields. The reaction was also applicable to diselenoic acid esters. On the contrary, selenothioic acid S-butyl ester underwent oxidative dimerization with triphenylphosphine to give a divinyl diselenide.

  硒代硫代酸 S-酯与亚磷酸三烷基酯的反应顺利进行，以良好到高产率提供 α-磷酰硫化物作为主要产物。该反应也适用于二硒酸酯。相反，硒代硫代酸 S-丁酯与三苯基膦发生氧化二聚反应得到二乙烯基二硒化物。
• 4-Penteneselenothioic acid S-alkyl esters: Synthesis via the seleno-Claisen rearrangement
  作者：Toshiaki Murai、Hiroya Takada、Kaori Kakami、Makiko Fujii、Masahiko Maeda、Shinzi Kato

  DOI：10.1016/s0040-4020(97)00556-5

  日期：1997.8

  Selenothioic acid S-alkyl esters were reacted with allylic bromides in the presence of Et3N. Mono-, di- or tri-allylatd products were selectively formed by changing reaction temperatures, times and allylic bromides used. The reaction proceeded with high regio- and stereoselectivity via the seleno-Claisen rearrangement. The selective synthesis of monoallylated esters was also attained by the reaction

  在Et 3 N存在下，使硒代硫代酸S-烷基酯与烯丙基溴反应。通过改变反应温度，时间和所用的烯丙基溴选择性地形成单，二或三烯丙基的产物。该反应通过seleno-Claisen重排以高度的区域选择性和立体选择性进行。还可以通过原位生成的烯醇硒酸锂与烯丙基溴的反应来实现单烯丙基化酯的选择性合成。
• Selective Allylations of Selenothioic Acid<i>S</i>-Alkyl Esters with Allylic Bromides
  作者：Toshiaki Murai、Hiroya Takada、Takahiro Kanda、Shinzi Kato

  DOI：10.1246/cl.1995.1057

  日期：1995.11

  Allylations of selenothioic acid S-alkyl esters with allylic bromides in the presence of Et3N in THF took place selectively at the α-position of selenocarbonyl group to give allylated products with high regio- and stereo-selectivity.

  在THF中，三乙胺的存在下，硒硫酸S-烷基酯与烯丙基溴化物的烯丙基化反应选择性地发生在硒羰基的α位，生成具有高区域选择性和立体选择性的烯丙基化产物。
• Ammonium Eneselenolates:  Stereochemistry and Electronic Properties
  作者：Toshiaki Murai、Shuuya Hayakawa、Shinzi Kato

  DOI：10.1021/jo015899x

  日期：2001.11.1

  Ammonium eneselenolates were generated with high efficiency by reacting selenothioic acid S-esters with a THF solution of TBAF. The methylation of ammonium eneselenolates gave ketene selenothioacetals as stereoisomeric mixtures. The ratio of the two stereoisomers depended on the duration of the reaction before the addition of Mel. Ammonium eneselenolates were characterized by examining their H-1, C-13, and Se-77 NMR spectra, which indicated that ammonium eneselenolates were present almost exclusively as Z-isomers. These results suggested that ammonium eneselenolates are kinetically generated as stereoisomeric mixtures, and isomerization of E-isomers to Z-isomers then takes place to result in the exclusive formation of Z-isomers. During the methylation of Z-isomers of ammonium eneselenolates, the isomerization of Z-isomers to E-isomers occurs to give stereoisomeric mixtures of ketene selenothioacetals. NMR spectra of ammonium eneselenolates implied that the electrons at the selenium atom are somewhat delocalized to the carbon-carbon double bond and the carbon-selenium bond shows partial double-bond character.

表征谱图