dimethyl 2-(3-butenyl)-2-(2-(2,6-dithiacyclohexyl)ethyl)malonate | 220485-29-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: dimethyl 2-(3-butenyl)-2-(2-(2,6-dithiacyclohexyl)ethyl)malonate
• 英文别名: Dimethyl 2-but-3-enyl-2-[2-(1,3-dithian-2-yl)ethyl]propanedioate
• CAS: 220485-29-0
• 化学式: C₁₅H₂₄O₄S₂
• 分子量: 332.485
• InChiKey: PUBNCAAJDJYJMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  103
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(3-butenyl)-2-(2-(2,6-dithiacyclohexyl)ethyl)malonate 在 lithium aluminium tetrahydride 、 正丁基锂 、 ammonium cerium(IV) nitrate 、 氰化钠 、 对甲苯磺酸 、 三乙胺 、 lithium bromide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 乙腈 为溶剂， 反应 7.5h， 生成 4-Bromomethyl-1-(tert-butyl-dimethyl-silanyl)-oct-7-en-1-one
  参考文献：
  名称：

  The Study of the Kinetics of Intramolecular Radical Cyclizations of Acylsilanes via the Intramolecular Competition Method

  摘要：

  The kinetics of the radical cyclizations of acylsilanes is probed by the construction of an intramolecular competition system. In this system, known rate constants of olefin cyclizations are used as the internal clock. At-benzene reflux temperature (80 degrees C), the cyclization rate constants for 5-exo cyclizations of acylsilanes with primary radicals are on the order of 10(6) s(-1). The corresponding rate constants for 5-exo cyclizations with secondary radicals and 6-exo cyclizations with primary radicals lie on the order of 10(5) s(-1). The 6-exo cyclizations of acylsilanes with secondary radicals are slower and fall in the range of 10(4) s(-1). Substituents on the silicon of the acylsilanes affect the rates of cyclization. Large silyl groups reduce the rate, and this is more serious for the g-exo type of cyclizations. Electron-withdrawing groups increase the rates of cyclization.

  DOI：

  10.1021/jo982079k
• 作为产物：
  描述：

  2-(2-bromoethyl)-1,3-dithiane 在 sodium hydride 作用下， 反应 5.67h， 生成 dimethyl 2-(3-butenyl)-2-(2-(2,6-dithiacyclohexyl)ethyl)malonate
  参考文献：
  名称：

  The Study of the Kinetics of Intramolecular Radical Cyclizations of Acylsilanes via the Intramolecular Competition Method

  摘要：

  The kinetics of the radical cyclizations of acylsilanes is probed by the construction of an intramolecular competition system. In this system, known rate constants of olefin cyclizations are used as the internal clock. At-benzene reflux temperature (80 degrees C), the cyclization rate constants for 5-exo cyclizations of acylsilanes with primary radicals are on the order of 10(6) s(-1). The corresponding rate constants for 5-exo cyclizations with secondary radicals and 6-exo cyclizations with primary radicals lie on the order of 10(5) s(-1). The 6-exo cyclizations of acylsilanes with secondary radicals are slower and fall in the range of 10(4) s(-1). Substituents on the silicon of the acylsilanes affect the rates of cyclization. Large silyl groups reduce the rate, and this is more serious for the g-exo type of cyclizations. Electron-withdrawing groups increase the rates of cyclization.

  DOI：

  10.1021/jo982079k

文献信息

• The Study of the Kinetics of Intramolecular Radical Cyclizations of Acylsilanes via the Intramolecular Competition Method
  作者：Weir-Torn Jiaang、Hsien-Chang Lin、Kuo-Hsiang Tang、Lih-Bin Chang、Yeun-Min Tsai

  DOI：10.1021/jo982079k

  日期：1999.1.1

  The kinetics of the radical cyclizations of acylsilanes is probed by the construction of an intramolecular competition system. In this system, known rate constants of olefin cyclizations are used as the internal clock. At-benzene reflux temperature (80 degrees C), the cyclization rate constants for 5-exo cyclizations of acylsilanes with primary radicals are on the order of 10(6) s(-1). The corresponding rate constants for 5-exo cyclizations with secondary radicals and 6-exo cyclizations with primary radicals lie on the order of 10(5) s(-1). The 6-exo cyclizations of acylsilanes with secondary radicals are slower and fall in the range of 10(4) s(-1). Substituents on the silicon of the acylsilanes affect the rates of cyclization. Large silyl groups reduce the rate, and this is more serious for the g-exo type of cyclizations. Electron-withdrawing groups increase the rates of cyclization.
• A Novel 1,3-Stannyl Shift Promoted Intramolecular Cyclizations of α-Stannyl Radicals with a Formyl Group
  作者：Sheng-Yueh Chang、Yar-Fang Shao、Shu-Fang Chu、Gang-Ting Fan、Yeun-Min Tsai

  DOI：10.1021/ol990199o

  日期：1999.9.1

  [GRAPHICS]Reactions of alpha-stannyl bromides and xanthates with tributyltin hydride generate a stannyl radicals, Intramolecular cyclizations of these radicals with a formyl group afford gamma-stannyl alkoxy radicals that undergo a 1,3-stannyl shift from carbon to oxygen. The carbon radicals obtained can be trapped inter- or intramolecularly. Approximately, the rates of 5-exo cyclizations of alpha-stannyl radicals with a formyl group and terminal olefin are similar.