[closo-1-CB9H8-1-COOMe-10-N=CPh] | 1206896-86-7

• 英文名称: [closo-1-CB9H8-1-COOMe-10-N=CPh]
• CAS: 1206896-86-7
• 化学式: C₁₀H₁₆B₉NO₂
• 分子量: 279.542
• InChiKey: HKPXNIAPGCISKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [closo-1-CB9H8-1-COOMe-10-N=CPh] 、 水 以 水 为溶剂， 生成 [closo-1-CB9H8-1-COOMe-10-NHC(O)Ph](1-)
  参考文献：
  名称：

  Anionic Amino Acid [closo-1-CB₉H₈-1-COO-10-NH₃]⁻ and Dinitrogen Acid [closo-1-CB₉H₈-1-COOH-10-N₂] as Key Precursors to Advanced Materials: Synthesis and Reactivity

  摘要：

  Amino acid [closo-1-CB9H8-1-COO-10-NH3](-) (4) was prepared by amination of iodo acid [closo-1-CB9H8-1-COOH1-0-1](-) (1) with LiHMDS in a practical and reproducible manner. The apparent dissociation constants, pK(2) = 5.6 and pK(1) > 11, were measured for 4[NMe4] in 50% aq. EtOH. Diazotization of 4 with NO+PF6- under mildly basic conditions afforded stable dinitrogen acid [closo-1-CB9H8-1-COOH-10-N-2] (5), Activation parameters (Delta H-double dagger = 33.9 +/- 1.4 kcal mol(-1) and Delta S-double dagger = 10 +/- 3.5 cal mol(-1) K-1) for thermolysis of its methyl ester [c/oso-1-CB9H8-1-COOMe-10-N-2] (11) in PhCN were established, and the heterolysis of the B-N bond is believed to be the rate-determining step. Electrochemical analysis showed a partially reversible reduction process for 11 (E-1/2(red) = - 1.03 V) and 5(-) (E-1/2(red) = -1.21 V), which are more cathodic than reduction of [closo-1-CB9H9-1-N-2] (17). The dinitrogen acid 5 was reacted with pyridine and N,N-dimethylthioformamide, to form pyridine acid 6 and protected mercapto acid 7, reSpOctively, through a boronium ylide intermediate 18, Compound 7 was converted to sulfonium acid 8. The molecular and crystal structures for 5 [C2H9B9N2O2 monoclinic, P2(1)/n, a = 7.022(2) angstrom, b 11.389(4) c = 12,815(4) angstrom, beta = 96.212(5)degrees; V= 1018.8(6) angstrom(3) Z = 4,] 6 [C7H14B9NO2, monoclinic, P2(1)/n, a 14.275(4) angstrom, b = 12.184(3) angstrom, c = 30.538(8)angstrom, beta = 95.377(4)degrees; V = 5288(3)angstrom(3), Z= 16], and 8[C7H19B9O2S, monoclinic, P2(1)/c, a = 15,988(5) angstrom, b = 13.377(6) angstrom, c = 9.655(3) angstrom, beta = 98.348(5)degrees; V= 2959.4(16)angstrom(3), Z= 8] were determined by X-ray crystallography and compared with results of density functional theory (DFT) and MP2 calculations. Electronic structures of 5, 6, and related species were elucidated with electronic spectroscopy and assessed computationally at the B3LYP/6-31 G(d,p), MP2/6-31G(d,p), and ZINDO//MP2 levels of theory.

  DOI：

  10.1021/ic9021323
• 作为产物：
  描述：

  [closo-1-CB9H8-1-COOMe-10-N2] 、 苯甲腈 以 苯甲腈 为溶剂， 生成 [closo-1-CB9H8-1-COOMe-10-N=CPh]
  参考文献：
  名称：

  Anionic Amino Acid [closo-1-CB₉H₈-1-COO-10-NH₃]⁻ and Dinitrogen Acid [closo-1-CB₉H₈-1-COOH-10-N₂] as Key Precursors to Advanced Materials: Synthesis and Reactivity

  摘要：

  Amino acid [closo-1-CB9H8-1-COO-10-NH3](-) (4) was prepared by amination of iodo acid [closo-1-CB9H8-1-COOH1-0-1](-) (1) with LiHMDS in a practical and reproducible manner. The apparent dissociation constants, pK(2) = 5.6 and pK(1) > 11, were measured for 4[NMe4] in 50% aq. EtOH. Diazotization of 4 with NO+PF6- under mildly basic conditions afforded stable dinitrogen acid [closo-1-CB9H8-1-COOH-10-N-2] (5), Activation parameters (Delta H-double dagger = 33.9 +/- 1.4 kcal mol(-1) and Delta S-double dagger = 10 +/- 3.5 cal mol(-1) K-1) for thermolysis of its methyl ester [c/oso-1-CB9H8-1-COOMe-10-N-2] (11) in PhCN were established, and the heterolysis of the B-N bond is believed to be the rate-determining step. Electrochemical analysis showed a partially reversible reduction process for 11 (E-1/2(red) = - 1.03 V) and 5(-) (E-1/2(red) = -1.21 V), which are more cathodic than reduction of [closo-1-CB9H9-1-N-2] (17). The dinitrogen acid 5 was reacted with pyridine and N,N-dimethylthioformamide, to form pyridine acid 6 and protected mercapto acid 7, reSpOctively, through a boronium ylide intermediate 18, Compound 7 was converted to sulfonium acid 8. The molecular and crystal structures for 5 [C2H9B9N2O2 monoclinic, P2(1)/n, a = 7.022(2) angstrom, b 11.389(4) c = 12,815(4) angstrom, beta = 96.212(5)degrees; V= 1018.8(6) angstrom(3) Z = 4,] 6 [C7H14B9NO2, monoclinic, P2(1)/n, a 14.275(4) angstrom, b = 12.184(3) angstrom, c = 30.538(8)angstrom, beta = 95.377(4)degrees; V = 5288(3)angstrom(3), Z= 16], and 8[C7H19B9O2S, monoclinic, P2(1)/c, a = 15,988(5) angstrom, b = 13.377(6) angstrom, c = 9.655(3) angstrom, beta = 98.348(5)degrees; V= 2959.4(16)angstrom(3), Z= 8] were determined by X-ray crystallography and compared with results of density functional theory (DFT) and MP2 calculations. Electronic structures of 5, 6, and related species were elucidated with electronic spectroscopy and assessed computationally at the B3LYP/6-31 G(d,p), MP2/6-31G(d,p), and ZINDO//MP2 levels of theory.

  DOI：

  10.1021/ic9021323