1-Benzyloxymethyl-5-[1,3]dioxolan-2-yl-4-iodo-1H-imidazole | 134420-50-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 1-Benzyloxymethyl-5-[1,3]dioxolan-2-yl-4-iodo-1H-imidazole
• 英文别名: 5-(1,3-Dioxolan-2-yl)-4-iodo-1-(phenylmethoxymethyl)imidazole
• CAS: 134420-50-1
• 化学式: C₁₄H₁₅IN₂O₃
• 分子量: 386.189
• InChiKey: HMBAOVMGAOLEIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-Benzyloxymethyl-5-[1,3]dioxolan-2-yl-4-iodo-1H-imidazole 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.0h， 以76%的产率得到1-<(benzyloxy)methyl>imidazole-5-carboxaldehyde ethylene acetal
  参考文献：
  名称：

  Regioselective formation of imidazol-2-yllithium, imidazol-4-yllithium, and imidazol-5-yllithium species

  摘要：

  Representative imidazol-2-yllithium, imidazol-4-yllithium, and imidazol-5-yllithium species have been prepared via halogen-metal exchange, and the propensity of the latter two to undergo isomerization and quench by electrophilic reagents has been studied. The C2-unsubstituted imidazol-5-yllithium species 3 is generated within 10 min at -78-degrees-C from 1-[(benzyloxy)methyl]-4,5-diiodoimidazole (1b) and affords the C5-formyl product 4 upon reaction with DMF, but gives the isomeric C2-formyl product 6 if allowed to equilibrate to the imidazol-2-yllithium species 5 for an additional 35 min at -78-degrees-C before quench. The less reactive electrophile diethyl carbonate is unable to trap 3 and instead reacts with 5 to afford tris[1-[(benzyloxy)methyl]-4-iodo-2-imidazolyl]carbinol (7). In contrast, 1-[(benzyloxy)methyl]-4-iodoimidazole-5-carboxaldehyde ethylene acetal (10) metalates to give the C2-unsubstituted imidazol-4-yllithium species 13, which undergoes a very rapid conversion to its imidazol-2-yllithium isomer 14, even at -100-degrees-C, giving the 2,5-dicarboxaldehyde 5-ethylene acetal 16 or the 2-deuterio-5-carboxaldehyde ethylene acetal 15 upon quench with DMF or D2O, respectively. Thus, in the presence of C2 unsubstitution, C5 functionalization could be accomplished when the electrophile was sufficiently reactive, while C4 functionalization could not. Short- and long-range H-1-C-13 heteronuclear (Hector) 2D NMR spectroscopic analyses were instrumental in the structural assignments of key compounds.

  DOI：

  10.1021/jo00013a042
• 作为产物：
  描述：

  1-(苄氧基)甲基-5-甲酰基-4-碘咪唑 、 乙二醇 在 吡啶 、 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 6.0h， 以91%的产率得到1-Benzyloxymethyl-5-[1,3]dioxolan-2-yl-4-iodo-1H-imidazole
  参考文献：
  名称：

  Regioselective formation of imidazol-2-yllithium, imidazol-4-yllithium, and imidazol-5-yllithium species

  摘要：

  Representative imidazol-2-yllithium, imidazol-4-yllithium, and imidazol-5-yllithium species have been prepared via halogen-metal exchange, and the propensity of the latter two to undergo isomerization and quench by electrophilic reagents has been studied. The C2-unsubstituted imidazol-5-yllithium species 3 is generated within 10 min at -78-degrees-C from 1-[(benzyloxy)methyl]-4,5-diiodoimidazole (1b) and affords the C5-formyl product 4 upon reaction with DMF, but gives the isomeric C2-formyl product 6 if allowed to equilibrate to the imidazol-2-yllithium species 5 for an additional 35 min at -78-degrees-C before quench. The less reactive electrophile diethyl carbonate is unable to trap 3 and instead reacts with 5 to afford tris[1-[(benzyloxy)methyl]-4-iodo-2-imidazolyl]carbinol (7). In contrast, 1-[(benzyloxy)methyl]-4-iodoimidazole-5-carboxaldehyde ethylene acetal (10) metalates to give the C2-unsubstituted imidazol-4-yllithium species 13, which undergoes a very rapid conversion to its imidazol-2-yllithium isomer 14, even at -100-degrees-C, giving the 2,5-dicarboxaldehyde 5-ethylene acetal 16 or the 2-deuterio-5-carboxaldehyde ethylene acetal 15 upon quench with DMF or D2O, respectively. Thus, in the presence of C2 unsubstitution, C5 functionalization could be accomplished when the electrophile was sufficiently reactive, while C4 functionalization could not. Short- and long-range H-1-C-13 heteronuclear (Hector) 2D NMR spectroscopic analyses were instrumental in the structural assignments of key compounds.

  DOI：

  10.1021/jo00013a042

文献信息

• Polyfunctionalisation of imidazole via sequential imidazolyl anion formation
  作者：David S. Carver、Stephen D. Lindell、Elizabeth A. Saville-Stones

  DOI：10.1016/s0040-4020(97)00939-3

  日期：1997.10

  A method for achieving the sequential functionalisation of the imidazole ring in the order C-5-->C-4-->C-2 is described. The chemistry proceeds via the regioselective formation of positionally stable imidazolyl anions which are reacted with electrophiles (aldehydes, alkyl halides, azides, formamides, isocyanates) to afford substituted imidazoles in 31-90% yield. (C) 1997 Elsevier Science Ltd.
• GROZIAK, MICHAEL P.;WEI, LULIN, J. ORG. CHEM., 56,(1991) N3, C. 4296-4300
  作者：GROZIAK, MICHAEL P.、WEI, LULIN

  DOI：——

  日期：——

表征谱图