三苯基甲基乙腈氧化物 | 13412-55-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 中文名称: 三苯基甲基乙腈氧化物
• 英文名称: triphenylacetonitrile oxide
• 英文别名: Triphenyl-acetonitriloxid；Triphenyl-acetonitrile oxide；2,2,2-triphenylacetonitrile oxide
• CAS: 13412-55-0
• 化学式: C₂₀H₁₅NO
• 分子量: 285.345
• InChiKey: GKKDMGZBMGDYEC-UHFFFAOYSA-N

物化性质

• 熔点：
  153-154 °C
• 密度：
  1.03±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  三苯基甲基乙腈氧化物 以 xylene 为溶剂， 生成 trityl isocyanate
  参考文献：
  名称：

  A kinetic study of the rearrangement of triarylacetonitrile oxides

  摘要：

  The thermal rearrangement of triphenylacetonitrile oxide (1a) to triphenylmethyl isocyanate (2) is a first-order process. Rate constants at five temperatures between 116 and 190-degrees-C were determined giving DELTA-H double-ended dagger = 9.3 +/- 1.1 kcal/mol and DELTA-S double-ended dagger = -58.2 +/- 2.4 cal/mol.K. The rearrangement of substituted triarylacetonitrile oxides (1b-d) occur only slightly faster than that of 1a. These results are interpreted in terms of a concerted single-step rearrangement in which the highly ordered transition state (6c) has a degree of radical character.

  DOI：

  10.1021/jo00026a024
• 作为产物：
  描述：

  雷酸银 、 三苯基氯甲烷 以 甲苯 为溶剂， 生成 三苯基甲基乙腈氧化物
  参考文献：
  名称：

  A kinetic study of the rearrangement of triarylacetonitrile oxides

  摘要：

  The thermal rearrangement of triphenylacetonitrile oxide (1a) to triphenylmethyl isocyanate (2) is a first-order process. Rate constants at five temperatures between 116 and 190-degrees-C were determined giving DELTA-H double-ended dagger = 9.3 +/- 1.1 kcal/mol and DELTA-S double-ended dagger = -58.2 +/- 2.4 cal/mol.K. The rearrangement of substituted triarylacetonitrile oxides (1b-d) occur only slightly faster than that of 1a. These results are interpreted in terms of a concerted single-step rearrangement in which the highly ordered transition state (6c) has a degree of radical character.

  DOI：

  10.1021/jo00026a024

文献信息

• A tandem 1,3-dipolar cycloaddition/electrophilic cyclization sequence: γ,δ-Unsaturated isoxazolines as precursors to ring-fused ethers
  作者：Mark J. Kurth、Michael J. Rodriguez

  DOI：10.1016/s0040-4020(01)89162-6

  日期：——

  A tandem 1,3-dipolar cycloaddition/electrophilic cyclization sequence affords cis-fused octahydrobenzo-and hexahydro-2H-cyclopenta[b]furans via the intermediacy of γ,δ-unsaturated isoxazolines.

  串联的1，3-偶极环加成/亲电环化序列通过γ，δ-不饱和异恶唑啉的中间体得到顺式稠合的八氢苯并-和六氢-2H-环戊[b]呋喃。
• Thermal Rearrangement of Nitrone and Nitrile Oxide Cycloadducts to Bicyclopropylidene.¹ Synthesis of 3-Spirocyclopropane-4-pyridone and Furo[2,3-<i>c</i>]pyridine Derivatives
  作者：Andrea Goti、Beatrice Anichini、Alberto Brandi、Sergei Kozhushkov、Corinna Gratkowski、Armin de Meijere

  DOI：10.1021/jo951838l

  日期：1996.1.1

  The same sequence of cycloaddition and rearrangement can be achieved in a "one-pot" operation with considerable benefit for the reaction yield. Bisspirocyclopropaneisoxazolines obtained from nitrile oxides are more stable than their saturated counterparts and rearrange only at higher temperature less chemoselectively. Opening of both spiro-fused cyclopropyl rings followed by aromatization produces interesting

  在不同的反应条件下，双环亚丙基平稳地经历1​​，3-偶极环加成反应到硝酮或腈氧化物上。从硝酮得到的应变的双螺环丙烷化的异恶唑烷在加热时容易选择性地重排，同时选择性打开两个螺合的环丙烷环之一。该方法以良好的产率产生了在羰基的α-位含有螺环丙烷部分的4-吡啶酮，7-吲哚嗪酮和2-喹啉嗪酮衍生物。可以在“一锅法”操作中实现相同的环加成和重排顺序，这对于反应产率具有相当大的益处。从腈类氧化物获得的双螺环丙烷异恶唑啉比其饱和对应物更稳定，并且仅在较高的温度下才具有较低的化学选择性进行重排。
• Diastereoselective Synthesis of 2-Cyanomethyl-3-hydroxy-5-iodomethyltetrahydrofuran from Isoxazolines by Iodoetheration
  作者：Hyoung Rae Kim、Hyoung Cheul Kim、Seung Woo Woo、Min Jung Seo、Dong Ju Jeon、Zaesung No

  DOI：10.1055/s-2002-34245

  日期：——

  Diastereoselective 1,3-dipolar cycloaddition reaction of nitrile oxides with 1,5-hexadien-3-ol afforded syn-5-(1-hydroxy-3-butenyl)isoxazolines, which underwent iodoetheration by iodine monochloride to give 2-cyanomethyl-3-hydroxy-5-iodomethyl­tetrahydrofuran with diastereoselectivity. The relative stereo­chemistry of iodomethyl group varied depending on both the 3-substituents and the hydroxy protecting groups.

  腈氧化物与 1,5-hexadien-3-ol 的非对映选择性 1,3 双极环加成反应生成了合成的 5-(1-羟基-3-丁烯基)异恶唑，这些异恶唑在一氯化碘的作用下发生碘醚化反应，以非对映选择性生成了 2-氰甲基-3-羟基-5-碘甲基四氢呋喃。碘甲基的相对立体化学性质因 3-取代基和羟基保护基的不同而不同。
• Photolysis of 3-triphenylmethyl-Δ²-isoxazolines: a new method for CC-double bond cleavage
  作者：Heinz Kaufmann、Jaroslav Kalvoda

  DOI：10.1039/c39760000210

  日期：——

  U.v. irradiation of triphenylmethyl-Δ2-isoxazolines, formed by 1,3-dipolar addition of triphenyl-acetonitrile oxide to olefins, results in the elimination of the Ph3C group and subsequent fragmentation of the heterocycle to give a carbonyl compound and a nitrile.

  三苯-Δ的紫外线照射2个-isoxazolines通过1,3-偶极加成三苯基-乙腈氧化物至烯烃形成，导致消除的Ph 3 C组和杂环的后续分段，得到羰基化合物和腈。
• Regiochemistry of the dipolar cycloadditions of nitrile oxides to unactivated olefins. Application to the stereoselective elaboration of β-hydroxycarbonyl compounds.
  作者：Stephen F. Martin、Brian Dupre

  DOI：10.1016/s0040-4039(00)81650-0

  日期：1983.1