5-tert-butyl-4-pivaloyl-2,3-dihydrofuran-2,3-dione | 128751-99-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: 5-tert-butyl-4-pivaloyl-2,3-dihydrofuran-2,3-dione
• 英文别名: 5-tert-Butyl-4-(2,2-dimethylpropanoyl)furan-2,3-dione
• CAS: 128751-99-5
• 化学式: C₁₃H₁₈O₄
• 分子量: 238.284
• InChiKey: RSIGNNHNCYZNJN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-tert-butyl-4-pivaloyl-2,3-dihydrofuran-2,3-dione 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：

  卡宾和酮烯在低温基质中的反应性。卡宾 CO 捕获、沃尔夫重排和乙烯酮-吡啶叶立德（两性离子）观察

  摘要：

  二碳烷氧基乙烯酮 8a 和 8b 是通过重氮酯 7 在低温基质中的光解或通过 7 的 FVT 随后进行基质分离获得的。在低至 6.5 K 的温度下，Ar 基质中重氮丙二酸酯 1 的光化学沃尔夫重排产生烷氧基（烷氧基羰基）烯酮 3，也可通过 FVT 为 1 获得。CO 基质中 1 在大于或等于 6.5 K 时的光解产生二烷氧基烯酮 8 . 烯酮 3、8 和 12 在 40 K 以上与吡啶反应，分别生成烯酮-吡啶叶立德（两性离子）9、10 和 13。

  DOI：

  10.1021/ja962672o
• 作为产物：
  描述：

  bis[5-tert-butyl-5-chloro-4-(2,2-dimethylpropanoyl)-2-oxofuran-3-yl] oxalate 80.0~90.0 ℃ 、1.33 kPa 条件下， 反应 24.0h， 以95%的产率得到5-tert-butyl-4-pivaloyl-2,3-dihydrofuran-2,3-dione
  参考文献：
  名称：

  On the Reaction of 2,2,6,6-Tetramethyl-3,5-heptanedione ("Dipivaloylmethane") with Oxalyl Chloride

  摘要：

  Refluxing of dipivaloylmethane (1) in an excess of oxalyl chloride gives a mixture containing the 5-chloro-furanone derivatives (2), (3), and (4), which then can be completely converted into the 5-tert-butyl-4-pivaloylfuran-2,3-dione (5). Compounds (2-5) are hydrolyzed to the carboxylic acid (6), which in reverse is easily recyclized to 5.

  DOI：

  10.3987/com-91-5679

文献信息

• Synthesis and chemical reactivity of methoxycarbonyl-1,3-dioxinyl(pivaloyl)ketene—a persistent α-oxoketene
  作者：Bianca C. Wallfisch、Ferdinand Belaj、Curt Wentrup、C. Oliver Kappe、Gert Kollenz

  DOI：10.1039/b111143d

  日期：2002.2.22

  Flash vacuum pyrolysis of an equimolar mixture of 4-pivaloyl- and 4-methoxycarbonyl-5-tert-butylfuran-2,3-dione affords the new and remarkably stable α-oxoketene 6 as the result of an unusual dimerization of the primarily formed monomeric α-oxoketenes 1 and 3, respectively. [2 + 2] Cycloaddition reactions of 6 and dialkylcarbodiimides furnish functionalized imino-β-lactams 7, while reaction with nucleophiles

  闪蒸真空热解 4-新戊酰和 4-甲氧羰基-5-叔丁基呋喃-2,3-二酮由于首先形成的单体α-氧杂环丁烯1和3的异常二聚作用，得到了新的且非常稳定的α-氧杂环丁烯6。[2 + 2] 6和二烷基碳二亚胺的环加成反应可提供功能化的亚氨基β-内酰胺7，而与亲核试剂的反应可将6完全降解成较小的片段。6和7的结构确认主要基于单晶X射线分析。
• 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。
• Tetra‐<i>tert</i>‐butyltrioxabicyclo[3.3.1]nonadienedicarboxylic Acid: Optical Resolution, Absolute Configuration and Application in Chiral Discrimination
  作者：Jennifer Kremsner、Bianca C. Wallfisch、Ferdinand Belaj、Georg Uray、C. Oliver Kappe、Curt Wentrup、Gert Kollenz

  DOI：10.1002/ejoc.200800109

  日期：2008.7

  exhibiting axial chirality, can easily be synthesized and serve as host for separating and/or transporting chiral guest molecules. Racemic 4 gives with (R)- and (S)-1-phenylethylamine the corresponding pure diastereomeric salts 7 and 8. The absolut configuration of the diacid 4 in the diastereomeric salt 7 containing (R)-1-phenylethylamine was confirmed to be R by X-ray crystal structure analysis, which

  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
• Saalfrank, Rolf W.; Lutz, Thomas, Angewandte Chemie, 1990, vol. 102, # 9, p. 1064 - 1066
  作者：Saalfrank, Rolf W.、Lutz, Thomas

  DOI：——

  日期：——
• 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.