4-Hydroxy-2-methyl-3a,4,9,9a-tetrahydro-4,9<1',2'>benzeno-1H-benzisoindole-1,3(2H)-dione | 118494-66-9

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: 4-Hydroxy-2-methyl-3a,4,9,9a-tetrahydro-4,9<1',2'>benzeno-1H-benzisoindole-1,3(2H)-dione
• 英文别名: 4-Hydroxy-2-methyl-3a,4,9,9a-tetrahydro-4,9[1',2']benzeno-1H-benz[f]isoindole-1,3(2H)-dione；1-Hydroxy-17-methyl-17-azapentacyclo[6.6.5.02,7.09,14.015,19]nonadeca-2,4,6,9,11,13-hexaene-16,18-dione
• CAS: 118494-66-9
• 化学式: C₁₉H₁₅NO₃
• 分子量: 305.333
• InChiKey: JYJCOMSKUPTVBL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  57.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-Hydroxy-2-methyl-3a,4,9,9a-tetrahydro-4,9<1',2'>benzeno-1H-benzisoindole-1,3(2H)-dione 以 乙醇 为溶剂， 生成 10-(1-Methyl-2,5-dioxopyrrolidin-3-yl)-9(10H)anthracenone
  参考文献：
  名称：

  手性碱催化的不对称Diels-Alder反应

  摘要：

  已经发现在催化量的各种手性β-氨基醇的存在下，蒽酮与N-甲基马来酰亚胺反应。以优异的产率获得了光学活性的环加合物3a。已经研究了反应的几个特征。

  DOI：

  10.1016/s0040-4039(00)70709-x
• 作为产物：
  描述：

  蒽酮 在 palladium on activated charcoal 氢气 作用下， 以 吡啶 为溶剂， 生成 4-Hydroxy-2-methyl-3a,4,9,9a-tetrahydro-4,9<1',2'>benzeno-1H-benzisoindole-1,3(2H)-dione
  参考文献：
  名称：

  Anthracenediols as reactive dienes in base-catalyzed cycloadditions: reduction-cycloaddition reactions of anthraquinones

  摘要：

  Anthraquinone is readily reduced to the hydroquinone (9,10-anthracenediol), which under basic conditions serves as a reactive diene for cyloaddition purposes. Catalytic hydrogenation in pyridine solvent provides convenient access to this species, and efficient reactions occur with dienophiles in situ, provided that they are sufficiently reactive. Thus N-methylmaleimide (NMM) gives the bicyclic bridgehead diol in near quantitative yield when the H2/Pd reduction of anthraquinone is carried out in pyridine containing 1 equiv of NMM. Fumaronitrile and maleonitrile similarly give high yields in stereospecific reactions, with the dienophile geometry retained in the cycloadduct. Less reactive dienophiles suffer competitive reduction. Dimethyl fumarate in situ gives cycloadduct (stereospecifically) in only 35-60% yield, with the remainder of the dienophile reduced to dimethyl succinate. Stepwise reduction followed by addition of dienophile leads to a higher yield in this and related reactions. The benzologues 5,12-naphthacenedione and 6,13-pentacenedione undergo analogous reactions with NMM, leading to novel bridgehead diols. The monimine of anthraquinone exhibits NMR features attributed to syn/anti isomerism. Under neutral or mildly basic conditions, the aromatic protons on the ring proximal to the NH are clearly distinguished (500 MHz) from those on the distal ring. The addition of acid causes rapid syn/anti NH exchange leading to time averaged symmetry. This imine behaves similarly to anthraquinone in the reduction/cycloaddition sequence. For example, with NMM in situ an essentially quantitative yield of the novel bridgehead amino alcohol adduct is obtained. Related benzologue reactions and attempts to extend the sequence to the oxime and methylene analogues of anthraquinone are described. Base-catalyzed ring opening of the cycloadduct of NMM/anthracenediol leads to a novel retro-bis-aldol reaction, resulting in the formation of anthraquinone and N-methylsuccinimide.

  DOI：

  10.1021/jo00004a009

文献信息

• Asymmetric base-catalyzed cycloaddition between anthrone and some dienophiles
  作者：Olivier Riant、Henri B. Kagan、Louis Ricard

  DOI：10.1016/s0040-4020(01)89385-6

  日期：1994.4

  presence of catalytic amounts of various chiral β-aminoalcohols. The cycloadduct 3a has been obtained in excellent yield with enantiomeric excess of up to 61%. Its absolute configuration has been assigned by X-ray crystallography. Several features of the reaction have been studied: variation of dienophile; competition between cycloaddition and formation of the optically active Michael adduct 4; solvent

  已经发现在催化量的各种手性β-氨基醇的存在下，蒽酮与N-甲基马来酰亚胺反应。已经以优异的产率获得了环加合物3a，对映体过量高达61％。其绝对构型已通过X射线晶体学确定。已经研究了反应的几个特征：亲双烯体的变化；环加成与旋光迈克尔加合物的形成之间的竞争4 ; 溶剂和温度的影响。机理研究与一致的[4 + 2]过程一致，提供了碱催化的不对称Diels-Alder反应的独特情况。
• Base-catalyzed reactions of anthrones with dienophiles
  作者：Michael Koerner、Bruce Rickborn

  DOI：10.1021/jo00296a024

  日期：1990.4
• Anthrones as reactive dienes in Diels-Alder reactions
  作者：Michael Koerner、Bruce Rickborn

  DOI：10.1021/jo00262a003

  日期：1989.1
• RIANT, OLIVIER;KAGAN, HENRI B., TETRAHEDRON LETT., 30,(1989) N2, C. 7403-7406
  作者：RIANT, OLIVIER、KAGAN, HENRI B.

  DOI：——

  日期：——
• KOERNER, MICHAEL;RICKBORN, BRUCE, J. ORG. CHEM., 55,(1990) N, C. 2662-2672
  作者：KOERNER, MICHAEL、RICKBORN, BRUCE

  DOI：——

  日期：——

表征谱图