1,3-dihydro-3,3-dimethoxy-6,11-dimethylheptaleno[1,2-c]furan-1-one | 312603-07-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 原羧酸衍生物
• 英文名称: 1,3-dihydro-3,3-dimethoxy-6,11-dimethylheptaleno[1,2-c]furan-1-one
• 英文别名: 5,5-Dimethoxy-9,15-dimethyl-4-oxatricyclo[8.5.0.02,6]pentadeca-1(15),2(6),7,9,11,13-hexaen-3-one；5,5-dimethoxy-9,15-dimethyl-4-oxatricyclo[8.5.0.02,6]pentadeca-1(15),2(6),7,9,11,13-hexaen-3-one
• CAS: 312603-07-9
• 化学式: C₁₈H₁₈O₄
• 分子量: 298.339
• InChiKey: CTCHIIZGUCWTKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (benzenesulfonyl)methyllithium 、 1,3-dihydro-3,3-dimethoxy-6,11-dimethylheptaleno[1,2-c]furan-1-one 在 正丁基锂 作用下， 反应 5.0h， 以21%的产率得到7,12-dimethyl-3-(phenylsulfonyl)benzo[a]heptalene-2,4-diol
  参考文献：
  名称：

  秋水仙素的可变合成研究：在庚烯部分构建环 A

  摘要：

  It is shown that heptalene-4,5-dicarboxylates 2, which react with lithiated methyl sulfones mainly in a Michael fashion at C(3) (cf. Scheme-2), so that the formation of 3-sulfonylbenzo[a]heptalene-2,4-diols 5 is repressed or completely suppressed, can be transformed into corresponding pseudo-esters 15 (Scheme 4). These pseudo-esters, on treatment with lithiated methyl sulfones, followed by addition of BuLi, furnish the 3-sulfonylbenzo[a]heptalene-2,4-diols 5 in excellent-to-moderate yields without formation of Michael adducts or their follow-up products (cf. Scheme 5 and 6). The reaction of the pseudo-ester 15a with Li[C-13]H2SO2Ph, followed by treatment with non-labeled FiCH(2)SO(2)Ph and then BuLi, led to the exclusive formation of 3-(phenylsulfonyl)-[1-C-13]benzo[a]heptalene-2,4-diol 5a* (Scheme 9). This experiment demonstrates that the (phenylsulfonyl)acetyl groups at C(4) and C(5) of the heptalene core retain their individual positions in the course of the benzo[a]heptalene-2,4-diol formation. These findings are only compatible with an intramolecular rearrangement mechanism as depicted in Scheme 10.

  DOI：

  10.1002/1522-2675(20000906)83:9<2383::aid-hlca2383>3.0.co;2-0
• 作为产物：
  描述：

  dimethyl 1,6-dimethylheptalene-4,5-dicarboxylate 在 氢氧化钾 作用下， 以 甲醇 、 乙醇 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 14.0h， 生成 1,3-dihydro-3,3-dimethoxy-6,11-dimethylheptaleno[1,2-c]furan-1-one
  参考文献：
  名称：

  秋水仙素的可变合成研究：在庚烯部分构建环 A

  摘要：

  It is shown that heptalene-4,5-dicarboxylates 2, which react with lithiated methyl sulfones mainly in a Michael fashion at C(3) (cf. Scheme-2), so that the formation of 3-sulfonylbenzo[a]heptalene-2,4-diols 5 is repressed or completely suppressed, can be transformed into corresponding pseudo-esters 15 (Scheme 4). These pseudo-esters, on treatment with lithiated methyl sulfones, followed by addition of BuLi, furnish the 3-sulfonylbenzo[a]heptalene-2,4-diols 5 in excellent-to-moderate yields without formation of Michael adducts or their follow-up products (cf. Scheme 5 and 6). The reaction of the pseudo-ester 15a with Li[C-13]H2SO2Ph, followed by treatment with non-labeled FiCH(2)SO(2)Ph and then BuLi, led to the exclusive formation of 3-(phenylsulfonyl)-[1-C-13]benzo[a]heptalene-2,4-diol 5a* (Scheme 9). This experiment demonstrates that the (phenylsulfonyl)acetyl groups at C(4) and C(5) of the heptalene core retain their individual positions in the course of the benzo[a]heptalene-2,4-diol formation. These findings are only compatible with an intramolecular rearrangement mechanism as depicted in Scheme 10.

  DOI：

  10.1002/1522-2675(20000906)83:9<2383::aid-hlca2383>3.0.co;2-0

文献信息

• Studies for a Variable Synthesis of Colchicinoids: Construction of Ring A on a Heptalene Moiety
  作者：Markus Meyer、Khaled Abou-Hadeed、Hans-Jürgen Hansen

  DOI：10.1002/1522-2675(20000906)83:9<2383::aid-hlca2383>3.0.co;2-0

  日期：2000.9.6

  It is shown that heptalene-4,5-dicarboxylates 2, which react with lithiated methyl sulfones mainly in a Michael fashion at C(3) (cf. Scheme-2), so that the formation of 3-sulfonylbenzo[a]heptalene-2,4-diols 5 is repressed or completely suppressed, can be transformed into corresponding pseudo-esters 15 (Scheme 4). These pseudo-esters, on treatment with lithiated methyl sulfones, followed by addition of BuLi, furnish the 3-sulfonylbenzo[a]heptalene-2,4-diols 5 in excellent-to-moderate yields without formation of Michael adducts or their follow-up products (cf. Scheme 5 and 6). The reaction of the pseudo-ester 15a with Li[C-13]H2SO2Ph, followed by treatment with non-labeled FiCH(2)SO(2)Ph and then BuLi, led to the exclusive formation of 3-(phenylsulfonyl)-[1-C-13]benzo[a]heptalene-2,4-diol 5a* (Scheme 9). This experiment demonstrates that the (phenylsulfonyl)acetyl groups at C(4) and C(5) of the heptalene core retain their individual positions in the course of the benzo[a]heptalene-2,4-diol formation. These findings are only compatible with an intramolecular rearrangement mechanism as depicted in Scheme 10.