meso-1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane | 177986-20-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: meso-1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane
• 英文别名: 3-[(7R,14S)-8-(2-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetrazacyclotetradec-1-yl]propanenitrile
• CAS: 177986-20-8
• 化学式: C₂₂H₄₂N₆
• 分子量: 390.616
• InChiKey: TWTBZJJWNOYAHD-BGYRXZFFSA-N

物化性质

• 沸点：
  544.6±50.0 °C(Predicted)
• 密度：
  0.899±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  78.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  高氯酸 、 meso-1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane 、 nickel(II) acetate tetrahydrate 以 甲醇 为溶剂， 以90%的产率得到(meso-1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate
  参考文献：
  名称：

  Stepwise selective reaction of two N-cyanoethyl groups attached to C-racemic tetraaza macrocyclic nickel(II) and copper(II) complexes in aqueous solutions

  摘要：

  Stepwise hydrolysis of two N-(CH2)(2)CN groups attached to [Ni(C-racemic-L-2)(OAc)](+) and [Cu(C-racemic-L-2)](2+) (L-2 = 1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been investigated. The reaction of [Ni(C-meso-L-2)](2+) has also been examined. Interestingly, [Ni(C-racemic-L-2)(OAc)](+) is readily hydrolyzed to [Ni(C-racemic-L-3)](2+) bearing one N-(CH2)(2)CONH2 and one N-(CH2)(2)CN pendant arms at pH <= 6, whereas [Cu(C-racemic-L-2)](2+) and [Ni(C-meso-L-2)](2+) are quite inert against hydrolysis under similar acidic conditions. Although [Cu(C-racemic-L-2)](2+) is hydrolyzed to [Cu(C-racemic-L-3)](2+) at pH 9, [Ni(C-meso-L-2)](2+) readily undergoes C-N bond cleavage to yield [Ni(C-meso-L-1)](2+) (L-1 = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in basic aqueous solutions. The hetero-functionalized complex [Ni(C-racemic-L-3)](2+) undergoes hydrolysis and C-N bond cleavage at pH 9 and 13, respectively; both [Ni(C-racemic-L-4)](2+) bearing two N-(CH2)(2)CONH2 pendant arms and [Ni(C-racemic-L-5)](2+) bearing one N-(CH2)(2)CONH2 group can be prepared selectively by controlling pH of the solution. However, [Cu(C-racemic-L-3)](2+) readily undergoes C-N bond cleavage to produce [Cu(C-racemic-L-5)](2+) even at pH 9. Crystal structure of [Ni(C-racemic-L-3)](2+) shows that the complex has severely distorted trigonal bipyramidal coordination geometry. Electronic absorption spectra of [Cu(C-racemic-L-3)](2+), [Ni(C-racemic-L-5)](2+), and [Cu(C-racemic-L-5)](2+) indicate that they also have trigonal bipyramidal coordination geometry. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.11.003

文献信息

• Stepwise selective reaction of two N-cyanoethyl groups attached to C-racemic tetraaza macrocyclic nickel(II) and copper(II) complexes in aqueous solutions
  作者：Shin-Geol Kang、Nahee Kim、Jong Hwa Jeong

  DOI：10.1016/j.ica.2010.11.003

  日期：2011.1

  Stepwise hydrolysis of two N-(CH2)(2)CN groups attached to [Ni(C-racemic-L-2)(OAc)](+) and [Cu(C-racemic-L-2)](2+) (L-2 = 1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been investigated. The reaction of [Ni(C-meso-L-2)](2+) has also been examined. Interestingly, [Ni(C-racemic-L-2)(OAc)](+) is readily hydrolyzed to [Ni(C-racemic-L-3)](2+) bearing one N-(CH2)(2)CONH2 and one N-(CH2)(2)CN pendant arms at pH <= 6, whereas [Cu(C-racemic-L-2)](2+) and [Ni(C-meso-L-2)](2+) are quite inert against hydrolysis under similar acidic conditions. Although [Cu(C-racemic-L-2)](2+) is hydrolyzed to [Cu(C-racemic-L-3)](2+) at pH 9, [Ni(C-meso-L-2)](2+) readily undergoes C-N bond cleavage to yield [Ni(C-meso-L-1)](2+) (L-1 = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in basic aqueous solutions. The hetero-functionalized complex [Ni(C-racemic-L-3)](2+) undergoes hydrolysis and C-N bond cleavage at pH 9 and 13, respectively; both [Ni(C-racemic-L-4)](2+) bearing two N-(CH2)(2)CONH2 pendant arms and [Ni(C-racemic-L-5)](2+) bearing one N-(CH2)(2)CONH2 group can be prepared selectively by controlling pH of the solution. However, [Cu(C-racemic-L-3)](2+) readily undergoes C-N bond cleavage to produce [Cu(C-racemic-L-5)](2+) even at pH 9. Crystal structure of [Ni(C-racemic-L-3)](2+) shows that the complex has severely distorted trigonal bipyramidal coordination geometry. Electronic absorption spectra of [Cu(C-racemic-L-3)](2+), [Ni(C-racemic-L-5)](2+), and [Cu(C-racemic-L-5)](2+) indicate that they also have trigonal bipyramidal coordination geometry. (C) 2010 Elsevier B.V. All rights reserved.