spiro<2,3-dihydro-8-methoxy-4H-1-benzopyran-4,1'-cyclohexane>-2,4'-dione | 149171-92-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 3,4-二氢香豆素
• 英文名称: spiro<2,3-dihydro-8-methoxy-4H-1-benzopyran-4,1'-cyclohexane>-2,4'-dione
• 英文别名: 8-methoxyspiro[3H-chromene-4,4'-cyclohexane]-1',2-dione
• CAS: 149171-92-6
• 化学式: C₁₅H₁₆O₄
• 分子量: 260.29
• InChiKey: QXLGIOBGXIOWKZ-UHFFFAOYSA-N

物化性质

• 沸点：
  444.4±45.0 °C(predicted)
• 密度：
  1.26±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  spiro<2,3-dihydro-8-methoxy-4H-1-benzopyran-4,1'-cyclohexane>-2,4'-dione 在 (PhSeO)2 作用下， 以 甲苯 为溶剂， 反应 0.5h， 以76%的产率得到spiro[2,3-dihydro-8-methoxy-4H-1-benzopyran-4,1'-cyclohex-2'-ene]-2,4' dione
  参考文献：
  名称：

  Synthetic approaches toward spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexan]-2-one derivatives via radical reactions: total synthesis of (.+-.)-lycoramine

  摘要：

  Syntheses of spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexan]-2-one derivatives by reaction sequences including a radical reaction and a total synthesis of (+/-)-lycoramine (2) are described. Radical reactions (Bu3SnH,AIBN) of 1-[(1'-cyclohexenylmethyl)oxy]-2-halobenzenes 23b-d in boiling benzene gave the corresponding spiro[2,3-dihydrobenzofuran-3,1'-cyclohexanes] 26a,b in good yields, whereas the reaction of 1-(1'-cyclohexenylethoxy)-2-bromobenzene (25) under similar conditions afforded a mixture of spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane] 27 and benzoxepin 28. Furthermore, the radical reaction of ethyl 2-[(2'-bromoaryl)oxy]-1-cyclohexenylacetate 37a produced ethyl 2-spiro[2,3-dihydrobenzofuran-3,1'-cyclohexane]carboxylate 38 in good yield. Compound 38 was converted to spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane]-2,4'-dione 40 by treatment With SmI2 and then with 3 N HCl. Spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane]-2,4'-dione 40 was transformed to (+/-)-lycoramine (2) in four steps and 43% overall yield.

  DOI：

  10.1021/jo00067a019
• 作为产物：
  描述：

  ethyl α-(2'-bromo-6'-methoxyphenoxy)-α-(4,4-(ethylenedioxy)cyclohex-1-enyl)acetate 在 盐酸 、 六甲基磷酰三胺 、 三氢化钐 、 偶氮二异丁腈 、 1,2-二碘乙烷 、 三正丁基氢锡 作用下， 以 邻二甲苯 为溶剂， 反应 2.83h， 生成 spiro<2,3-dihydro-8-methoxy-4H-1-benzopyran-4,1'-cyclohexane>-2,4'-dione
  参考文献：
  名称：

  Synthetic approaches toward spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexan]-2-one derivatives via radical reactions: total synthesis of (.+-.)-lycoramine

  摘要：

  Syntheses of spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexan]-2-one derivatives by reaction sequences including a radical reaction and a total synthesis of (+/-)-lycoramine (2) are described. Radical reactions (Bu3SnH,AIBN) of 1-[(1'-cyclohexenylmethyl)oxy]-2-halobenzenes 23b-d in boiling benzene gave the corresponding spiro[2,3-dihydrobenzofuran-3,1'-cyclohexanes] 26a,b in good yields, whereas the reaction of 1-(1'-cyclohexenylethoxy)-2-bromobenzene (25) under similar conditions afforded a mixture of spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane] 27 and benzoxepin 28. Furthermore, the radical reaction of ethyl 2-[(2'-bromoaryl)oxy]-1-cyclohexenylacetate 37a produced ethyl 2-spiro[2,3-dihydrobenzofuran-3,1'-cyclohexane]carboxylate 38 in good yield. Compound 38 was converted to spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane]-2,4'-dione 40 by treatment With SmI2 and then with 3 N HCl. Spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane]-2,4'-dione 40 was transformed to (+/-)-lycoramine (2) in four steps and 43% overall yield.

  DOI：

  10.1021/jo00067a019

文献信息

• USRE41366E1
  申请人：——

  公开号：USRE41366E1

  公开（公告）日：2010-06-01
• Synthetic approaches toward spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexan]-2-one derivatives via radical reactions: total synthesis of (.+-.)-lycoramine
  作者：Miyuki Ishizaki、Kunihiko Ozaki、Akira Kanematsu、Takeshi Isoda、Osamu Hoshino

  DOI：10.1021/jo00067a019

  日期：1993.7

  Syntheses of spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexan]-2-one derivatives by reaction sequences including a radical reaction and a total synthesis of (+/-)-lycoramine (2) are described. Radical reactions (Bu3SnH,AIBN) of 1-[(1'-cyclohexenylmethyl)oxy]-2-halobenzenes 23b-d in boiling benzene gave the corresponding spiro[2,3-dihydrobenzofuran-3,1'-cyclohexanes] 26a,b in good yields, whereas the reaction of 1-(1'-cyclohexenylethoxy)-2-bromobenzene (25) under similar conditions afforded a mixture of spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane] 27 and benzoxepin 28. Furthermore, the radical reaction of ethyl 2-[(2'-bromoaryl)oxy]-1-cyclohexenylacetate 37a produced ethyl 2-spiro[2,3-dihydrobenzofuran-3,1'-cyclohexane]carboxylate 38 in good yield. Compound 38 was converted to spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane]-2,4'-dione 40 by treatment With SmI2 and then with 3 N HCl. Spiro[2,3-dihydro-4H-1-benzopyran-4,1'-cyclohexane]-2,4'-dione 40 was transformed to (+/-)-lycoramine (2) in four steps and 43% overall yield.