4,4,5-trimethyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione | 104216-83-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异苯并呋喃
• 英文名称: 4,4,5-trimethyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione
• 英文别名: (+/-)-3,3,4-trimethyl-cyclohex-4-ene-1r,2c-dicarboxylic acid-anhydride；(+/-)-3,3,4-Trimethyl-cyclohex-4-en-1r,2c-dicarbonsaeure-anhydrid；(3aR,7aR)-6,7,7-trimethyl-4,7a-dihydro-3aH-2-benzofuran-1,3-dione
• CAS: 104216-83-3
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: JPUKWHGZDAGGTJ-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  4,4,5-trimethyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione 在 sodium carbonate 作用下， 反应 2.0h， 以81%的产率得到(+/-)-(1R*,2R*)-3,3,4-trimethylcyclohex-4-ene-1,2-dicarboxylic acid
  参考文献：
  名称：

  New preparation of (3aR*,6S*,7aR*)-6,7,7-trimethylhexahydro-2-benzofuran-1(3H)-one: formal synthesis of (±)-γ-irone

  摘要：

  A four-step synthesis of (3aR*,6S*,7aR*)-6,7.7-trimethylhexahydro-2-benzofuran-1(3H)-one 2 has been developed. Lactone 2 is an intermediate in a synthesis of gamma -irone. Opening of the Diels-Alder adduct 5 with ethanol afforded hemiester 6b with 87:13 regioselectivity. Subsequent chemoselective reduction of the ester group in 6b yielded hydroxyacid 14 which was lactonized to the cis-fused bicyclic lactone 15. Finally, hydrogenation of 15 into 2 occured with complete diastereoselectivity. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)01059-0
• 作为产物：
  描述：

  3,4-二甲基-1-戊炔-3-醇 在 potassium hydrogensulfate 、 palladium on activated charcoal 、 Lindlar's catalyst 、 苯 作用下， 生成 4,4,5-trimethyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione
  参考文献：
  名称：

  Nasarow; Mawrow, Zhurnal Obshchei Khimii, 1959, vol. 29, p. 1158,1164; engl. Ausg. S. 1130, 1135

  摘要：

  DOI：

文献信息

• Goldman, Chemistry and industry, 1963, p. 1036
  作者：Goldman

  DOI：——

  日期：——
• Regioselective Synthesis and Diels−Alder Reaction of 3,4-Dimethylpenta-1,3-diene. Conformational Study of Bicyclic Adducts Structures by ¹H NMR (NOESY, ASIS) and Molecular Modeling (MM2, AM1, RHF, and DFT)
  作者：Pascal Gosselin、Christophe Bourdy、Stéphane Mille、Angélique Perrotin

  DOI：10.1021/jo991173d

  日期：1999.12.1

  A three-step, regioselective synthesis of 3,4-dimethylpenta-1,3-diene 1 has been developed. The condensation of acetone diethylacetal with ethyl propenyl ether yielded, after hydrolysis of the resulting triethoxy adduct 10, 2,3-dimethyl-2-butenal 7. Wittig reaction of 7 with methylenetriphenylphosphorane afforded desired diene 1 in 31% overall yield, easily scalable to the 10 g level, Diels-Alder reaction of 1 with maleic anhydride in benzene was known to afford a 50:50 mixture of "normal" (2) and "rearranged" (3) adducts. In THF as solvent, 2 has been reproducibly obtained in over 90% yield as a 98:2 mixture with 3. H-1 NMR spectroscopy (NOESY, ASIS) and molecular modeling (MM2, AM1, ab initio) have been used jointly to determine the conformation of 2 and 3, All are consistent with a folded structure of "rearranged" 3. On the other hand, only RHF/6-31G* and B3LYP/6-31G* ab initio models were in agreement with NMR spectroscopy for an extended conformation of adduct 2. In this case, neither MM2 nor AM1 models gave results consistent with NMR: discrepancies as high as 30 degrees were noted for some dihedrals between these models and ab initio ones.
• Stereochemistry Related to the Diels-Alder Adducts of 4-Methyl-1,3-pentadienes
  作者：Iwao Ichikizaki、Atsuaki Arai

  DOI：10.1246/bcsj.37.432

  日期：1964.3
• Nasarow; Mawrow, Zhurnal Obshchei Khimii, 1959, vol. 29, p. 1158,1164; engl. Ausg. S. 1130, 1135
  作者：Nasarow、Mawrow

  DOI：——

  日期：——
• New preparation of (3aR*,6S*,7aR*)-6,7,7-trimethylhexahydro-2-benzofuran-1(3H)-one: formal synthesis of (±)-γ-irone
  作者：Pascal Gosselin、Angélique Perrotin、Stéphane Mille

  DOI：10.1016/s0040-4020(00)01059-0

  日期：2001.1

  A four-step synthesis of (3aR*,6S*,7aR*)-6,7.7-trimethylhexahydro-2-benzofuran-1(3H)-one 2 has been developed. Lactone 2 is an intermediate in a synthesis of gamma -irone. Opening of the Diels-Alder adduct 5 with ethanol afforded hemiester 6b with 87:13 regioselectivity. Subsequent chemoselective reduction of the ester group in 6b yielded hydroxyacid 14 which was lactonized to the cis-fused bicyclic lactone 15. Finally, hydrogenation of 15 into 2 occured with complete diastereoselectivity. (C) 2001 Elsevier Science Ltd. All rights reserved.