4a-methyl-3,4,5,6,8,8a-hexahydro-1H-naphthalene-2,7-dione | 13899-23-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4a-methyl-3,4,5,6,8,8a-hexahydro-1H-naphthalene-2,7-dione
• 英文别名: cis-6-methylbicyclo[4.4.0]decane-3,9-dione；cis-4a-Methyl-decalin-2,7-dione；cis-10-Methyldecahydronaphthalin-2,7-dion
• CAS: 13899-23-5
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: BYAJWGMJDDKYIF-DKTWLAJQSA-N

物化性质

• 沸点：
  295.9±23.0 °C(Predicted)
• 密度：
  1.084±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.11
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4a-methyl-3,4,5,6,8,8a-hexahydro-1H-naphthalene-2,7-dione 在 N-溴代丁二酰亚胺(NBS) 、 三乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 2.25h， 生成 cis-3,6(dieq)-Dibromo-4a-methyldecalin-2,7-dione
  参考文献：
  名称：

  Intramolecular Ring-Opening Of Cyclopropanones by Enolate Anions

  摘要：

  Treatment of cis-4a-methyldecalin-2,7-dione with 2 equiv of bromine gave cis-3,6(dieq)-dibromo-4a-methyldecalin-2,7-dione (9). Dehydrobromination of 9 with LiBr/Li2CO3 in DMF gave cis-6-methylbicyclo[4,4.0]deca-4,7-diene-3,9-dione (3). However, dehydrobromination of 9 with DBU in THF gave 1-bromo-5-methyltricyclo[4.4.0.0(1,7)]decane-2,8-dione (11). Bromination of cis-1-carbomethoxy-2-hydroxgy-4a-methylbicyclo[4.4.0]-1-decen-7-one (7), with cupric bromide in CHCl3/EtOAc provided cis-6(eq)-bromo-1-carbomethoxy-2-hydroxy-4a-methylbicyclo[4.4.0]-1-decen-7-one (13), whereas bromination of 7 with 2 equiv of bromine in CHCl3 provided cis-6(eq)-bromo-8(eq)-bromo-1-carbomethoxy-2-hydroxy-4a-methylbicyclo [4.4.0]-1-decen-7-one (14). Dehydrobromination of 13 with LiBr/Li2CO3 in DMF resulted in the loss of HBr with the formation of the methyl cis-3,4,4a,7,8,8a-hexahydro-2-hydroxy-4a-methyl-7-oxo-1-naphthoate (16) However, dehydrobromination of 13 with DBU in THF gave 16 (17%), 7-carbomethoxy-5-methyltricyclo[4.4.0.0(1,7)]decane-2,8-dione (17) (41%), and 2-carbomethoxy-1-hydroxy-8-methyltetracyclo[4.4.0.0(1,6).0(2,4)]decan-5-one (18) (40%). Dehydrobromination of the dibromo keto ester 14 gave only the tetracyclic ketol ester 20. Bromination of keto ester 7 with NBS and triethylamine gave the two epimers of methyl cis-3,4,4a,5,6,7,8,8a-octahydro-1-bromo-4a-methyl-2,7-dioxo-1(2H)-naphthoate (15) Dehydrobromination of 15a/b nith a variety of bases did not give the tricyclic diketo ester 22 but instead resulted in reductive debromination to regenerate starting material 7. The formation of 17 and 18 from 13 and of 20 from 14 are interpreted as occurring by novel intramolecular nucleophilic ring-openings of cyclopropanone-Favorskii intermediates by enolate anions.

  DOI：

  10.1021/jo00108a016
• 作为产物：
  描述：

  4-(3-butenyl)-4-methyl-2-cyclohexenone 生成 4a-methyl-3,4,5,6,8,8a-hexahydro-1H-naphthalene-2,7-dione
  参考文献：
  名称：

  Reductive cyclization of mercurial enones

  摘要：

  DOI：

  10.1021/jo00132a064

文献信息

• 由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体及其合成方法
  申请人：徐州博康信息化学品有限公司

  公开号：CN111763147A

  公开（公告）日：2020-10-13

  本发明公开了由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体及其合成方法，提供一种新的树脂单体，其结构式如下所示：其中R1为饱和烷烃或者环烷烃，R2为氢或者甲基，其合成方法为：在惰性气体保护下，(4as，8ar)‑4a‑甲基六氢化萘‑2,7(1H，3H)‑二酮(Ⅰ)与烷基格氏试剂或者环烷基格氏试剂反应得到中间体(Ⅱ)；在碱性条件下，中间体(Ⅱ)与丙烯酰氯或者甲基丙烯酰氯反应得到树脂单体(Ⅲ)。本发明提供的树脂单体与其它树脂单体聚合形成的聚合树脂具有更好的耐刻蚀性能，有利于改善显影后图形的边缘粗糙度，大大提高了光刻图案的分辨率。
• Aldol Condensation versus Conjugate Addition. Intramolecular Cyclization Using a Combination of Lewis Acid and 1,2-Diol.
  作者：Satoshi YAMADA、Hiroshi SUEMUNE

  DOI：10.1248/cpb.48.1171

  日期：——

  The reactivity of 3-substituted 4-methyl-4-(3-oxobutyl)-2-cyclohexen-1-ones (1) in the presence of a combination of a Lewis acid and a 1, 2-diol was studied. The results suggest several factors that influence 6-membered ring formation, including two types of intramolecular aldol reaction and intramolecular 1, 4-addition, due to the C3-substituent, Lewis acid, and the presence of diol. In this study, novel methodology to prepare two types of decalin skeleton could be developed.

  研究了在路易斯酸和1,2-二醇的组合存在下，3-取代的4-甲基-4-(3-氧基丁基)-2-环己烯-1-酮（1）的反应性。结果表明，影响六元环形成的几个因素，包括由于C3取代基、路易斯酸和二醇的存在而导致的两种类型的分子内醛醇反应和分子内1,4-加成。在本研究中，开发了制备两种类型去氢化萘骨架的新方法。
• Reactions of cyclohexadienes. Part VI. Further reactions of Diels–Alder adducts from 1-methoxycyclohexadienes
  作者：A. J. Birch、J. S. Hill

  DOI：10.1039/j39660002324

  日期：——

  Diels–Alder adducts of some 1-methoxycyclohexa-1,3-dienes and but-1-en-3-one, after formylation or acetylation, are rearranged by acid, and can be ultimately converted into derivatives of cis-decahydronaphthalene-2,7-dione.

  甲酰化或乙酰化后，某些1-甲氧基环己-1,3-二烯和1--1-烯基的Diels-Alder加合物被酸重排，最终可转化为顺式-十氢萘-2的衍生物， 7-dione。