3-Formyloxy-2-methyl-1-cyclohexen-1-carboxaldehyde | 194937-80-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-Formyloxy-2-methyl-1-cyclohexen-1-carboxaldehyde
• 英文别名: (3-Formyl-2-methylcyclohex-2-en-1-yl) formate
• CAS: 194937-80-9
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: JQNNPRAPRIMZPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-Formyloxy-2-methyl-1-cyclohexen-1-carboxaldehyde 在 potassium carbonate 、 L-脯氨酸 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 生成 (5aS,6R)-6-hydroxy-3,5a-dimethyl-6,7,8,9-tetrahydropyrano[4,3-b]chromen-1-one
  参考文献：
  名称：

  A One-Pot Condensation of Pyrones and Enals. Synthesis of 1H,7H-5a,6,8,9-Tetrahydro-1-oxopyrano[4,3-b][1]benzopyrans

  摘要：

  Condensation of various 6-substituted 4-hydroxypyrones 1 with 1-cyclohexenecarboxaldehydes in the presence of L-proline in ethyl acetate gave high yields of substituted 1H,7H-5a,6,8,9-tetrahydro-1-oxopyrano[4,3-b][1]benzopyrans. The reaction presumably occurs via the 1,2-addition of the pyrone with the aldehyde followed by dehydration and then cyclization through a 6 Pi electrocyclic process. A remarkable asymmetric induction was obtained from a stereogenic center (C4) of the cyclohexenecarboxaldehyde [such as (S)-perillaldehyde] to provide only the C5a,7-trans tricyclic pyrone products. On the other hand, condensation of S-(formyloxy)- or 3-hydroxy-2-methyl-1-cyclohexene-carboxaldehydes with pyrones 1 gave mixtures of C5a,6-cis and -trans products. Several of the tricyclic pyrones strongly inhibit acetylcholinesterase activity, DNA synthesis, and tumor cell growth in vitro.

  DOI：

  10.1021/jo970642d
• 作为产物：
  描述：

  [3-(1,3-Dithian-2-yl)-2-methylcyclohex-2-en-1-yl] formate 在 N-氯代丁二酰亚胺 、 silver nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.5h， 以59%的产率得到3-Formyloxy-2-methyl-1-cyclohexen-1-carboxaldehyde
  参考文献：
  名称：

  A One-Pot Condensation of Pyrones and Enals. Synthesis of 1H,7H-5a,6,8,9-Tetrahydro-1-oxopyrano[4,3-b][1]benzopyrans

  摘要：

  Condensation of various 6-substituted 4-hydroxypyrones 1 with 1-cyclohexenecarboxaldehydes in the presence of L-proline in ethyl acetate gave high yields of substituted 1H,7H-5a,6,8,9-tetrahydro-1-oxopyrano[4,3-b][1]benzopyrans. The reaction presumably occurs via the 1,2-addition of the pyrone with the aldehyde followed by dehydration and then cyclization through a 6 Pi electrocyclic process. A remarkable asymmetric induction was obtained from a stereogenic center (C4) of the cyclohexenecarboxaldehyde [such as (S)-perillaldehyde] to provide only the C5a,7-trans tricyclic pyrone products. On the other hand, condensation of S-(formyloxy)- or 3-hydroxy-2-methyl-1-cyclohexene-carboxaldehydes with pyrones 1 gave mixtures of C5a,6-cis and -trans products. Several of the tricyclic pyrones strongly inhibit acetylcholinesterase activity, DNA synthesis, and tumor cell growth in vitro.

  DOI：

  10.1021/jo970642d

文献信息

• <i>cis</i>-3,5a-Dimethyl-1-oxo-5a,6,8,9-tetrahydro-1<i>H</i>,7<i>H</i>-pyrano[4,3-<i>b</i>][1]benzopyran-6-yl Formate
  作者：P. D. Robinson、D. H. Hua、Y. Chen、C. Y. Meyers

  DOI：10.1107/s0108270197008603

  日期：1997.11.15

  Characterization of the title compound, C15H16O5, by X-ray diffraction affirms its linearly fused tricyclic structure and the chair conformation of the cyclohexane ring on which the methyl and adjacent formyloxy groups are cis, the former being axial and the latter equatorial. The C=C bond gamma,delta to the carbonyl is longer, while the C=C bond alpha,beta to the carbonyl is shorter than their counterparts in a 3-substituted 4-hydroxy-6-methyl-2-pyrone.
• US5958970A
  申请人：——

  公开号：US5958970A

  公开（公告）日：1999-09-28
• US6384045B1
  申请人：——

  公开号：US6384045B1

  公开（公告）日：2002-05-07
• [EN] TRICYCLIC AND TETRACYCLIC PYRONES<br/>[FR] PYRONES TRICYCLIQUES ET TETRACYCLIQUES
  申请人：KANSAS STATE UNIVERSITY RESEARCH FOUNDATION

  公开号：WO1998039010A1

  公开（公告）日：1998-09-11

  (EN) This invention provides cancer-active tricyclic and tetracyclic oxypyrones and a method of synthesizing these compounds. Preferred compounds have aryl groups at the 3-position of the oxypyrone ring. The tricyclic oxypyrone synthetic method is a simple condensation reaction of pyrones with cyclohexenecarboxaldehydes, providing high yields and using few steps. The tetracyclic oxypyrone synthetic method is a simple condensation reaction of carvones with pyrones.(FR) La présente invention concerne des oxypyrones tricycliques et tétracycliques actifs contre le cancer, ainsi qu'une méthode de synthétisation de ces composés. De préférence, les composés comprennent des groupes aryle à la position 3 du noyau d'oxypyrone. La méthode de synthétisation d'oxypyrone tricyclique consiste en une simple réaction de condensation de pyrones avec des cyclohexènecarboxaldéhydes, produisant des rendements élevés et nécessitant peu d'opérations. La méthode de synthétisation d'oxypyrone tétracyclique consiste en une simple réaction de condensation de carvones avec des pyrones.
• A One-Pot Condensation of Pyrones and Enals. Synthesis of 1<i>H</i>,7<i>H</i>-5a,6,8,9-Tetrahydro-1-oxopyrano[4,3-<i>b</i>][1]benzopyrans
  作者：Duy H. Hua、Yi Chen、Hong-Sig Sin、Maria J. Maroto、Paul D. Robinson、Steven W. Newell、Elisabeth M. Perchellet、James B. Ladesich、Jonathan A. Freeman、Jean-Pierre Perchellet、Peter K. Chiang

  DOI：10.1021/jo970642d

  日期：1997.10.1

  Condensation of various 6-substituted 4-hydroxypyrones 1 with 1-cyclohexenecarboxaldehydes in the presence of L-proline in ethyl acetate gave high yields of substituted 1H,7H-5a,6,8,9-tetrahydro-1-oxopyrano[4,3-b][1]benzopyrans. The reaction presumably occurs via the 1,2-addition of the pyrone with the aldehyde followed by dehydration and then cyclization through a 6 Pi electrocyclic process. A remarkable asymmetric induction was obtained from a stereogenic center (C4) of the cyclohexenecarboxaldehyde [such as (S)-perillaldehyde] to provide only the C5a,7-trans tricyclic pyrone products. On the other hand, condensation of S-(formyloxy)- or 3-hydroxy-2-methyl-1-cyclohexene-carboxaldehydes with pyrones 1 gave mixtures of C5a,6-cis and -trans products. Several of the tricyclic pyrones strongly inhibit acetylcholinesterase activity, DNA synthesis, and tumor cell growth in vitro.