2,7-diazatetracyclo[6.2.2.2^3,6.0^2,7]tetradec-4-ene | 105616-08-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吖庚因类
• 英文名称: 2,7-diazatetracyclo[6.2.2.2^3,6.0^2,7]tetradec-4-ene
• 英文别名: 2,7-diazatetracyclo[6.2.2.23,6.02,7]tetradec-4-ene
• CAS: 105616-08-8
• 化学式: C₁₂H₁₈N₂
• 分子量: 190.288
• InChiKey: XJVSHYCJDMKQNA-UHFFFAOYSA-N

物化性质

• 沸点：
  284.1±43.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,7-diazatetracyclo[6.2.2.2^3,6.0^2,7]tetradec-4-ene 在 palladium-barium carbonate 氢气 、 potassium carbonate 作用下， 生成 2,7-diazatetracyclo[6.2.2.2^3,6.0^2,7]tetradecane
  参考文献：
  名称：

  Diels-Alder reaction of protonated azo compounds. Isolation of a tetraalkyldiazenium dication

  摘要：

  DOI：

  10.1021/ja00323a058
• 作为产物：
  描述：

  生成 2,7-diazatetracyclo[6.2.2.2^3,6.0^2,7]tetradec-4-ene
  参考文献：
  名称：

  Intermolecular Electron-Transfer Reactions Involving Hydrazines

  摘要：

  The self-exchange electron-transfer (ET) rate constant k(22) for 1,2,3,4,5-pentamethylferrocene was determined by NMR line broadening to be 8.5(+/-0.8) x 10(6) M(-1) s(-1) (25 degrees C, CD3CN/0.09 M Et(4)NBF(4)) and k(11) for the bis-N,N-bicyclic hydrazine, 9,9'-bi-9-azabicyclo[3.3.1]nonane, to be 8.7(0.5) x 10(3) M(-1) s(-1) (25 degrees C, CH2Cl2). These self-exchange rate constants are used to analyze cross reactions of these molecules with hydrazines, ferrocenes, and tetramethyl-p-phenylenediamine (TMPD) using Marcus theory. Cross-reaction rate constants for eight reactions are reported. Included are six cross-reactions between methylferrocenes and four cyclic hydrazines, one hydrazine, hydrazine-reaction, and the reduction of TMPD(+) by a cyclic hydrazine. These are the first cross-reaction rate constants reported for hydrazine-hydrazine and hydrazine-TMPD(+) ET reactions. The crossreaction rate constants are used to test the application of Marcus theory to hydrazine ET reactions and to extract estimates of hydrazine self-exchange ET rate constants in systems for which direct measurement is presently impossible.

  DOI：

  10.1021/jo9510090

文献信息

• Reactions of Bis(N,N'-bicyclic) Diazenium Dications
  作者：Stephen F. Nelsen、Yichun Wang

  DOI：10.1021/jo00090a028

  日期：1994.6

  Eleven bis(N,N'-bicyclic) diazenium dications were generated from the corresponding hydrazines by NOPF6 oxidation. Their reactivity depends greatly upon the sizes of the bicyclic rings. (We designate bicyclic ring size using the number of atoms in the two bridges in addition to the dinitrogen bridge all the compounds share.) Compounds with 21 rings alkylate acetonitrile at 240 K by opening a C-alpha-N+ bond to produce a trialkyldiazenium cation, with Delta G(double dagger) for the reaction increasing by at least 5.5 kcal/mol as the second bicyclic ring size increases. Compounds with an unsaturated bridge also alkylate acetonitrile; 22/u22(2+) only cleaves the u22 bridge and reacts faster than 21/22(2+), which only cleaves the 21 bridge. C-alpha-N+ cleavage of 22 and larger rings by acetonitrile has not been observed. 21/22(2+) is significantly more acidic than 22/22(2+), but both are beta-deprotonated by pyridine to produce aminoaziridinium cations at 240 K. At least mostly the exo 21 ring proton is lost from 21/22(2+). Dications with 23 and 24 bridges deprotonate at the alpha-carbon instead of the beta-carbon, and 22/23(2+) is slightly more kinetically acidic than 21/22(2+). 22/24(2+) is deprotonated rapidly by ether at 235 K.
• NELSEN, S. F.;BLACKSTOCK, S. C.;FRIGO, T. B., J. AMER. CHEM. SOC., 1984, 106, N 11, 3366-3367
  作者：NELSEN, S. F.、BLACKSTOCK, S. C.、FRIGO, T. B.

  DOI：——

  日期：——