dipivaloylketene | 133753-20-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dipivaloylketene
• CAS: 133753-20-5
• 化学式: C₁₂H₁₈O₃
• 分子量: 210.273
• InChiKey: SVCOVSNBNDICPN-UHFFFAOYSA-N

物化性质

• 沸点：
  296.7±40.0 °C(Predicted)
• 密度：
  0.970±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  dipivaloylketene 在 吡啶 作用下， 生成 6-tert-butyl-2-(dipivaloylmethylene)-5-pivaloyl-1,3-dioxin-4(2H)-one
  参考文献：
  名称：

  [2+4] Cycloaddition reactions of neat dipivaloylketene

  摘要：

  DOI：

  10.1007/bf00810021
• 作为产物：
  描述：

  5-tert-butyl-4-pivaloyl-2,3-dihydrofuran-2,3-dione 以100%的产率得到dipivaloylketene
  参考文献：
  名称：

  四叔丁基三氧杂双环[3.3.1]壬二烯二甲酸：光学分辨率、绝对构型及在手性鉴别中的应用

  摘要：

  对映体纯桥联双二恶英 4 是一种不对称的二元羧酸，具有轴向手性，可以很容易地合成并用作分离和/或传输手性客体分子的主体。外消旋体4与(R)-和(S)-1-苯乙胺产生相应的纯非对映体盐7和8。含有(R)-1-苯乙胺的非对映体盐7中二酸4的绝对构型被证实为R通过 X 射线晶体结构分析，这也证实了它的凹面性质。酸敏感性纯对映异构体 (R)-4 和 (S)-4 的释放可通过使用硅胶干式快速色谱法方便地实现。CD 光谱显示 (S)-对映异构体在 206 nm 处具有正 Cotton 效应。对映体纯度由具有 (R,R)-1 的非对映体盐的 1H NMR 鉴别证明，2-双(4-甲氧基苯基)乙烷-1,2-二胺为碱。二元羧酸 (R)-4 可用作手性助剂，如外消旋 N,N-二叔丁基-1,2-双(4-甲氧基苯基)乙烷-1,2-二胺 9 的难拆分所证明。 (© Wiley-VCH Verlag GmbH & Co

  DOI：

  10.1002/ejoc.200800109

文献信息

• Synthesis of functionalized macrocyclic derivatives of trioxabicyclo[3.3.0]nonadiene
  作者：Sabine Leber、Gert Kollenz、Curt Wentrup

  DOI：10.3762/bjoc.8.83

  日期：——

  C₇₂-Macrocyclic systems functionalized with nitroaryl and arylamino groups were synthesized from the bisdioxine diacid dichloride 1,3,5,7-tetra-tert-butyl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4,8-dicarbonyl dichloride (3).

  从1,3,5,7-四-tert-丁基-2,6,9-三氧杂双环[3.3.1]非-3,7-二烯-4,8-二羧酸二氯化物（3）合成了功能化有硝基芳基和芳基氨基基团的C₇₂大环系统。
• Preparation and Chemistry of an Unexpectedly Stable α-Oxoketene−Pyridine Zwitterion, 2,2-Bis(tert-butylcarbonyl)-1-[4-(dimethylamino)pyridinio]ethen-1-olate
  作者：Gert Kollenz、Susanne Holzer、C. Oliver Kappe、Turkaram S. Dalvi、Walter M. F. Fabian、Heinz Sterk、Ming Wah Wong、Curt Wentrup

  DOI：10.1002/1099-0690(200104)2001:7<1315::aid-ejoc1315>3.0.co;2-2

  日期：2001.4

  demonstrate that the ring nitrogen atom of DMAP is involved in generating the new zwitterionic C-N bond. Reactions of 4 with NH and OH nucleophiles in solution afforded the corresponding dipivaloyl acetic acid derivatives 6 and 7, whereas acetone or benzylidene aniline undergo cycloaddition reactions of the hetero-Diels-Alder type.

  在乙腈中用 4-(二甲氨基)吡啶 (DMAP) 处理二戊酰基乙烯酮 1 及其二聚体 2 和 3 得到 α-氧代烯酮-吡啶两性离子 4，为淡黄色固体。这是从真正的 alpha-oxoketene 获得的稳定两性离子的第一个例子。在室温下的无水溶液中，化合物 4 大部分裂解为反应物 1 和 DMAP。在 -60 摄氏度，平衡完全向两性离子 4 移动，如 C-13 NMR 测量所示。使用密度泛函理论 (B3LYP/6-311+G**) 的计算与 4 的形成和相对稳定性非常吻合。 N-15 标记实验表明 DMAP 的环氮原子参与生成新的两性离子 CN键。
• Dipivaloylketene and its dimers. [2+4] Versus [2+2] cycloaddition reactions of .alpha.-oxo ketenes
  作者：C. Oliver Kappe、Gerald Faerber、Curt Wentrup、Gert Kollenz

  DOI：10.1021/jo00052a018

  日期：1992.12

  Dipivaloylketene (8) is generated by preparative flash vacuum pyrolysis of furandione 6. While dimerization of 8 in apolar and several polar solvents leads to the previously reported [2 + 4] dimer 7, dimerization in the presence of DMSO, tributylphosphine oxide, or pyridine instead surprisingly occurs across the C=O bond of the ketene function, affording dioxinone 9. This is a novel type of alpha-oxo ketene dimerization. The reversibility of both dimerizations and mechanistic pathways for the formation of 9 are discussed. Cycloaddition reactions of 8 with heterocumulenes 10a,b and 12a-c yield [2 + 4] cycloadducts 11a,b and 13a-c, respectively. Oxazinones 13a-c can add a second molecule of 8 to generate novel spiro heterocycles 14a-c. In contrast, oxo ketene 7 reacts with carbodiimides 12a,b, to furnish [2 + 2] adducts 15a,b. This is the first unequivocal example of a direct [2 + 2] cycloaddition reaction of an alpha-oxo ketene. The unexpected formation of these compounds was confirmed by X-ray crystallography (15a). General aspects of [2 + 2] versus [2 + 4] cycloaddition in alpha-oxo ketenes are discussed.
• Reactions of dipivaloylketene dimer with nucleophiles: new access to the 2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene ring system (bridged bis-dioxines)
  作者：C. Oliver Kappe、Gert Kollenz、Walter M. F. Fabian、Curt Wentrup、Gerald Faerber

  DOI：10.1021/jo00064a024

  日期：1993.6

  Novel and convenient methods to prepare several functionalized 2,6,9-trioxabicyclo[3.3.1]nonadienes (''bridged bis-dioxines'') 6, 10, 11, and 12 are described. In general, these are obtained by addition of nucleophiles to alpha-oxoketene 5 in a multistep reaction sequence, where the specific reaction pathway depends strongly on the type of nucleophile employed: Aromatic amines with electron-donating substituents afford the trioxabicyclononadienes 6, while with aliphatic amines or thiolates, 2 equiv of the corresponding dipivaloylacetamides 13 or thioesters 14, respectively, are formed. In the case of OH nucleophiles, the primary 1:1 adducts 8 are isolable, characterized by an X-ray analysis of 8a. Under acidic conditions, 8 can be cyclized to the bifunctionalized bis-dioxines 10. The bis-carboxylic acid 10c serves as a valuable intermediate to synthesize other derivatives, e.g. the bis-acid chloride 11 and the bis-ester 12. Mechanistic pathways leading to the various reaction products are discussed in detail and supported by semiempirical molecular orbital calculations using the AM1 method. The spontaneous formation of the bis-dioxine skeleton in the reaction 5 --> 6 is likely to proceed via an unusual [4 + 4] type tandem cyclization reaction.
• Kappe, C. Oliver; Evans, Richard A.; Kennard, Colin H. L., Journal of the American Chemical Society, 1991, vol. 113, # 11, p. 4234 - 4237
  作者：Kappe, C. Oliver、Evans, Richard A.、Kennard, Colin H. L.、Wentrup, Curt

  DOI：——

  日期：——