meso-1,8-bis(carbamoylethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane | 1005453-17-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: meso-1,8-bis(carbamoylethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane
• 英文别名: C-meso-bis(N-carbamoylethyl)5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane；3-[(7R,14S)-8-(3-amino-3-oxopropyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetrazacyclotetradec-1-yl]propanamide
• CAS: 1005453-17-7
• 化学式: C₂₂H₄₆N₆O₂
• 分子量: 426.646
• InChiKey: WHZQTCJDSIYSAN-HDICACEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  117
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  高氯酸 、 meso-1,8-bis(carbamoylethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane 、 copper(II) acetate monohydrate 以 甲醇 为溶剂， 以90%的产率得到[Cu(C-meso-bis(N-carbamoylethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)][ClO4]2
  参考文献：
  名称：

  Synthesis of two configurational isomers of a 14-membered tetraaza macrocycle bearing N-CH2CH2CONH2 pendent arms and their copper(II) complexes: Crystal structures of the complexes

  摘要：

  Two isomers of 1,8-bis(N-carbamoylethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L-2) bearing two N-CH2CH2CONH2 groups, C-meso-L-2 and C-racemic-L-2, have been prepared and characterized. Each isomer reacts with Cu(II) ion to form a five-coordinate complex, [Cu(C-meso-L-2)](ClO4)(2) (1) or [Cu(C-racemic-L-2)](ClO4)(2) (2), in which only one pendent amide group is coordinated to the metal ion. The crystal structure of 1 center dot CH3CN shows that the complex possesses trans-III-type N-configuration and has a slightly distorted square-pyramidal coordination geometry with a relatively long axial Cu-O (N-CH2CH2CONH2) bond (2.207(3) angstrom). On the other hand, 2 exhibits trans-V configuration and has a slightly distorted trigonal bipyramidal coordination geometry with a very short equatorial Cu-O (N-CH2CH2CONH2) bond (2.007(3) angstrom); the Cu-O distance is distinctly shorter than the Cu-N distances (2.062(4)-2.090(4) angstrom). The complex 1 exhibits a d-d transition band at approximately 565 nm, whereas the band for 2 is observed at approximately 770 nm. (c) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2007.05.057

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.
• Synthesis of two configurational isomers of a 14-membered tetraaza macrocycle bearing N-CH2CH2CONH2 pendent arms and their copper(II) complexes: Crystal structures of the complexes
  作者：Shin-Geol Kang、Nahee Kim、Jong Hwa Jeong

  DOI：10.1016/j.ica.2007.05.057

  日期：2008.1

  Two isomers of 1,8-bis(N-carbamoylethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L-2) bearing two N-CH2CH2CONH2 groups, C-meso-L-2 and C-racemic-L-2, have been prepared and characterized. Each isomer reacts with Cu(II) ion to form a five-coordinate complex, [Cu(C-meso-L-2)](ClO4)(2) (1) or [Cu(C-racemic-L-2)](ClO4)(2) (2), in which only one pendent amide group is coordinated to the metal ion. The crystal structure of 1 center dot CH3CN shows that the complex possesses trans-III-type N-configuration and has a slightly distorted square-pyramidal coordination geometry with a relatively long axial Cu-O (N-CH2CH2CONH2) bond (2.207(3) angstrom). On the other hand, 2 exhibits trans-V configuration and has a slightly distorted trigonal bipyramidal coordination geometry with a very short equatorial Cu-O (N-CH2CH2CONH2) bond (2.007(3) angstrom); the Cu-O distance is distinctly shorter than the Cu-N distances (2.062(4)-2.090(4) angstrom). The complex 1 exhibits a d-d transition band at approximately 565 nm, whereas the band for 2 is observed at approximately 770 nm. (c) 2007 Elsevier B.V. All rights reserved.