N³,4-ethenocytidine hydrochloride | 36207-55-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N³,4-ethenocytidine hydrochloride
• 英文别名: ethenocytidine hydrochloride；3,n4-Ethenocytidine hydrochloride；6-[(2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]imidazo[1,2-c]pyrimidin-5-one;hydrochloride
• CAS: 36207-55-3
• 化学式: C₁₁H₁₃N₃O₅*ClH
• 分子量: 303.702
• InChiKey: NHULVQYOCYAWTE-RQDZQORCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.47
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  108
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2,2-二溴乙醇 、 胞苷 在 N-ethylmorpholinium acetate 作用下， 反应 168.0h， 生成 N³,4-ethenocytidine hydrochloride
  参考文献：
  名称：

  Formation of etheno adducts of adenosine and cytidine from 1-halooxiranes. Evidence for a mechanism involving initial reaction with the endocyclic nitrogen atoms

  摘要：

  The etheno derivatives of nucleic acid bases contain an additional ring and are of interest because of their useful fluorescence properties and their potential as mutagenic lesions in DNA. The mechanism of formation from 2-haloacetaldehydes is known to involve initial Schiff base formation at an exocyclic nitrogen; however, mechanisms of formation from the more relevant 1-substituted oxiranes have not been established. The reaction of N6-methyladenosine (5) with 1-chlorooxirane yielded the stable carbinolamine 7,8-dihydro-8-hydroxy-9-methyl-3-beta-D-ribofuranosylimidazo[2,1-i]purinium species (10), consistent with initial attack of the N1 atom of adenine at the methylene of 1-chlorooxirane. No products indicative of initial reaction at the N6 atom of adenine were found. Reaction of 2,2-dibromoethanol with adenosine or cytidine at pH 9.2 yielded 1,N6-ethenoadenosine (1) or 3,N4-ethenocytidine (2), respectively, presumably via the base-catalyzed formation of 1-bromooxirane from the bromohydrin. When reactions were done with 2,2-dibromo[1-C-13]ethanol, 1 contained label only at C-7 and 2 contained label only at C-3. A role for 2-bromoacetaldehyde in these reactions was ruled out by the lack of incorporation of deuterium from (H2O)-H-2 into 1 under conditions where the exchange of the methylene protons of 2-bromoacetaldehyde with the solvent was relatively rapid. The collective results are most consistent with a mechanism in which the basic endocyclic nitrogen (N1 of adenine or N3 of cytosine) reacts with the methylene carbon of the 1-halooxirane, and, after ring opening and loss of the leaving group, the resulting aldehyde reacts with the exocyclic nitrogen to form the additional ring.

  DOI：

  10.1021/ja00029a041

文献信息

• Formation of etheno adducts of adenosine and cytidine from 1-halooxiranes. Evidence for a mechanism involving initial reaction with the endocyclic nitrogen atoms
  作者：F. Peter Guengerich、Veronica D. Raney

  DOI：10.1021/ja00029a041

  日期：1992.1

  The etheno derivatives of nucleic acid bases contain an additional ring and are of interest because of their useful fluorescence properties and their potential as mutagenic lesions in DNA. The mechanism of formation from 2-haloacetaldehydes is known to involve initial Schiff base formation at an exocyclic nitrogen; however, mechanisms of formation from the more relevant 1-substituted oxiranes have not been established. The reaction of N6-methyladenosine (5) with 1-chlorooxirane yielded the stable carbinolamine 7,8-dihydro-8-hydroxy-9-methyl-3-beta-D-ribofuranosylimidazo[2,1-i]purinium species (10), consistent with initial attack of the N1 atom of adenine at the methylene of 1-chlorooxirane. No products indicative of initial reaction at the N6 atom of adenine were found. Reaction of 2,2-dibromoethanol with adenosine or cytidine at pH 9.2 yielded 1,N6-ethenoadenosine (1) or 3,N4-ethenocytidine (2), respectively, presumably via the base-catalyzed formation of 1-bromooxirane from the bromohydrin. When reactions were done with 2,2-dibromo[1-C-13]ethanol, 1 contained label only at C-7 and 2 contained label only at C-3. A role for 2-bromoacetaldehyde in these reactions was ruled out by the lack of incorporation of deuterium from (H2O)-H-2 into 1 under conditions where the exchange of the methylene protons of 2-bromoacetaldehyde with the solvent was relatively rapid. The collective results are most consistent with a mechanism in which the basic endocyclic nitrogen (N1 of adenine or N3 of cytosine) reacts with the methylene carbon of the 1-halooxirane, and, after ring opening and loss of the leaving group, the resulting aldehyde reacts with the exocyclic nitrogen to form the additional ring.