3,4-diacetyl-1,2,3,4-tetramethylcyclobutene | 55109-35-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-diacetyl-1,2,3,4-tetramethylcyclobutene
• 英文别名: cis-3,4-diacetyl-1,2,3,4-tetramethylcyclobutene；cis-3,4-diacetyl-1,2,3,4-tetramethyl-1-cyclobutene；3,4-cis-Diacetyl-1,2,3,4-tetramethyl-1-cyclobuten；1-[(1S,4R)-4-acetyl-1,2,3,4-tetramethylcyclobut-2-en-1-yl]ethanone
• CAS: 55109-35-8
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: FAPUCZQWUVCJSI-TXEJJXNPSA-N

物化性质

• 熔点：
  58 °C
• 沸点：
  259.3±40.0 °C(Predicted)
• 密度：
  0.973±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,4-diacetyl-1,2,3,4-tetramethylcyclobutene 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (1α,2α,6α,7α)1,2,4,4,6,7,8,9-octamethyl-3,5-dioxa-4-silabicyclo[5.2.0]-8-nonene
  参考文献：
  名称：

  Nucleophilic addition to 3,4-cis-diacetyl-1,2,3,4-tetramethyl-1-cyclobutene: remarkably fast intramolecular hemiketalization

  摘要：

  Reduction of 3,4-cis-diacetyl-1,2,3,4-tetramethyl-1-cyclobutene 1 with NaBH4 yielding 2-hydroxyoxoianes 2a and 2b with complete diastereoselectivity at the anomeric carbon atom suggests that a highly stereoselective intramolecular hemiketalizaiion process leading to the formation of the 2-hydroxyoxolane unit is much faster than the attack of the second molecule of the nucleophile on the second carbonyl group. Further reduction of 2a at 0 degreesC Lives selectively the meso-diol 3a. Reaction of 1 with MeLi or MeMgBr also involves the participation of the adjacent carbonyl. thereby yielding hydroxyoxolane 5a selectively. A mechanistic rationale is proposed oil the basis of the relative energies of all isomeric hemiketals, 2a-d and 5a and b, (calculated by the PM3 method) and the relative stabilities of the conformers of 1 (calculated by the MM2 method). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.12.037
• 作为产物：
  描述：

  1,2,3,4,5,6-HEXAMETHYLBICYCLO[2.2.0]HEXA-2,5-DIENE 在 potassium permanganate 作用下， 以 丙酮 为溶剂， 生成 3,4-diacetyl-1,2,3,4-tetramethylcyclobutene
  参考文献：
  名称：

  Criegee,R.; Rustaiyan,A., Chemische Berichte, 1975, vol. 108, p. 749 - 753

  摘要：

  DOI：

文献信息

• Polycyclic ozonides and peroxides derived from Hexamethyl(Dewar Benzene)
  作者：Kevin J McCullough、Shogo Tanaka、Koichi Teshima、Masatomo Nojima

  DOI：10.1016/s0040-4020(01)90489-2

  日期：——

  A stable, crystalline diozonide, derived from Hexamethyl(Dewar Benzene) 1, has been shown by X-ray crystallographic analysis to be the endo,endo-isomer 3c which had been predicted to be less stable than the endo,exo-isomer 3b. Acidolysis of the trans-ozonide 5 in CF3CO2H/CH2Cl2 gave a stable crystalline tricyclic peroxide 6 whereas the isomeric cis-ozonide 7 decomposed under similar conditions.

  X射线晶体学分析表明，衍生自六甲基（杜瓦市苯）1的稳定的结晶二唑酮是内消旋异构体3c，据预测它不如内消旋异构体3b稳定。所述的酸解反式-ozonide 5中CF 3 CO 2 H / CH 2氯2给了一个稳定的结晶三环过氧化物6而异构体顺式-ozonide 7相似的条件下分解。
• McCullough, Kevin J.; Sugimoto, Toshiya; Tanaka, Shogo, Journal of the Chemical Society. Perkin transactions I, 1994, # 6, p. 643 - 652
  作者：McCullough, Kevin J.、Sugimoto, Toshiya、Tanaka, Shogo、Kusabayashi, Shigekazu、Nojima, Masatomo

  DOI：——

  日期：——
• McCullough Kevin J., Tanaka Shogo, Teshima Kichi, Nojima Masatomo, Tetrahedron, 50 (1994) N 25, S 7625-7634
  作者：McCullough Kevin J., Tanaka Shogo, Teshima Kichi, Nojima Masatomo

  DOI：——

  日期：——
• CRIEGEE R.; RUSTAIYAN A., CHEM. BER. <CHBE-AM>, 1975, 108, NO 3, 749-753
  作者：CRIEGEE R.、 RUSTAIYAN A.

  DOI：——

  日期：——