2,2,3,3-tetramethylcyclopropanecarboxylic acid propargyl ester | 135609-57-3

• 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: 2,2,3,3-tetramethylcyclopropanecarboxylic acid propargyl ester
• 英文别名: ethynyl 2,2,3,3-tetramethylcyclopropanecarboxylate；Prop-2-ynyl 2,2,3,3-tetramethylcyclopropane-1-carboxylate
• CAS: 135609-57-3
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: KIGIXBIDGIBDGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2,3,3-tetramethylcyclopropanecarboxylic acid propargyl ester 在 potassium carbonate 、 重水 作用下， 以 乙腈 为溶剂， 反应 1.5h， 以99%的产率得到3-deutero-prop-2-ynyl 2,2,3,3-tetramethylcyclopropanecarboxylate
  参考文献：
  名称：

  Mild Reaction Conditions for the Terminal Deuteration of Alkynes

  摘要：

  Routinely employed syntheses of terminally deuterated alkynes often utilize strong bases (i.e., LDA, n-BuLi, or Grignard reagents) or low (i.e., -78 degrees C) or elevated (i.e., 56 degrees C) reaction temperatures; furthermore many of these procedures afford average yields and in some cases less than optimum deuterium incorporation. Herein we report the application of alternative extremely mild reaction conditions that readily afford quantitative yields of terminally deuterated alkynes in a matter of minutes with exceptional isotope incorporation at ambient temperature.

  DOI：

  10.1021/ol2029178
• 作为产物：
  描述：

  在 rhodium(II) acetate dimer 、 盐酸 、 acetate buffer 、 sodium nitrite 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 2,2,3,3-tetramethylcyclopropanecarboxylic acid propargyl ester
  参考文献：
  名称：

  Synthesis and carbene decomposition of functionally substituted diazoacetate esters. 6. Propargyl diazoacetate

  摘要：

  A synthesis of propargyl diazoacetate (I) was carried out and its chemical transformations were studied. The reaction of (I) in the presence of Rh(OAc)2 at 25-degrees-C with 1-pentyne gives the propargyl ester of 1-propylcyclopropene-3-carboxylic acid in 80% yield, while reaction with 2,3-dimethyl-2-butene at 60-degrees-C results in the propargyl ester of tetramethylcyclopropanecarboxylic acid in 10% yield. Compound (I) reacts under the same conditions (35-60-degrees-C) with ether, CH2Cl2 and water, with the formation of propargyl esters of ethoxy-acetic, 2,3-dichloropropionic, and a mixture of glycols and 2-{[(propyn-2-yl)oxycarbonyl]methoxy} acetic acids in yields of up to 35%. A spontaneous oligomerization of (I) was observed as a result of a dipolar [1, 3]-cycloaddition of the CH = N2 fragment of one molecule of (I) to the terminal-triple bond of the second molecule with the formation of oligomers of 3-hydroxymethylpyrazole-5-carboxylic acid.

  DOI：

  10.1007/bf00961353

文献信息

• SHAPIRO, E. A.;DYATKIN, A. B.;NEFEDOV, O. M., IZV. AN CCCP. CEP. XIM.,(1991) N, S. 1051-1056
  作者：SHAPIRO, E. A.、DYATKIN, A. B.、NEFEDOV, O. M.

  DOI：——

  日期：——
• Mild Reaction Conditions for the Terminal Deuteration of Alkynes
  作者：Sean P. Bew、Glyn D. Hiatt-Gipson、Jenny. A. Lovell、Christophe Poullain

  DOI：10.1021/ol2029178

  日期：2012.1.20

  Routinely employed syntheses of terminally deuterated alkynes often utilize strong bases (i.e., LDA, n-BuLi, or Grignard reagents) or low (i.e., -78 degrees C) or elevated (i.e., 56 degrees C) reaction temperatures; furthermore many of these procedures afford average yields and in some cases less than optimum deuterium incorporation. Herein we report the application of alternative extremely mild reaction conditions that readily afford quantitative yields of terminally deuterated alkynes in a matter of minutes with exceptional isotope incorporation at ambient temperature.
• Synthesis and carbene decomposition of functionally substituted diazoacetate esters. 6. Propargyl diazoacetate
  作者：E. A. Shapiro、A. B. Dyatkin、O. M. Nefedov

  DOI：10.1007/bf00961353

  日期：1991.5

  A synthesis of propargyl diazoacetate (I) was carried out and its chemical transformations were studied. The reaction of (I) in the presence of Rh(OAc)2 at 25-degrees-C with 1-pentyne gives the propargyl ester of 1-propylcyclopropene-3-carboxylic acid in 80% yield, while reaction with 2,3-dimethyl-2-butene at 60-degrees-C results in the propargyl ester of tetramethylcyclopropanecarboxylic acid in 10% yield. Compound (I) reacts under the same conditions (35-60-degrees-C) with ether, CH2Cl2 and water, with the formation of propargyl esters of ethoxy-acetic, 2,3-dichloropropionic, and a mixture of glycols and 2-[(propyn-2-yl)oxycarbonyl]methoxy} acetic acids in yields of up to 35%. A spontaneous oligomerization of (I) was observed as a result of a dipolar [1, 3]-cycloaddition of the CH = N2 fragment of one molecule of (I) to the terminal-triple bond of the second molecule with the formation of oligomers of 3-hydroxymethylpyrazole-5-carboxylic acid.