3-烯丙基苯并恶唑-2(3H)-酮 | 13444-14-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶唑类
• 中文名称: 3-烯丙基苯并恶唑-2(3H)-酮
• 英文名称: N-allyl benzoxazol-2-one
• 英文别名: 3-allylbenzoxazolone；3-allyl-3H-benzooxazol-2-one；3-allyl-3H-benzoxazol-2-one；3-Allyl-3H-benzoxazol-2-on；3-Allyl-benzoxazolin-2-on；3-Allylbenzoxazolinon；2-Benzoxazolinone, 3-allyl-；3-prop-2-enyl-1,3-benzoxazol-2-one
• CAS: 13444-14-9
• 化学式: C₁₀H₉NO₂
• mdl: MFCD00796223
• 分子量: 175.187
• InChiKey: JOYZQLOOESWHTK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  3-烯丙基苯并恶唑-2(3H)-酮 在 正丁基锂 、 四(3,5-二(三氟甲基)苯基)硼酸钠 、 C₄₈H₅₈AuClNO₂P 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 15.5h， 生成 (5aS,7R,9aR,9bR)-1-cyclopropyl-5a,6,7,9a-tetrahydro-3H,5H-7,9b-methanopyrrolo[2,1-a]isoindole-3,10-dione
  参考文献：
  名称：

  通过配体协同金催化实现苯酚的不对称脱芳构化

  摘要：

  通过在金协同催化下使用手性双功​​能膦配体实现了苯酚的不对称脱芳构化。该转化表现出显着的通用性，提供了具有高产率（高达 99%）和优异的对映选择性（ee 高达 99%）的所需产物。

  DOI：

  10.1002/anie.202309256
• 作为产物：
  描述：

  苯基羟胺 在 四(三苯基膦)钯 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 8.0h， 生成 3-烯丙基苯并恶唑-2(3H)-酮
  参考文献：
  名称：

  Synthesis of 3-Alkylbenzoxazolones from N-Alkyl-N-arylhydroxylamines by Contiguous O-Trichloroacetylation, Trichloroacetoxy ortho-Shift, and Cyclization Sequence

  摘要：

  Benzoxazolone pharmacophore is present in clinical pharmaceuticals, drug candidates, and many compounds having a wide spectrum of biological activities. The methods available for the synthesis of benzoxazolones have limited diversity due to problems in accessibility and air-sensitivity of diversely substituted o-aminophenols from which they are generally prepared by cyclocarbonylation with phosgene or its equivalents. The present paper describes a mild method for the synthesis of 3-alkylbenzoxazolones from easily accessible and air-stable nitroarenes. Nitroarenes were converted to N-alkyl-N-arylhydroxylamines in two steps involving partial reduction to arylhydroxylamines followed by selective N-alkylation. Treatment of N-alkyl-N-arylhydroxylamines with trichloroacetyl chloride and triethylamine afforded 3-alkylbenzoxazolones generally in good yields through an uninterrupted three-step sequence involving O-trichloroacetylation, N -> C-ortho trichloroacetoxy shift, and cyclization in a single pot at ambient temperatures. The present method is mild, wide in scope, economical, and regioselective. Many sensitive groups like alkyl and aryl esters, amide, cyano, and the carbon-carbon double bond survive the reaction.

  DOI：

  10.1021/jo401985h

文献信息

• Palladium-Catalyzed Dehydrative Cross-Coupling of Allylic Alcohols and <i>N</i>-Heterocycles Promoted by a Bicyclic Bridgehead Phosphoramidite Ligand and an Acid Additive
  作者：Kyungjun Kang、Jaewook Kim、Ansoo Lee、Woo Youn Kim、Hyunwoo Kim

  DOI：10.1021/acs.orglett.6b00001

  日期：2016.2.5

  A mild and efficient dehydrative cross-coupling reaction between allylic alcohols and N-heterocycles using palladium catalysis is reported. A bicyclic bridgehead phosphoramidite (briphos) ligand together with Pd(dba)2 is a highly efficient catalyst, and an acid additive involved in the rate-determining step promotes the catalytic cycle. The coupling reaction of allylic alcohols with N-heterocycles

  报道了使用钯催化的在烯丙基醇和N-杂环之间的温和且有效的脱水交叉偶联反应。双环桥头亚磷酰胺（briphos）配体与Pd（dba）2一起是高效催化剂，速率确定步骤中涉及的酸添加剂促进了催化循环。烯丙基醇与包括咪唑，苯并咪唑和三唑的N-杂环的偶合反应在温和的反应条件下进行，使用钯/硫磷和五氟苯酚的收率很高。
• The Reaction of Dialkyl Carbonates with<i>o</i>-Aminophenol Catalysed by K₂CO₃: A Novel High-Yield Synthesis of<i>N</i>-Alkylbenzoxazol-2-ones
  作者：Maurizio Selva

  DOI：10.1055/s-2003-42464

  日期：——

  At 130-150 °C and in the presence of catalytic K2CO3, o-aminophenol (1) readily reacts with dialkyl carbonates (2: ROCO2R; 2a: R = Me, 2b: Et, 2c: Allyl, 2d: Bn) to give the corresponding N-alkylbenzoxazol-2-ones (3a-d) in high yields (88-98%). This reaction is a rare example where dialkyl carbonates may simultaneously act as carbonylating and alkylating agents likely through a BAc2/BAl2 sequence. Moreover, compounds 2a-c serve also as solvents. In the case of 2d, 1,2-dimethoxyethane (DME) is the reaction medium.

  在 130-150 °C 和催化 K2CO3 存在下，邻氨基苯酚 (1) 很容易与碳酸二烷基酯（2：ROCO2R；2a：R = Me，2b：Et，2c：烯丙基，2d：Bn）反应，得到相应的N-烷基苯并恶唑-2-酮(3a-d)的产率很高(88-98%)。该反应是碳酸二烷基酯可能通过 BAc2/BAl2 序列同时充当羰基化剂和烷基化剂的罕见例子。此外，化合物2a-c也用作溶剂。在2d的情况下，1,2-二甲氧基乙烷(DME)是反应介质。
• Photochemical rearrangements of 1,2-benzisoxazolinones
  作者：Thomas H. Kinstle、Larry J. Darlage、C. L. McIntosh

  DOI：10.1021/jo00807a017

  日期：1971.4
• Synthesis of 3-Alkylbenzoxazolones from <i>N</i>-Alkyl-<i>N</i>-arylhydroxylamines by Contiguous <i>O</i>-Trichloroacetylation, Trichloroacetoxy <i>ortho</i>-Shift, and Cyclization Sequence
  作者：Ram N. Ram、Vineet Kumar Soni

  DOI：10.1021/jo401985h

  日期：2013.12.6

  Benzoxazolone pharmacophore is present in clinical pharmaceuticals, drug candidates, and many compounds having a wide spectrum of biological activities. The methods available for the synthesis of benzoxazolones have limited diversity due to problems in accessibility and air-sensitivity of diversely substituted o-aminophenols from which they are generally prepared by cyclocarbonylation with phosgene or its equivalents. The present paper describes a mild method for the synthesis of 3-alkylbenzoxazolones from easily accessible and air-stable nitroarenes. Nitroarenes were converted to N-alkyl-N-arylhydroxylamines in two steps involving partial reduction to arylhydroxylamines followed by selective N-alkylation. Treatment of N-alkyl-N-arylhydroxylamines with trichloroacetyl chloride and triethylamine afforded 3-alkylbenzoxazolones generally in good yields through an uninterrupted three-step sequence involving O-trichloroacetylation, N -> C-ortho trichloroacetoxy shift, and cyclization in a single pot at ambient temperatures. The present method is mild, wide in scope, economical, and regioselective. Many sensitive groups like alkyl and aryl esters, amide, cyano, and the carbon-carbon double bond survive the reaction.
• Asymmetric Dearomatization of Phenols via Ligand‐Enabled Cooperative Gold Catalysis
  作者：Yongliang Zhang、Ke Zhao、Xinyi Li、Carlos D. Quintanilla、Liming Zhang

  DOI：10.1002/anie.202309256

  日期：2023.9.18

  Asymmetric dearomatization of phenols was achieved by employing chiral bifunctional phosphine ligands in cooperative gold catalysis. This transformation demonstrated a remarkable generality, affording the desired product with high yields (up to 99 %) and excellent enantioselectivities (ee up to 99 %).

  通过在金协同催化下使用手性双功​​能膦配体实现了苯酚的不对称脱芳构化。该转化表现出显着的通用性，提供了具有高产率（高达 99%）和优异的对映选择性（ee 高达 99%）的所需产物。