3-benzoyloxymethyl-2-(2-butynoyl)-7-chloro-5,8-dimethoxy-1-(methoxymethoxy)naphthalene | 337975-28-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3-benzoyloxymethyl-2-(2-butynoyl)-7-chloro-5,8-dimethoxy-1-(methoxymethoxy)naphthalene
• 英文别名: [3-But-2-ynoyl-6-chloro-5,8-dimethoxy-4-(methoxymethoxy)naphthalen-2-yl]methyl benzoate
• CAS: 337975-28-7
• 化学式: C₂₆H₂₃ClO₇
• 分子量: 482.917
• InChiKey: FYLXCYNUSLASSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-benzoyloxymethyl-2-(2-butynoyl)-7-chloro-5,8-dimethoxy-1-(methoxymethoxy)naphthalene 在 盐酸 作用下， 以 四氢呋喃 、 异丙醇 为溶剂， 反应 24.0h， 以65%的产率得到5-benzoyloxymethyl-9-chloro-7,10-dimethoxy-2-methylnaphtho[1,2-b]pyran-4-one
  参考文献：
  名称：

  Synthesis of espicufolin based on 6-endo ring closure of o-alkynoylnaphthols †

  摘要：

  通过DBH或I2/N-甲基吗啉实现3-乙酰氧基甲基-7-氯-5,8-二甲氧基-1-萘酚5的区域选择性卤化，得到相应的2-卤代-1-萘酚8和11，将其转化为1-甲氧基甲氧基-3-(烷-2-炔酰氧基甲基)-2-卤代萘17和18的产率良好。在-78 °C 下，通过与 BuLi 进行卤素-锂交换引发的 2-卤代萘的分子内酰基转移反应以高产率生成 1-甲氧基甲氧基-2-炔酰基-3-(羟甲基)萘 21。将羟甲基保护为苯甲酸酯后，通过甲氧基甲基的脱保护，然后在弱酸性条件下自发的 6-内环闭合，很容易形成 γ-吡喃酮环。具有1-甲基丙基的吡喃酮衍生物被成功转化为espicufolin 1。

  DOI：

  10.1039/b007859j
• 作为产物：
  描述：

  But-2-ynoic acid 3-bromo-6-iodo-5,8-dimethoxy-4-methoxymethoxy-naphthalen-2-ylmethyl ester 在 吡啶 、 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 3-benzoyloxymethyl-2-(2-butynoyl)-7-chloro-5,8-dimethoxy-1-(methoxymethoxy)naphthalene
  参考文献：
  名称：

  A novel synthetic approach to benzo[h]chromones via sequential intramolecular alkynoyl transfer followed by 6-endo ring closure

  摘要：

  An intramolecular acyl transfer reaction took place on treatment of 1-methoxymethoxy-3-(2-alkynoyloxy)methyl-2-iodonaphthalenes with n-BuLi at -78 degrees C to give 1-methoxymethoxy-2-alkynoyl-3-hydroxymethylnaphthalenes in high yields. After protection of the hydroxymethyl group as benzoates, formation of a phi-pyrone ring was easily achieved by deprotection of the MOM group followed by spontaneous 6-endo-digonal ring closure under mild acidic conditions. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00037-x

文献信息

• Synthesis of espicufolin based on 6-endo ring closure of o-alkynoylnaphthols †
  作者：Hidemitsu Uno、Katsuji Sakamoto、Erina Honda、Kaori Fukuhara、Noboru Ono、Junya Tanaka、Masahiro Sakanaka

  DOI：10.1039/b007859j

  日期：——

  Regioselective halogenation of 3-acetoxymethyl-7-chloro-5,8-dimethoxy-1-naphthol 5 was achieved by DBH or I2/N-methylmorpholine to give the corresponding 2-halogeno-1-naphthols 8 and 11, which were converted to 1-methoxymethoxy-3-(alk-2-ynoyloxymethyl)-2-halogenonaphthalenes 17 and 18 in good yields. An intramolecular acyl-transfer reaction of the 2-halogenonaphthalenes triggered by halogen–lithium exchange with BuLi at −78 °C gave 1-methoxymethoxy-2-alkynoyl-3-(hydroxymethyl)naphthalenes 21 in high yields. After protection of the hydroxymethyl group as a benzoate, formation of a γ-pyrone ring was easily achieved by deprotection of the methoxymethyl group followed by spontaneous 6-endo ring closure under mildly acidic conditions. The pyrone derivative having a 1-methylpropyl group was successfully converted to espicufolin 1.

  通过DBH或I2/N-甲基吗啉实现3-乙酰氧基甲基-7-氯-5,8-二甲氧基-1-萘酚5的区域选择性卤化，得到相应的2-卤代-1-萘酚8和11，将其转化为1-甲氧基甲氧基-3-(烷-2-炔酰氧基甲基)-2-卤代萘17和18的产率良好。在-78 °C 下，通过与 BuLi 进行卤素-锂交换引发的 2-卤代萘的分子内酰基转移反应以高产率生成 1-甲氧基甲氧基-2-炔酰基-3-(羟甲基)萘 21。将羟甲基保护为苯甲酸酯后，通过甲氧基甲基的脱保护，然后在弱酸性条件下自发的 6-内环闭合，很容易形成 γ-吡喃酮环。具有1-甲基丙基的吡喃酮衍生物被成功转化为espicufolin 1。
• A novel synthetic approach to benzo[h]chromones via sequential intramolecular alkynoyl transfer followed by 6-endo ring closure
  作者：Katsuji Sakamoto、Erina Honda、Noboru Ono、Hidemitsu Uno

  DOI：10.1016/s0040-4039(00)00037-x

  日期：2000.3

  An intramolecular acyl transfer reaction took place on treatment of 1-methoxymethoxy-3-(2-alkynoyloxy)methyl-2-iodonaphthalenes with n-BuLi at -78 degrees C to give 1-methoxymethoxy-2-alkynoyl-3-hydroxymethylnaphthalenes in high yields. After protection of the hydroxymethyl group as benzoates, formation of a phi-pyrone ring was easily achieved by deprotection of the MOM group followed by spontaneous 6-endo-digonal ring closure under mild acidic conditions. (C) 2000 Elsevier Science Ltd. All rights reserved.