3-n-propyl-6,7-(methylenedioxy)isocoumarin | 163597-63-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异香豆素及其衍生物
• 英文名称: 3-n-propyl-6,7-(methylenedioxy)isocoumarin
• 英文别名: 6,7-methylenedioxy-3-propylisocoumarin；xyridine A；xyridin A；3-propyl-6,7-(methylenedioxy)isocoumarin；5H-1,3-Dioxolo[4,5-g][2]benzopyran-5-one, 7-propyl-；7-propyl-[1,3]dioxolo[4,5-g]isochromen-5-one
• CAS: 163597-63-5
• 化学式: C₁₃H₁₂O₄
• 分子量: 232.236
• InChiKey: UQMOOBFMUJITLL-UHFFFAOYSA-N

物化性质

• 熔点：
  64-65 °C(Solv: ethyl acetate (141-78-6); ligroine (8032-32-4))
• 沸点：
  384.3±42.0 °C(Predicted)
• 密度：
  1.287±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-n-propyl-6,7-(methylenedioxy)isocoumarin 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 4.0h， 以70%的产率得到4,5-methylenedioxy-2-(2-oxopentyl)benzoic acid
  参考文献：
  名称：

  y草的代谢产物木霉素A和B的合成及生物活性

  摘要：

  从中轻松合成标题异香豆素。Xyris indica完成了。丁酰氯和2-氧代丁酰氯与3，4-亚甲基二氧基高邻苯二甲酸的缩合分别得到木酮A和木酮B。将木酮A皂化为相应的酮酸，其还原后得到（±）-3,4-二氢-6,7-亚甲基二氧基-3-丙基异香豆素。在体外检查所有合成的化合物的抗菌和抗真菌活性。

  DOI：

  10.1002/jhet.5570400222
• 作为产物：
  描述：

  5,6-二甲氧基茚酮 在 盐酸 、 sodium hydroxide 、 聚合甲醛 、 三氯化铝 、 adogen 464 、 亚硝酸甲酯 、 双氧水 、 溶剂黄146 作用下， 以 甲醇 、 水 、 氯苯 为溶剂， 反应 9.25h， 生成 3-n-propyl-6,7-(methylenedioxy)isocoumarin
  参考文献：
  名称：

  Ahmed, Hafiz Badar-Ud-Din; Rama, Nasim Hasan; Malana, Muhammad Aslam, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2006, vol. 45, # 3, p. 820 - 822

  摘要：

  DOI：

文献信息

• Pd-Catalyzed/Iodide-Promoted α-Arylation of Ketones for the Regioselective Synthesis of Isocoumarins
  作者：Alessandra Casnati、Raimondo Maggi、Giovanni Maestri、Nicola Della Ca’、Elena Motti

  DOI：10.1021/acs.joc.7b01355

  日期：2017.8.4

  synthesized directly from 2-halobenzoates and ketones through a palladium-catalyzed α-arylation step followed by an intramolecular cyclization process. The addition of iodide anions to the reaction mixture increased yields and selectivities especially when 2-bromobenzoates were employed. This phosphine-free one-pot synthesis features a high functional group tolerance and gives access to richly decorated

  已经通过钯催化的α-芳基化步骤，接着进行分子内环化过程，从2-卤代苯甲酸酯和酮直接合成了多种异香豆素。向反应混合物中加入碘化物阴离子增加了产率和选择性，特别是当使用2-溴苯甲酸酯时。这种无膦的一锅合成功能具有较高的官能团耐受性，可使用装饰精美的异香豆素。这种通用方法成功地完成了具有抗菌和抗真菌活性的重要天然产物木霉素A的全合成。
• Novel One-pot Synthesis of Polysubstituted Isocoumarins from Arynes and Trifluoroacetylated β-Diketones
  作者：Kentaro Okuma、Koki Hirano、Yukiko Tanabe、Ryoichi Itoyama、Atsumi Miura、Noriyoshi Nagahora、Kosei Shioji

  DOI：10.1246/cl.131112

  日期：2014.4.5

  Polysubstituted isocoumarins such as thunberginol A were synthesized by the reaction of substituted 2-(trimethylsilyl)phenyl triflate with trifluoromethylated β-diketones in the presence of CsF. The reaction proceeded via carbon–carbon bond insertion of aryne followed by intramolecular cyclization and CF3 anion extrusion. The –C(···O)CF3 unit has high potential for not only the nucleophilic moiety but also a useful leaving group of CF3.

  多取代的异香豆素如Thunberginol A是通过在CsF存在下，将取代的2-(三甲基硅基)苯三氟甲磺酸酯与三氟甲基化的β-二酮反应合成的。该反应是通过芳基炔的碳-碳键插入，再进行分子内环化和CF3阴离子的挤出进行的。-C(···O)CF3单元不仅具有成为亲核基团的高潜力，还具有作为CF3有用离去基团的优点。
• Access to divergent benzo-heterocycles via a catalyst-dependent strategy in the controllable cyclization of o-alkynyl-N-methoxyl-benzamides
  作者：Dong Ding、Tao Mou、Jiahui Xue、Xuefeng Jiang

  DOI：10.1039/c7cc01861d

  日期：——

  regio-selectively controllable approach for construction of diverse benzo-heterocycles is established. A new strategy for using the ligand effect in gold catalysis to control the regioselectivity in the cyclization of o-alkynyl-N-methoxyl-benzamide is successfully achieved. Meanwhile, the chemoselectivity between nitrogen and oxygen nucleophiles is precisely switched by gold and platinum catalysts.

  建立了化学和区域选择性可控制的方法来构建各种苯并杂环。成功实现了在金催化中利用配体效应来控制邻炔基-N-甲氧基-苯甲酰胺环化反应中区域选择性的新策略。同时，氮和氧亲核试剂之间的化学选择性可通过金和铂催化剂精确切换。
• A Single-Step Synthesis of Xyridins A and B, Metabolites from Xyris indica
  作者：Aamer Saeed

  DOI：10.1007/s10593-005-0262-9

  日期：2005.8
• Reaction of arynes with trifluoroacetylated β-diketones: Novel formation of isocoumarins and phenanthrenes
  作者：Kentaro Okuma、Yukiko Tanabe、Takuto Fukami、Yuto Ishibashi

  DOI：10.1002/hc.21444

  日期：2018.12

  AbstractPolysubstituted isocoumarins were synthesized by the reaction of substituted 2‐(trimethylsilyl)aryl triflates with trifluoromethylated β‐diketones in the presence of CsF. The reaction proceeded through carbon‐carbon bond insertion of aryne and intramolecular cyclization to form intermediates of alcohol anions, which extruded trifluoromethyl anion to afford isocoumarins. By using CuBr as a catalyst, 2 eq. of aryne reacted with β‐diketones to afford phenanthrenes and 1,2‐diarylethanones. Although reaction of 2‐(trimethylsilyl)phenyl triflate with 1,1,1‐trifluoro‐4′‐methylbenzoylacetone in the presence of CsF gave 3‐(4′‐methylphenyl)isocoumarin in 67% yield, addition of 0.2 eq. of CuCN resulted in the formation of 9‐(4‐methylbenzoyl)‐10‐trifluoromethylphenanthrene in 35% yield.