2,12-Dimethoxy-1β-hydroxy-2,12-picradiene-11,16-dione 16-ethylene acetal | 139276-57-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,12-Dimethoxy-1β-hydroxy-2,12-picradiene-11,16-dione 16-ethylene acetal
• 英文别名: (1'R,2'S,3'S,6'S,7'S,9'R,13'R,17'S)-3'-hydroxy-4',15'-dimethoxy-2',6',14',17'-tetramethylspiro[1,3-dioxolane-2,11'-10-oxatetracyclo[7.7.1.02,7.013,17]heptadeca-4,14-diene]-16'-one
• CAS: 139276-57-6
• 化学式: C₂₄H₃₄O₇
• 分子量: 434.53
• InChiKey: JXKPHIDDIXDPLE-BLFZPVLPSA-N

物化性质

• 沸点：
  577.1±50.0 °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)：
  1.8
• 重原子数：
  31
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,12-Dimethoxy-1β-hydroxy-2,12-picradiene-11,16-dione 16-ethylene acetal 在 草酰氯 、 二甲基亚砜 作用下， 以58%的产率得到2,12-Dimethoxy-2,12-picradiene-1,11,16-trione 16-(ethylene ketal)
  参考文献：
  名称：

  A partial synthesis of (-)-shinjulactone H from (+)-quassin

  摘要：

  A partial synthesis of (-)-shinjulactone H (3) from (+)-quassin (1) required the selective manipulation of two similar O-methyldiosphenol groups. Protection of the delta-lactone in 1 as an ortho ester, selective reduction of the C-1 carbonyl group, hydrolysis of the resulting enol ether in the A ring, and catalytic hydrogenation of the O-methyldiosphenol in the C ring delivered an intermediate possessing an alpha-ketol group in the A ring and an alpha-methoxy ketone group in the C ring. Demethylation and concomitant alpha-ketol tautomerization in the A ring delivered (-)-shinjulactone H (3).

  DOI：

  10.1021/jo00034a008
• 作为产物：
  描述：

  2,12-Dimethoxy-2,12-picradiene-1,11,16-trione 16-(ethylene ketal) 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 生成 2,12-Dimethoxy-1β-hydroxy-2,12-picradiene-11,16-dione 16-ethylene acetal
  参考文献：
  名称：

  A partial synthesis of (-)-shinjulactone H from (+)-quassin

  摘要：

  A partial synthesis of (-)-shinjulactone H (3) from (+)-quassin (1) required the selective manipulation of two similar O-methyldiosphenol groups. Protection of the delta-lactone in 1 as an ortho ester, selective reduction of the C-1 carbonyl group, hydrolysis of the resulting enol ether in the A ring, and catalytic hydrogenation of the O-methyldiosphenol in the C ring delivered an intermediate possessing an alpha-ketol group in the A ring and an alpha-methoxy ketone group in the C ring. Demethylation and concomitant alpha-ketol tautomerization in the A ring delivered (-)-shinjulactone H (3).

  DOI：

  10.1021/jo00034a008

文献信息

• Hydrolysis of 1,4,6-trioxaspiro[4.5]decanes to .delta.-lactones using 2,3-dichloro-5,6-dicyanobenzoquinone in aqueous acetone
  作者：Sundar Vasudevan、David S. Watt

  DOI：10.1021/jo00081a013

  日期：1994.1

  A selective hydrolysis of 1,4,6-trioxaspiro[4.5]decane orthoesters by 2,3-dichloro-5,6-dicyanoquinone (DDQ) in aqueous acetone in the presence of other acid-sensitive ketals is suggested to involve the formation of a charge-transfer complex followed by hydrolysis. A hydride-transfer mechanism for this oxidation was excluded.