[closo-1-CB9H8-1-COOH-10-N2] | 1206896-79-8

• 英文名称: [closo-1-CB9H8-1-COOH-10-N2]
• 英文别名: closo-1-CB9H8-1-CO2H-10-N2
• CAS: 1206896-79-8
• 化学式: C₂H₉B₉N₂O₂
• 分子量: 190.405
• InChiKey: UVTPDGWHXCNIMI-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：

  重氮甲烷 、 [closo-1-CB9H8-1-COOH-10-N2] 以 乙醚 为溶剂， 以78%的产率得到[closo-1-CB9H8-1-COOMe-10-N2]
  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：

  nitrosyl hexafluorophosphate 、 [closo-1-CB9H8-1-COOH-10-NH3] 以 吡啶 、 乙腈 为溶剂， 以78%的产率得到[closo-1-CB9H8-1-COOH-10-N2]
  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

文献信息

• Transmission of Electronic Effects through the {<i>closo</i>-1-CB₉} and {<i>closo</i>-1-CB₁₁} Cages: Apparent Dissociation Constants for Series of [<i>closo</i>-1-CB₉H₈-1-COOH-10-X] and [<i>closo</i>-1-CB₁₁H₁₀-1-COOH-12-X] Acids
  作者：Jacek G. Pecyna、Bryan Ringstrand、Piotr Kaszyński

  DOI：10.1021/ic300298e

  日期：2012.5.7

  for series 1 and ρ = 1.00 ± 0.09 for series 2. These values are higher than for derivatives of PhCH═CHCOOH (ρ = 0.70 ± 0.09 in 55% EtOH) and correspond to 56% and 65% efficiencies in transmission of electronic effects by [closo-1-CB9H10]− (E) and [closo-1-CB11H12]− (F), respectively, as compared to benzene (A). Experimental results were supported with DFT calculations of relative acidity for series

  表观电离常数p ķ一个'的一系列羧酸[闭合碳-1-CB 9 ħ 8 -1-COOH-10-X] -（1）和[闭合碳-1-CB 11 ħ 10 -1-COOH- 12-X] -（2），其中X = H，I，n -C 6 H 13，+ NMe 3，+ N 2，+ SMe 2，OC 5 H 11，在EtOH / H 2中测量O（1/1，v / v）在24°C下。该p的相关性分析ķ一个使用哈米特取代基常数σ'的值p（X），得到反应常数ρ= 0.87±0.04对于系列1和ρ= 1.00±串联0.09 2。这些值高于PhCH = CHCOOH的衍生物（在55％的EtOH中，ρ= 0.70±0.09），并且对应于[ closo -1-CB 9 H 10 ] -（E的电子效应传递效率，分别为56％和65％。）和[ closo -1-CB 11 H 12 ] -（F）与苯（A）。DFT计算得出了在水性介质中衍
• Diazotization of the Amino Acid [<i>closo</i>-1-CB₉H₈-1-COOH-6-NH₃] and Reactivity of the [<i>closo</i>-1-CB₉H₈-1-COO-6-N₂]⁻ Anion
  作者：Bryan Ringstrand、Piotr Kaszynski、Victor G. Young

  DOI：10.1021/ic102557s

  日期：2011.3.21

  2] (3[6]) was conducted by diazotization of a mixture of amino acids [closo-1-CB9H8-1-COOH-6-NH3] (1[6]) and [closo-1-CB9H8-1-COOH-10-NH3] (1[10]) with NO+BF4− in the presence of a heterocyclic base (pyridine, 4-methoxypyridine, 2-picoline, or quinoline). The 10-amino acid 1[10] formed an isolable stable 10-dinitrogen acid 3[10], while the 6-dinitrogen carboxylate 3[6]− reacted in situ, giving products

  二硝酸[ closo -1-CB 9 H 8 -1-COOH-10-N 2 ]（3 [10]）和[ closo -1-CB 9 H 8 -1-COOH-6的反应性的比较研究-N 2 ]（3 [6]）通过氨基酸[ closo -1-CB 9 H 8 -1-COOH-6-NH 3 ]（1 [6]）和[ closo -1 -CB 9 H 8 -1-COOH-10-NH 3 ]（1 [10]）与NO + BF 4−在杂环碱（吡啶，4-甲氧基吡啶，2-甲基吡啶或喹啉）存在下。10个氨基酸1 [10]形成可分离的稳定10-二硝基酸3 [10]，而6-二氮羧酸酯3 [6] -原位反应，在B6位上杂环取代N的产物溶剂（4 [6]）。通过X射线晶体学测定吡啶鎓酸4 [6] a的分子和晶体结构。1-CB 9的6-二氮衍生物的电子结构和反应性}群集在理论水平的B3LYP / 6-31G（d，p）和MP2 /
• The preparation of [closo-1-CB9H8-1-COOH-10-(4-C3H7C5H9S)] as intermediate to polar liquid crystals
  作者：Jacek Pecyna、Richard P. Denicola、Bryan Ringstrand、Aleksandra Jankowiak、Piotr Kaszynski

  DOI：10.1016/j.poly.2011.06.022

  日期：2011.9

  The preparation of iodo acid [closo-1-CB9H8-1-COOH-10-I](-) (1) is optimized and scaled from 1 to 40 g of B10H14. The improved preparation of the [arachno-6-CB9H13-6-COOH](-) (5) uses four times smaller volume and can be run conveniently in up to 40 g scale in a 3-L vessel. The optimized oxidation of 5 to [closo-2-CB9H9-2-COOH](-) (4) requires less oxidant, 12 times smaller volume, and significantly shorter reaction time. The overall yields of the iodo acid 1 as the [NMe4](+) salt are typically 8-10% (10-12 g) for 40 g of B10H14. The iodo acid 1 was transformed to amino acid 8, then to dinitrogen acid 10, and finally to sulfonium acid 2[3] in overall yield of about 13%. The search for a more efficient phosphine ligand for the Pd-catalyzed amination process was not fruitful. Three routes to the sulfonium acid 2[n] were investigated, and the best yield of about 47% was obtained for Cs2CO3-assisted cycloalkylation. Liquid crystalline ester of acid 2[3] and 4-butoxyphenol was prepared and investigated. (C) 2011 Elsevier Ltd. All rights reserved.