cis-2,4-bis(1,1-dimethylpropyl)cycbutanone | 166325-50-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-2,4-bis(1,1-dimethylpropyl)cycbutanone
• 英文别名: (2S,4R)-2,4-bis(2-methylbutan-2-yl)cyclobutan-1-one
• CAS: 166325-50-4
• 化学式: C₁₄H₂₆O
• 分子量: 210.36
• InChiKey: BDUDNPPMLMDEOO-PHIMTYICSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-2,4-bis(1,1-dimethylpropyl)cycbutanone 在 溴 作用下， 以 四氯化碳 为溶剂， 反应 48.0h， 生成 cis-2,4-dibromo-2,4-bis(1,1-dimethylpropyl)cycbutanone
  参考文献：
  名称：

  Preparation and Structure Investigations of Simple Bicyclo[1.1.0]butanones

  摘要：

  Four 1,3-dialkyl-substituted bicyclo[1.1.0]butanones have been prepared, All have been completely characterized by H-1 and C-13 NMR spectroscopy, but O-17 NMR proved to be particularly diagnostic. The di-t-Bu 4 and di-tert-amyl 5 members can be obtained in the condensed phase by working quickly and at subambient temperatures, but attempts to obtain X-ray quality crystals have not been successful. The synthetic procedure involves a very rapid and efficient 1,3-elimination of two bromine atoms from 1,3-dibromocyclobutan-2-ones using the salt PPN+Cr(CO)(4)NO-. This reaction is particularly well-suited for exploratory in situ low-temperature MMR experiments, Molecular orbital calculations show these ketones to have the typical bent bicyclobutane structure, but the central C1-C3 bond is very long and the carbonyl carbon is distinctly nonplanar. Both of these features can be attributed to a strong interaction of the C1-C3 ''bond'' with the carbonyl group, and several qualitative orbital interaction schemes are presented to show that bicyclobutanones have on one hand some oxyallyl character and, on the other, some similarities with the bonding in esters. Nucleophiles react with bicyclobutanones in a nonconcerted process to add across the C1-C3 bond.

  DOI：

  10.1021/ja00121a009
• 作为产物：
  描述：

  di-2,4-(1-methylidene)cyclobutanone 、 乙基溴化镁 生成 cis-2,4-bis(1,1-dimethylpropyl)cycbutanone
  参考文献：
  名称：

  Preparation and Structure Investigations of Simple Bicyclo[1.1.0]butanones

  摘要：

  Four 1,3-dialkyl-substituted bicyclo[1.1.0]butanones have been prepared, All have been completely characterized by H-1 and C-13 NMR spectroscopy, but O-17 NMR proved to be particularly diagnostic. The di-t-Bu 4 and di-tert-amyl 5 members can be obtained in the condensed phase by working quickly and at subambient temperatures, but attempts to obtain X-ray quality crystals have not been successful. The synthetic procedure involves a very rapid and efficient 1,3-elimination of two bromine atoms from 1,3-dibromocyclobutan-2-ones using the salt PPN+Cr(CO)(4)NO-. This reaction is particularly well-suited for exploratory in situ low-temperature MMR experiments, Molecular orbital calculations show these ketones to have the typical bent bicyclobutane structure, but the central C1-C3 bond is very long and the carbonyl carbon is distinctly nonplanar. Both of these features can be attributed to a strong interaction of the C1-C3 ''bond'' with the carbonyl group, and several qualitative orbital interaction schemes are presented to show that bicyclobutanones have on one hand some oxyallyl character and, on the other, some similarities with the bonding in esters. Nucleophiles react with bicyclobutanones in a nonconcerted process to add across the C1-C3 bond.

  DOI：

  10.1021/ja00121a009

文献信息

• Preparation and Structure Investigations of Simple Bicyclo[1.1.0]butanones
  作者：A. Rauk、T. S. Sorensen、F. Sun

  DOI：10.1021/ja00121a009

  日期：1995.4

  Four 1,3-dialkyl-substituted bicyclo[1.1.0]butanones have been prepared, All have been completely characterized by H-1 and C-13 NMR spectroscopy, but O-17 NMR proved to be particularly diagnostic. The di-t-Bu 4 and di-tert-amyl 5 members can be obtained in the condensed phase by working quickly and at subambient temperatures, but attempts to obtain X-ray quality crystals have not been successful. The synthetic procedure involves a very rapid and efficient 1,3-elimination of two bromine atoms from 1,3-dibromocyclobutan-2-ones using the salt PPN+Cr(CO)(4)NO-. This reaction is particularly well-suited for exploratory in situ low-temperature MMR experiments, Molecular orbital calculations show these ketones to have the typical bent bicyclobutane structure, but the central C1-C3 bond is very long and the carbonyl carbon is distinctly nonplanar. Both of these features can be attributed to a strong interaction of the C1-C3 ''bond'' with the carbonyl group, and several qualitative orbital interaction schemes are presented to show that bicyclobutanones have on one hand some oxyallyl character and, on the other, some similarities with the bonding in esters. Nucleophiles react with bicyclobutanones in a nonconcerted process to add across the C1-C3 bond.