1-Methylthio-1-dodecyne | 130612-89-4

• 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: 1-Methylthio-1-dodecyne
• 英文别名: 1-Methylsulfanyldodec-1-yne
• CAS: 130612-89-4
• 化学式: C₁₃H₂₄S
• 分子量: 212.4
• InChiKey: GPTOMKUCOHNYNX-UHFFFAOYSA-N

物化性质

• 沸点：
  294.5±23.0 °C(Predicted)
• 密度：
  0.883±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  14
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  1-Methylthio-1-dodecyne 在 水 、 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (E)-2-Decyl-5-phenyl-2-pentenal
  参考文献：
  名称：

  Regioselectivity in the reaction of tantalum-unsymmetrical acetylene complexes with carbonyl compounds. Stereoselective preparation of 1-alkenyl sulfides, .alpha.,.beta.-unsaturated esters, and amides

  摘要：

  Tantalum-alkyne complexes, derived by treatment of alkynes with low-valent tantalum (TaCl5 and zinc), react in situ with carbonyl compounds to give (E)-allylic alcohols stereoselectively. When unsymmetrical acetylenes are employed in the reaction, two regioisomeric allylic alcohols are produced. The regioselectivity of the reaction depends on the steric and electronic effects of the substituents on the acetylenes. For example, treatment of tantalum-alkyne complexes derived from methyl alkynyl sulfides with carbonyl compounds yields (E)-3-hydroxy-1-propenyl methyl sulfides in a regioselective manner. Tantalum-alkyne complexes derived from acetylenic esters react with carbonyl compounds regioselectively at the alpha-position of the esters to give Z-isomers of trisubstituted alpha,beta-unsaturated esters. In contrast, tantalum-alkyne complexes derived from acetylenic amides react with carbonyl compounds predominantly at the beta-position of the amides. The regioselectivity of the reaction between acetylenic amides and aldehydes, however, cannot be explained solely in terms of the steric and electronic effects of the substituents. Strong coordination of the amide group to the tantalum center could also be responsible for the observed selectivity, which is opposite to that observed with tantalum-acetylenic ester complexes.

  DOI：

  10.1021/jo00051a023
• 作为产物：
  描述：

  2-Dodec-1-ynylsulfanylethyl(trimethyl)silane 以 四氢呋喃 为溶剂， 生成 1-Methylthio-1-dodecyne
  参考文献：
  名称：

  Preparation of 1-alkynyl 2-(trimethylsilyl)ethyl sulfides as thiolate anion precursors for self-assembled monolayers

  摘要：

  Syntheses of 1-alkynyl 2-(trimethylsilyl)ethyl sulfides are reported. Deprotection of 2-(trimethylsilyl)ethyl groups using fluoride ions permits the formation of thiolate anions which are trapped by in situ alkylation with methyl iodide and can be used to produce self-assembled monolayers on gold. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00540-1

文献信息

• Copper-Catalyzed Extended Pummerer Reactions of Ketene Dithioacetal Monoxides with Alkynyl Sulfides and Ynamides with an Accompanying Oxygen Rearrangement
  作者：Kei Murakami、Junichi Imoto、Hiroshi Matsubara、Suguru Yoshida、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1002/chem.201204072

  日期：2013.4.26

  and ynamides provided a wide variety of γ,γ‐disulfanyl‐β,γ‐unsaturated carbonyl compounds with an accompanying oxygen rearrangement. The products can be easily converted into 1,4‐dicarbonyl compounds and substituted heteroaromatics. DFT calculations and mechanistic experiments revealed a new interesting stepwise addition/oxygen rearrangement mechanism.

  描述了通过亚砜活化金属催化的扩展Pummerer反应的第一个例子。烯酮二硫缩醛一氧化碳与炔基硫醚和乙酰胺的铜催化反应提供了多种γ，γ-二硫烷基-β，γ-不饱和羰基化合物，并伴有氧重排。产物可以很容易地转化为1,4-二羰基化合物和取代的杂芳族化合物。DFT计算和机理实验揭示了一种新的有趣的逐步加成/氧重排机理。
• Selective Cyclotrimerization of Acetylenes<i>via</i>Tantalum-Alkyne Complexes
  作者：Kazuhiko Takai、Masashi Yamada、Kiitiro Utimoto

  DOI：10.1246/cl.1995.851

  日期：1995.9

  Tantalum-alkyne complexes prepared from internal acetylenes and low-valent tantalum (TaCl5 and Zn) in DME and benzene react with terminal diynes in the presence of THF and pyridine to give tetrasubstituted benzene derivatives in good to excellent yields.

  由内部乙炔和低价钽（TaCl5 和 Zn）在二甲醚和苯中制备的钽-炔络合物，在四氢呋喃和吡啶存在下与末端二炔反应，生成四取代苯衍生物，收率良好甚至极佳。
• Reaction of Tantalum–Alkyne Complexes with Isocyanates or Acyl Cyanides. Stereoselective Functionalization of Carbon–Carbon Triple Bonds
  作者：Yasutaka Kataoka、Yoshiyuki Oguchi、Kazuyuki Yoshizumi、Seiji Miwatashi、Kazuhiko Takai、Kiitiro Utimoto

  DOI：10.1246/bcsj.65.1543

  日期：1992.6

  produces tantalum-alkyne complexes (not isolated), which react in situ with phenyl isocyanate (or butyl isocyanate) to give (E)-α,β-unsaturated amides stereoselectively. The tantalum–alkyne complexes also react with acyl cyanides in the presence of BF3·OEt2 to give α-cyanohydrins. In both reactions, filtration of the reaction mixture containing the tantalum–alkyne complexes before addition of isocyanates

  用源自 TiCl5 和锌的低价钽处理炔烃产生钽-炔烃配合物（未分离），其与异氰酸苯酯（或异氰酸丁酯）原位反应，立体选择性地生成 (E)-α,β-不饱和酰胺。在 BF3·OEt2 存在下，钽-炔配合物也与酰基氰反应生成 α-氰醇。在这两个反应中，在加入异氰酸酯（或酰基氰化物）之前过滤含有钽-炔配合物的反应混合物对于获得良好的收率是必不可少的。
• Reaction of Tantalum–Alkyne Complexes with Isocyanates Leading to (<i>E</i>)-α,β-Unsaturated Amides. Stereoselective Functionalization of Carbon-Carbon Triple Bonds
  作者：Kazuhiko Takai、Yasutaka Kataoka、Kazuyuki Yoshizumi、Yoshiyuki Oguchi、Kiitiro Utimoto

  DOI：10.1246/cl.1991.1479

  日期：1991.8

  alkynes with low-valent tantalum derived from TaCl5 and zinc produces tantalum-alkyne complexes (not isolated), which react with phenylisocyanate (or butylisocyanate) to give (E)-α,β-unsaturated amides stereoselectively.

  用源自 TaCl5 和锌的低价钽处理炔烃会产生钽-炔烃配合物（未分离），其与异氰酸苯酯（或异氰酸丁酯）反应生成 (E)-α,β-不饱和酰胺立体选择性。
• Reaction of Tantalum-Alkyne Complexes with Hydrazones. Stereoselective Synthesis of (E)-Allylic Hydrazines.
  作者：Kazuhiko Takai、Seiji Miwatashi、Yasutaka Kataoka、Kiitiro Utimoto

  DOI：10.1246/cl.1992.99

  日期：——

  Treatment of tantalum-alkyne complexes with dimethylhydrazones by the assistance of Me 3 Al in a mixed solvent of DME, benzene, and THF at 45°C for 16 h gives (E)-allylic hydrazines stereoselectively

  在二甲醚、苯和四氢呋喃的混合溶剂中，在 Me 3 Al 的帮助下，在 45°C 下用二甲基腙处理钽-炔配合物 16 小时，立体选择性地得到 (E)-烯丙基肼