1,1-dimethyl-3-dimethylamino-1,2-dihydropentalene | 1258868-79-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,1-dimethyl-3-dimethylamino-1,2-dihydropentalene
• 英文别名: N,N,3,3-tetramethyl-2H-pentalen-1-amine
• CAS: 1258868-79-9
• 化学式: C₁₂H₁₇N
• 分子量: 175.274
• InChiKey: BLNRQQBOTTYYJC-UHFFFAOYSA-N

物化性质

• 沸点：
  305.4±9.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,1-dimethyl-3-dimethylamino-1,2-dihydropentalene 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 (6-(dimethyliminio)-4,4-dimethyl-1,4,5,6-tetrahydropentalen-2-yl)bis(perfluorophenyl)hydroborate
  参考文献：
  名称：

  Reaction of Aminodihydropentalenes with HB(C₆F₅)₂: The Crucial Role of Dihydrogen Elimination

  摘要：

  The aminodihydropentalene derivative la reacts with the Lewis acidic RB(C6F5)(2) boranes (2a-c) by C-C bond cleavage to yield the formal borylene insertion products 3. In contrast, 1a,b react with HB(C6F5)(2) at 55 degrees C by elimination of dihydrogen to yield the iminium-stabilized zwitterionic heterofulvenes 10a,b. The reaction pathways were studied by preparation of the kinetically controlled intermediates 7a,b and the thermodynamically controlled products 9a,b, monitored by variable-temperature NMR experiments, and supported by DFT calculations. The trapping reactions of 9a with HCl and PhCHO, respectively, led to the addition products 13 and 14. Compounds 3c, 7a,b, 10a,b, 11, 13, and 14 were characterized by X-ray diffraction.

  DOI：

  10.1021/ja1092369
• 作为产物：
  描述：

  N.N-二甲基异丁烯酰胺 以 四氢呋喃 为溶剂， 生成 1,1-dimethyl-3-dimethylamino-1,2-dihydropentalene
  参考文献：
  名称：

  Zirconocene complexes bearing novel 3-dimethylamino-1,2-dihydropentalene derived ligand systems

  摘要：

  N,N-二甲基丙烯酰胺 6a–c 与环戊二烯化物的偶联导致形成取代的 3-二甲基氨基-1,2-二氢戊烯 2a–c。去质子化，然后用 CpZrCl3·DME 金属化，得到取代的二茂锆 12a–c。 3-二甲氨基-1-甲基-二氢并环戊二烯 2a 与 ZrCl2(NMe2)2·2THF 的反应导致一对氨基二氢并环戊二烯衍生物之间发生独特的偶联，从而产生不对称桥联的新型柄型二茂锆骨架 (9a)。相反，用该Zr-酰氨基试剂处理1,1-二甲基取代的底物2b导致完全去质子化并形成未桥联的双(二甲基氨基氢五烯基)ZrCl 2 络合物10b。通过X射线衍射对化合物2a、9a、meso-10b、12a和12c进行了表征。

  DOI：

  10.1039/c0dt00515k

文献信息

• Carbon–Carbon Bond Cleavage by Strongly Electrophilic Boranes
  作者：Bao‐Hua Xu、Gerald Kehr、Roland Fröhlich、Gerhard Erker

  DOI：10.1002/chem.201002047

  日期：2010.11.8

  Make and break: Strongly electrophilic boranes RB(C6F5)2 (R=Me, CH2CH2Ph) react with an aminodihydropentalene substrate by CC bond cleavage with concomitant borylene insertion to yield the ring‐enlarged zwitterionic borate/iminium product.

  产生和破坏：强亲电子的硼烷RB（C 6 F 5）2（R = Me，CH 2 CH 2 Ph）通过CC键断裂与伴随的亚芳基插入而与氨基二氢戊烯底物反应生成环扩大的两性离子硼酸酯/亚胺盐产品。
• Reaction of Aminodihydropentalenes with HB(C₆F₅)₂: The Crucial Role of Dihydrogen Elimination
  作者：Bao-Hua Xu、Gerald Kehr、Roland Fröhlich、Stefan Grimme、Gerhard Erker

  DOI：10.1021/ja1092369

  日期：2011.3.16

  The aminodihydropentalene derivative la reacts with the Lewis acidic RB(C6F5)(2) boranes (2a-c) by C-C bond cleavage to yield the formal borylene insertion products 3. In contrast, 1a,b react with HB(C6F5)(2) at 55 degrees C by elimination of dihydrogen to yield the iminium-stabilized zwitterionic heterofulvenes 10a,b. The reaction pathways were studied by preparation of the kinetically controlled intermediates 7a,b and the thermodynamically controlled products 9a,b, monitored by variable-temperature NMR experiments, and supported by DFT calculations. The trapping reactions of 9a with HCl and PhCHO, respectively, led to the addition products 13 and 14. Compounds 3c, 7a,b, 10a,b, 11, 13, and 14 were characterized by X-ray diffraction.
• Zirconocene complexes bearing novel 3-dimethylamino-1,2-dihydropentalene derived ligand systems
  作者：Bao-Hua Xu、Gerald Kehr、Roland Fröhlich、Elisa Nauha、Gerhard Erker

  DOI：10.1039/c0dt00515k

  日期：——

  Coupling of the N,N-dimethylacrylamides 6a–c with cyclopentadienide resulted in the formation of the substituted 3-dimethylamino-1,2-dihydropentalnenes 2a–c. Deprotonation followed by metallation with CpZrCl3·DME gave the substituted zirconocenes 12a–c. The reaction of 3-dimethylamino-1-methyl-dihydropentalene 2a with ZrCl2(NMe2)2·2THF resulted in a unique coupling between a pair of the aminodihydropentalene derivatives to yield an unsymmetrically bridged novel ansa-zirconocene framework (9a). Treatment of the 1,1-dimethyl-substituted substrate 2b with this Zr-amido reagent in contrast resulted in a clean deprotonation and formation of the unbridged bis(dimethylaminohydropentalenyl)ZrCl2 complexes 10b. The compounds 2a, 9a, meso-10b, 12a and 12c were characterized by X-ray diffraction.

  N,N-二甲基丙烯酰胺 6a–c 与环戊二烯化物的偶联导致形成取代的 3-二甲基氨基-1,2-二氢戊烯 2a–c。去质子化，然后用 CpZrCl3·DME 金属化，得到取代的二茂锆 12a–c。 3-二甲氨基-1-甲基-二氢并环戊二烯 2a 与 ZrCl2(NMe2)2·2THF 的反应导致一对氨基二氢并环戊二烯衍生物之间发生独特的偶联，从而产生不对称桥联的新型柄型二茂锆骨架 (9a)。相反，用该Zr-酰氨基试剂处理1,1-二甲基取代的底物2b导致完全去质子化并形成未桥联的双(二甲基氨基氢五烯基)ZrCl 2 络合物10b。通过X射线衍射对化合物2a、9a、meso-10b、12a和12c进行了表征。