丙炔-3-¹³C | 60221-68-3

• 分子结构分类: 有机化合物 - 乙炔化物
• 中文名称: 丙炔-3-¹³C
• 英文名称: [3-13C]propyne
• 英文别名: [3-¹³C]propyne；Propin；Propyne-3-13C, 99 atom % 13C；(313C)prop-1-yne
• CAS: 60221-68-3
• 化学式: C₃H₄
• 分子量: 41.0538
• InChiKey: MWWATHDPGQKSAR-VQEHIDDOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  丙炔-3-¹³C 在 [Cp₂ZrD(Cl)]x 、 甲醇 作用下， 以 四氢呋喃 、 xylene 、 乙醚 为溶剂， 反应 4.0h， 生成 2-deuterio(313C)prop-1-ene
  参考文献：
  名称：

  Chain Epimerization during Propylene Polymerization with Metallocene Catalysts:  Mechanistic Studies Using a Doubly Labeled Propylene

  摘要：

  The mechanisms of chain epimerization during propylene polymerization with methylaluminoxane-activated rac-(EBTHI)ZrCl2 and rac-(EBI)ZrCl2 catalysts (EBTHI = ethylenebis(eta(5)-tetrahydroindenyl); EBI = ethylenebis(eta(5)-indenyl)) have been studied using specifically isotopically labeled propylene: CH2=(CDCH3)-C-13. These isospecific catalysts provide predominantly the expected [mmmm] pentads with [-(CH2CDCH3-)-C-13] repeating units (C-13 NMR). Under relatively low propylene concentrations at 50 and 75 degreesC, where stereoerrors attributable to chain epimerization are prevalent, 13C NMR spectra reveal C-13-labeled methylene groups along the polymer main chain, together with [(CDCH3)-C-13] units in [mmmr], [mmrr], and [mrrm] pentads and [(CHCH3)-C-13] units in [mmmmmm] and [mmmmmr] heptads, as well as [mrrm] pentads. The isotopomeric reglomisplacements; and stereoerrors are consistent with a mechanism involving beta-D elimination, olefin rotation and enantiofacial interconversions, and insertion to a tertiary alkyl intermediate [Zr-C(CH2D)((CH3)-C-13)P] (P = polymer chain), followed by the reverse steps to yield two stereoisomers of [Zr-CHDCH((CH3)-C-13)P] and [Zr-(CH2CH)-C-13(CH2D)P], as well as unrearranged [Zr-CH2CD((CH3)-C-13)P]. The absence of observable [-(CH2CHCH2D)-C-13-] in the [mrrm] pentad region of the C-13 NMR spectra provides evidence that an allyl/clihydrogen complex does not mediate chain epimerization.

  DOI：

  10.1021/ja0123296
• 作为产物：
  描述：

  碘甲烷-13C 、 乙炔钠 以 四氢呋喃 、 xylene 为溶剂， 反应 9.0h， 生成 丙炔-3-¹³C
  参考文献：
  名称：

  Chain Epimerization during Propylene Polymerization with Metallocene Catalysts:  Mechanistic Studies Using a Doubly Labeled Propylene

  摘要：

  The mechanisms of chain epimerization during propylene polymerization with methylaluminoxane-activated rac-(EBTHI)ZrCl2 and rac-(EBI)ZrCl2 catalysts (EBTHI = ethylenebis(eta(5)-tetrahydroindenyl); EBI = ethylenebis(eta(5)-indenyl)) have been studied using specifically isotopically labeled propylene: CH2=(CDCH3)-C-13. These isospecific catalysts provide predominantly the expected [mmmm] pentads with [-(CH2CDCH3-)-C-13] repeating units (C-13 NMR). Under relatively low propylene concentrations at 50 and 75 degreesC, where stereoerrors attributable to chain epimerization are prevalent, 13C NMR spectra reveal C-13-labeled methylene groups along the polymer main chain, together with [(CDCH3)-C-13] units in [mmmr], [mmrr], and [mrrm] pentads and [(CHCH3)-C-13] units in [mmmmmm] and [mmmmmr] heptads, as well as [mrrm] pentads. The isotopomeric reglomisplacements; and stereoerrors are consistent with a mechanism involving beta-D elimination, olefin rotation and enantiofacial interconversions, and insertion to a tertiary alkyl intermediate [Zr-C(CH2D)((CH3)-C-13)P] (P = polymer chain), followed by the reverse steps to yield two stereoisomers of [Zr-CHDCH((CH3)-C-13)P] and [Zr-(CH2CH)-C-13(CH2D)P], as well as unrearranged [Zr-CH2CD((CH3)-C-13)P]. The absence of observable [-(CH2CHCH2D)-C-13-] in the [mrrm] pentad region of the C-13 NMR spectra provides evidence that an allyl/clihydrogen complex does not mediate chain epimerization.

  DOI：

  10.1021/ja0123296

文献信息

• Synthesis of [3-D3]-, [3-13C]-, and [1,2-13C2]Propynes and Their Use for the Synthesis of [5-D3-Methyl]-, [5-13C-Methyl]-, and [5,6-13C2-2,5-Cyclohexadienyl]ubiquinones 3
  作者：Claude Boullais、Christelle Rannou、Emmanuel Réveillère、Charles Mioskowski

  DOI：10.1002/(sici)1099-0690(200003)2000:5<723::aid-ejoc723>3.0.co;2-q

  日期：2000.3

  Three selectively labeled propynes were prepared either with deuterium or carbon-13 at position 3 and doubly labeled with carbon-13 at positions 1 and 2 by an alkylation reaction from the corresponding labeled or unlabeled monolithio acetylides and dimethylsulfates. Their lithiation with nBuLi gave the corresponding propynyllithium derivatives which reacted with dimethyl squarate to afford the corresponding

  三种选择性标记的丙炔在 3 位用氘或碳 13 制备，并在 1 和 2 位用碳 13 双重标记，通过来自相应标记或未标记的单硫代乙炔和硫酸二甲酯的烷基化反应。它们与 nBuLi 锂化得到相应的丙炔基锂衍生物，该衍生物与方酸二甲酯反应得到相应的炔丙醇。这些在对二甲苯中热解以提供[5-D3-甲基]-、[5-13C-甲基]-和[5,6-13C2-2,5-环己二烯基]泛醌。在BF3催化下将法呢基侧链引入到标记的醌上，得到[5-D3-甲基]-、[5-13C-甲基]-和[5,6-13C2-2,5-环己二烯基]泛醌 3（分别为 6c、6b、6a）。