1-(methoxymethyl)-2-bromo-4,5-dicyanoimidazole | 134848-52-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-(methoxymethyl)-2-bromo-4,5-dicyanoimidazole
• 英文别名: 2-bromo-1-(methoxymethyl)imidazole-4,5-dicarbonitrile
• CAS: 134848-52-5
• 化学式: C₇H₅BrN₄O
• 分子量: 241.047
• InChiKey: QTWZTGZIGYKFMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.99
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  74.63
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  1-(methoxymethyl)-2-bromo-4,5-dicyanoimidazole 在 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 1,1'-tetramethylene-4,4',5,5'-tetracyano-2,2'-biimidazole
  参考文献：
  名称：

  Synthesis and properties of new derivatives of 4,5-dicyanoimidazole and 4,4',5,5'-tetracyano-2,2'-biimidazole

  摘要：

  The synthesis and properties of new derivatives of 4,5-dicyanoimidazole (1, HDcim) and 4,4',5,5'-tetracyano-2,2'-biimidazole (2, H2Tcbiim) are reported. Conditions for selective metalation at the 2-position of N-protected 4,5-dicyanoimidazoles are described. Various protecting groups were used. Oxidative coupling of N-protected 2-lithio-4,5-dicyanoimidazoles with cupric chloride gives new 1,1'-disubstituted derivatives of 4,4',5,5'-tetracyano-2,2'-biimidazole (13-15, R2Tcbiim where R = CH3, CH2OCH3, CH2Ph). Ullmann coupling of 1-methyl-2-bromo-4,5-dicyanoimidazole (6) gives (CH3)2Tcbiim (13). Deprotection of R2Tcbiim (when R = CH3 or CH2OCH3) gives H2Tcbiim (2). Several new routes to H2Tcbiim are now available. Reaction of H2Tcbiim with 1,n-dihaloalkanes (n = 2, 3, and 4) gives the corresponding 1,1'-alkyl-bridged derivatives 16-18 or (CH2)nTcbiim (n = 2, 3, and 4). (CH2)2Tcbiim (16) has also been synthesized via an intramolecular Ullmann coupling reaction of 19. The physical, structural, and electronic properties of these new cyanoimidazoles have been investigated by using UV-visible spectroscopy and cyclic voltammetry. Dicyanoimidazoles and tetracyanobiimidazoles are moderate to weak electron acceptors. (CH2)2Tcbiim (16) forms a 1:1 complex with tetrathiafulvalene (TTF). The donor (D)-acceptor (A) complex, [TTF][(CH2)2Tcbiim], forms as red needles from acetonitrile solution. X-ray crystallography of [TTF][(CH2)2Tcbiim] shows extended alternate or "mixed" stacking (...DADADA...). The photoluminescence spectrum of the complex shows an emission band centered at 660 nm with onset of emission at 530 nm.

  DOI：

  10.1021/ja00016a038
• 作为产物：
  描述：

  氯甲基甲基醚 、 2-溴-4,5-二氰基咪唑 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以89%的产率得到1-(methoxymethyl)-2-bromo-4,5-dicyanoimidazole
  参考文献：
  名称：

  Synthesis and properties of new derivatives of 4,5-dicyanoimidazole and 4,4',5,5'-tetracyano-2,2'-biimidazole

  摘要：

  The synthesis and properties of new derivatives of 4,5-dicyanoimidazole (1, HDcim) and 4,4',5,5'-tetracyano-2,2'-biimidazole (2, H2Tcbiim) are reported. Conditions for selective metalation at the 2-position of N-protected 4,5-dicyanoimidazoles are described. Various protecting groups were used. Oxidative coupling of N-protected 2-lithio-4,5-dicyanoimidazoles with cupric chloride gives new 1,1'-disubstituted derivatives of 4,4',5,5'-tetracyano-2,2'-biimidazole (13-15, R2Tcbiim where R = CH3, CH2OCH3, CH2Ph). Ullmann coupling of 1-methyl-2-bromo-4,5-dicyanoimidazole (6) gives (CH3)2Tcbiim (13). Deprotection of R2Tcbiim (when R = CH3 or CH2OCH3) gives H2Tcbiim (2). Several new routes to H2Tcbiim are now available. Reaction of H2Tcbiim with 1,n-dihaloalkanes (n = 2, 3, and 4) gives the corresponding 1,1'-alkyl-bridged derivatives 16-18 or (CH2)nTcbiim (n = 2, 3, and 4). (CH2)2Tcbiim (16) has also been synthesized via an intramolecular Ullmann coupling reaction of 19. The physical, structural, and electronic properties of these new cyanoimidazoles have been investigated by using UV-visible spectroscopy and cyclic voltammetry. Dicyanoimidazoles and tetracyanobiimidazoles are moderate to weak electron acceptors. (CH2)2Tcbiim (16) forms a 1:1 complex with tetrathiafulvalene (TTF). The donor (D)-acceptor (A) complex, [TTF][(CH2)2Tcbiim], forms as red needles from acetonitrile solution. X-ray crystallography of [TTF][(CH2)2Tcbiim] shows extended alternate or "mixed" stacking (...DADADA...). The photoluminescence spectrum of the complex shows an emission band centered at 660 nm with onset of emission at 530 nm.

  DOI：

  10.1021/ja00016a038