2-Methyl-2-phenylethynyl-[1,3]dithiolane | 183270-57-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 2-Methyl-2-phenylethynyl-[1,3]dithiolane
• 英文别名: 2-Methyl-2-(2-phenylethynyl)-1,3-dithiolane
• CAS: 183270-57-7
• 化学式: C₁₂H₁₂S₂
• 分子量: 220.359
• InChiKey: AEJJJBUAAUSCKJ-UHFFFAOYSA-N

物化性质

• 沸点：
  352.6±37.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Methyl-2-phenylethynyl-[1,3]dithiolane 在 (1,1'-双(二苯基膦)二茂铁)二氯化镍 、 potassium iodide 作用下， 以 四氢呋喃 、 正戊烷 、 苯 为溶剂， 反应 12.5h， 生成 3-methyl-1-phenyl-1,2-butadiene
  参考文献：
  名称：

  Umpolung of Carbon−Sulfur Bonds. Novel Synthesis of Substituted Allenes from Propargylic Dithioacetals

  摘要：

  Umpolung of the carbon-sulfur bonds can be achieved by treatment of propargylic dithioacetals 1 with organocuprates. The organocopper intermediates 3 gave the corresponding allenyl thioethers 4 upon protonolysis. When alkyl halides were used, propargylic thioethers 5 were obtained exclusively. Transmetalation of organocopper intermediates 3 with ZnBr2 followed by Pd(PPh3)(4)- catalyzed coupling with vinylic or aryl halides afforded the corresponding allenyl thioethers 4. Either 4 or 5 reacted with Grignard reagents in the presence of NiCl2(dppf) to yield the corresponding allenes 9 or 10, respectively. The overall reaction can be considered to use 1 as allene-1,3-zwitterion synthons. The relative reactivities of a propargylic ether versus a propargylic dithioacetal toward an organocopper reagent were compared. The sulfur moiety apparently has higher reactivity toward the copper reagent.

  DOI：

  10.1021/jo991032b
• 作为产物：
  描述：

  1,2-乙二硫醇 、 4-苯基-3-丁炔-2-酮 在 ruthenium trichloride 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以61%的产率得到2-Methyl-2-phenylethynyl-[1,3]dithiolane
  参考文献：
  名称：

  氯化钌（III）催化羰基化合物的硫缩醛化：范围，选择性和局限性

  摘要：

  在室温下，在乙腈中催化量的氯化钌存在下，各种羰基化合物可以轻松快速地转化为相应的环状和酰基二硫缩醛。该方案的一些主要优点是化学选择性高，操作简便，反应时间短，产率高以及与其他保护基团的相容性。

  DOI：

  10.1002/adsc.200404323

文献信息

• Propargylic Dithioacetal as an Allene 1,3-Dication Synthon. Nickel-Catalyzed Cross-Coupling Reactions of Propargylic Dithioacetals with Grignard Reagents
  作者：Hsian-Rong Tseng、Tien-Yau Luh

  DOI：10.1021/jo961514c

  日期：1996.1.1
• Novel Coupling Reactions of Dithioacetals with Organocuprate Reagents. Propargylic Dithioacetal as an Allene−1,3-Zwitterion Synthon
  作者：Hsian-Rong Tseng、Tien-Yau Luh

  DOI：10.1021/jo970700v

  日期：1997.7.1
• Umpolung of Carbon−Sulfur Bonds. Novel Synthesis of Substituted Allenes from Propargylic Dithioacetals
  作者：Hsian-Rong Tseng、Chin-Fa Lee、Lian-Ming Yang、Tien-Yau Luh

  DOI：10.1021/jo991032b

  日期：1999.11.1

  Umpolung of the carbon-sulfur bonds can be achieved by treatment of propargylic dithioacetals 1 with organocuprates. The organocopper intermediates 3 gave the corresponding allenyl thioethers 4 upon protonolysis. When alkyl halides were used, propargylic thioethers 5 were obtained exclusively. Transmetalation of organocopper intermediates 3 with ZnBr2 followed by Pd(PPh3)(4)- catalyzed coupling with vinylic or aryl halides afforded the corresponding allenyl thioethers 4. Either 4 or 5 reacted with Grignard reagents in the presence of NiCl2(dppf) to yield the corresponding allenes 9 or 10, respectively. The overall reaction can be considered to use 1 as allene-1,3-zwitterion synthons. The relative reactivities of a propargylic ether versus a propargylic dithioacetal toward an organocopper reagent were compared. The sulfur moiety apparently has higher reactivity toward the copper reagent.
• Ruthenium(III) Chloride-Catalyzed Thioacetalization of Carbonyl Compounds: Scope, Selectivity, and Limitations
  作者：Surya?Kanta De

  DOI：10.1002/adsc.200404323

  日期：2005.4

  A variety of carbonyl compounds can be easily and rapidly converted to the corresponding cyclic and acylic dithioacetals in the presence of a catalytic amount of ruthenium chloride in acetonitrile at room temperature. Some of the major advantages of this protocol are high chemoselectivity, operational simplicity, very short reaction times, high yields, and also compatibility with other protecting groups

  在室温下，在乙腈中催化量的氯化钌存在下，各种羰基化合物可以轻松快速地转化为相应的环状和酰基二硫缩醛。该方案的一些主要优点是化学选择性高，操作简便，反应时间短，产率高以及与其他保护基团的相容性。