3-iodo-6-methoxy-4-(4-methoxybenzylthio)-1H-2-benzothiopyran | 210626-08-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-iodo-6-methoxy-4-(4-methoxybenzylthio)-1H-2-benzothiopyran
• 英文别名: 3-iodo-6-methoxy-4-[(4-methoxyphenyl)methylsulfanyl]-1H-isothiochromene
• CAS: 210626-08-7
• 化学式: C₁₈H₁₇IO₂S₂
• 分子量: 456.368
• InChiKey: VHMKFSYURXCHDA-UHFFFAOYSA-N

物化性质

• 沸点：
  544.8±50.0 °C(Predicted)
• 密度：
  1.62±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  69.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-iodo-6-methoxy-4-(4-methoxybenzylthio)-1H-2-benzothiopyran 在 TrBF₄ 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以60%的产率得到1H-3-iodo-4-(4-methoxybenzylthio)-6-methoxybenzothiopyrylium tetrafluoroborate
  参考文献：
  名称：

  Versatile Route to Functionalized 1H-2-Benzothiopyrans and 1H-2-Naphthothiopyrans by Electrophilic Cyclization of Bis(arylmethylthio)acetylenes:  2-Benzo- and 2-Naphthothiopyrylium Salts

  摘要：

  Substituted 1H-2-benzothiopyrans find applications as pharmaceutically active compounds or synthons for more complex sulfur heterocycles. However, restricted variability in their synthesis limits the application for research or industrial purposes. To develop a direct and fast route to substituted and functionalized 1H-2-benzothiopyrans, we investigated the ring closure of symmetrical bis(arylmethylthio)acetylenes with iodine monochloride or bromine. This facile reaction yielded 1H-3-halo-4-arylmethylthio-2-benzo- and 2-naphthothiopyrans via postulated vinyl cations in yields of 47-86%. Substituted 2-benzo- and 2-naphthothiopyrylium salts were prepared by hydride abstraction with triphenylcarbenium tetrafluoroborate from the products, further enhancing the synthetic potential of the found cyclization reaction.

  DOI：

  10.1021/jo972334l
• 作为产物：
  描述：

  p-methoxybenzyl thiocyanate 在 氨 、 sodium 、 一氯化碘 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 0.67h， 生成 3-iodo-6-methoxy-4-(4-methoxybenzylthio)-1H-2-benzothiopyran
  参考文献：
  名称：

  Versatile Route to Functionalized 1H-2-Benzothiopyrans and 1H-2-Naphthothiopyrans by Electrophilic Cyclization of Bis(arylmethylthio)acetylenes:  2-Benzo- and 2-Naphthothiopyrylium Salts

  摘要：

  Substituted 1H-2-benzothiopyrans find applications as pharmaceutically active compounds or synthons for more complex sulfur heterocycles. However, restricted variability in their synthesis limits the application for research or industrial purposes. To develop a direct and fast route to substituted and functionalized 1H-2-benzothiopyrans, we investigated the ring closure of symmetrical bis(arylmethylthio)acetylenes with iodine monochloride or bromine. This facile reaction yielded 1H-3-halo-4-arylmethylthio-2-benzo- and 2-naphthothiopyrans via postulated vinyl cations in yields of 47-86%. Substituted 2-benzo- and 2-naphthothiopyrylium salts were prepared by hydride abstraction with triphenylcarbenium tetrafluoroborate from the products, further enhancing the synthetic potential of the found cyclization reaction.

  DOI：

  10.1021/jo972334l

文献信息

• Electrophilic Cyclisation of Bis(4-methoxybenzylthio)acetylene − Competition Between Ar2-6 and Ar1-5 Routes, Yielding 1H-2-Benzothiopyrans or Spiro Derivatives of Cyclohexadienone
  作者：Thomas R. Appel、Nasser A. M. Yehia、Ute Baumeister、Helmut Hartung、Ralph Kluge、Dieter Ströhl、Egon Fanghänel

  DOI：10.1002/1099-0690(200301)2003:1<47::aid-ejoc47>3.0.co;2-b

  日期：2003.1

  (Ar1-5 route). The fate of the ipso σ complex is determined by the presence or absence of nucleophiles in the reaction medium. When nucleophiles are excluded, the σ complex is stabilised by 1,2-migration and formation of 1H-2-benzothiopyran 2a. In the presence of water, the σ complex yields spirocyclohexadienone dihydrothiophenes 3a and 3d. In the presence of 3-methylbenzyl alcohol, the methoxy substituent

  在亲核试剂（如水或醇）存在或不存在的情况下，用一氯化碘处理双（4-甲氧基苄硫基）乙炔 (1) 会产生不同的产物。通常，双（苄硫基）乙炔的亲电环化通过原位形成的乙烯基阳离子（Ar2-6 环化）对芳环进行分子内邻位攻击，产生 1H-2-苯并噻喃 2。然而，在 1 的情况下，芳环 ipso 位置的高电子密度有利于 ipso 攻击（Ar1-5 路线）。ipso σ 复合物的命运取决于反应介质中亲核试剂的存在与否。当排除亲核试剂时，σ 复合物通过 1,2-迁移和 1H-2-苯并噻喃 2a 的形成而稳定。在水存在下，σ 复合物产生螺环己二烯酮二氢噻吩 3a 和 3d。在3-甲基苄醇存在下，2-苯并噻喃环的甲氧基取代基被产物2d中的3-甲基苄氧基交换。这些发现与 2a、2c、2d 和 2f 由 ipso - 而不是 ortho - 攻击对 4-甲氧基苯环的形成一致。使用 ICl 和质子诱导的环化都获得了类似的结果。在一锅法合成中，3a