乙基5,6,7,8-四氟-2-甲基-4-氧代-4H-苯并吡喃-3-羧酸酯 | 4487-61-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 中文名称: 乙基5,6,7,8-四氟-2-甲基-4-氧代-4H-苯并吡喃-3-羧酸酯
• 英文名称: 3-ethoxycarbonyl-2-methyl-5,6,7,8-tetrafluoro-4H-1,4-dihydrobenzopyran-4-one
• 英文别名: 3-Ethoxycarbonyl-2-methyl-5,6,7,8-tetrafluorochromone；Ethyl 5,6,7,8-tetrafluoro-2-methyl-4-oxochromene-3-carboxylate
• CAS: 4487-61-0
• 化学式: C₁₃H₈F₄O₄
• 分子量: 304.198
• InChiKey: APHVYXJZVANHDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  8

安全信息

• 海关编码：
  2918300090

反应信息

• 作为反应物：
  描述：

  乙基5,6,7,8-四氟-2-甲基-4-氧代-4H-苯并吡喃-3-羧酸酯 以 乙醇 、 二甲基亚砜 为溶剂， 反应 0.5h， 生成 5,6,7,8-tetrafluoro-3-(1-(methylamino)ethylidene)-3,4-dihydro-2H-benzopyrane-2,4-dione
  参考文献：
  名称：

  2(3)-ethoxycarbonyl-5,6,7,8-四氟色酮与甲胺的反应

  摘要：

  摘要 2-乙氧基羰基-5,6,7,8-四氟色酮与甲胺的反应因溶剂性质和胺的量而异：在 DMSO 和 MeCN 中，C(7) 原子上的氟原子最初被取代，然后C(2) 和/或 C(9) 受到攻击，而在乙醇中，反应涉及 C(2) 原子并打开吡喃酮环。3-乙氧羰基-5,6,7,8-四氟-2-甲基色酮与甲胺反应，无论溶剂如何，都会打开色酮环并形成中间体乙基 3-(3,4,5, 6-四氟-2-羟基苯基)-2-(1-甲基氨基)亚乙基-3-氧代丙酸酯，经过分子内环化得到5,6,7,8-四氟-3-(1-甲基-氨基)亚乙基-3 ,4-二氢-2H-苯并吡喃-2,4-二酮。

  DOI：

  10.1007/s11172-006-0091-8
• 作为产物：
  描述：

  Ethyl 2-pentafluorobenzoyl-3-oxobutanoate 反应 1.0h， 以92%的产率得到乙基5,6,7,8-四氟-2-甲基-4-氧代-4H-苯并吡喃-3-羧酸酯
  参考文献：
  名称：

  Fluoroaryl containing β,β′-dioxoesters in the synthesis of fluorobenzopyran-4(2)-ones

  摘要：

  Fluoroaryl containing beta, beta'-dioxoesters and their copper(II) chelates have been prepared by acylation of ethyl acetoacetate with 2,6-dimethoxy-3,4,5-trifluorobenzoyl, 2-methoxy-3,4,5,6-tetrafluorobenzoyl and pentafluorobenzoyl chlorides. Cyclization of these beta,beta'-dioxoesters leads to formation of substituted fluorochromones. Depending on conditions, 2-methyl-5-methoxy-6,7,8-trifluoro-3-ethoxycarbonylchromone hydrolyzed to 5-hydroxy-2-methyl-6,7,8-trifluorochromone or 5-hydroxy-2-methyl-6,7,8-trifluorochromone-3-carboxylic acid. The same chromone reacts with morpholine to form a seven-substituted product and ammonium hydroxide to give 3-iminoacetyl-4-hydroxy-5-methoxy-6,7,8-trifluorocoumarin. Hydrolysis of the latter affords 3-acetyl-4-hydroxy-5-methoxy-6,7,8-trifluorocoumarin Ethyl-2-(2,6-dimethoxy-3,4,5-trifluorobenzoyl)-3-oxobutanoates undergoes ketone-splitting to 1-(2,6-dimethoxy-3,4,5-trifluorophenyl)-1.3-butandione. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-1139(01)00346-3

文献信息

• Reactions of 4-hydroxy-5,6,7,8-tetrafluorocoumarin derivatives with S-nucleophiles
  作者：I.T Bazyl′、S.P Kisil′、Ya.V Burgart、V.I Saloutin

  DOI：10.1016/s0022-1139(99)00210-9

  日期：2000.4

  In the reactions with o-aminothiophenol, 4-hydroxy-(3-(imino)acetyl)-5,6,7,8-tetrafluorocoumarins give products of S-substitution at the C-7 atom. 7-Substituted 5,6,8-trifluorocoumarins form benzothiazole as a result of heterocyclic ring opening; 3-ethoxycarbonyl-2-methyl-5,6,7,8-tetrafluorochromone undergoes acid splitting to 2-(2-hydroxy-3,4,5,6-tetrafluorophenyl)benzothiazole. Under alkaline conditions

  与反应ø -氨基苯硫酚，4 -羟基-（3 -（亚氨基）乙酰基）-5,6,7,8-四氟香豆素在C-7原子处产生S取代的产物。由于杂环开环，7-取代的5,6,8-三氟香豆素形成苯并噻唑；3-乙氧基羰基-2-甲基-5,6,7,8-四氟色酮经历酸裂解反应生成2-（2-羟基-3,4,5,6-四氟苯基）苯并噻唑。在碱性条件下，S-取代的香豆素分解为苯乙酮。在酸性介质中，4-羟基-3-亚氨基乙酰基-5,6,8-三氟-7-（2-氨基苯硫基）香豆素得到7-（2-氨基苯硫基）-2-甲基-5,6,8-三氟色酮。从7-（2-氨基苯硫基）-4-羟基-5,6,8-的缩合分离出4-羟基-5,6-二氟-2-H-吡喃并[6,5-a]吩噻嗪-2-one。 NaH存在下的三氟香豆素。
• 一种3,4,5,6-四氟水杨酸的制备方法
  申请人：常州佳德医药科技有限公司

  公开号：CN106928046B

  公开（公告）日：2019-10-18

  本发明公开了一种3,4,5,6‑四氟水杨酸的制备方法，以2,3,4,5,6‑五氟苯甲酰氯为原料，经过与乙酰乙酸乙酯缩合络合铜离子得中间产物，再经酸化，加热环合得产物5,6,7,8‑四氟‑2‑甲基‑4‑氧代‑4H‑苯并吡喃‑3‑羧酸乙酯；上述产物在氢氧化钠溶液中搅拌，缓慢滴加过量过氧化氢溶液，保温搅拌，经TLC检测发现无上述产物后则反应完毕；再加入硫代硫酸钠除去过量过氧化氢，升温1h，冷却到常温加入盐酸调节pH，甲基叔丁基醚提取，经无水硫酸钠干燥，滤液蒸馏，粗品经二氯甲烷重结晶，制得3,4,5,6‑四氟水杨酸。本发明对设备要求低，副产物为水无污染，收率为78‑83％，粗品纯度高达97％。
• A route to ethyl α-pentafluorobenzoyl-β-oxobutanoate via its copper(II) chelate
  作者：Yanina V. Burgart、Sergei P. Kisil、Viktor I. Saloutin、Oleg N. Chupakhin

  DOI：10.1070/mc2001v011n02abeh001399

  日期：2001.1
• Reactions of ethyl 5,6,7,8-tetrafluoro-2-methylchromone-3-carboxylate and 3-acetimidoyl-5,6,7,8-tetrafluoro-4-hydroxycoumarin with S-nucleophiles
  作者：I. T. Bazyl'、S. P. Kisil'、S. N. Frolov、Ya. V. Burgart、V. I. Saloutin

  DOI：10.1007/bf02496408

  日期：1999.8

  The reactions of ethyl 5,6,7,8-tetrafluoro-2-methylchromone-3-carboxylate with mercaptoacetic acid and 1,2-ethanedithiol afforded C(7)-substitution products. The above-mentioned chromone reacted with 2-mercaptoethanol to yield 7-mono- or 5,7,8-trisubstituted products depending on the reaction conditions. The reaction of 3-acetimidoyl-5,6,7,8-tetrafluoro-4-hydroxycoumarin with 2-mercaptoethanol afforded a 5,7,8-trisubstituted product. The acyl-lactone rearrangement of mono- and trisubstituted chromones yielded the corresponding coumarins.
• Luminescent Zinc(II) Complexes of Fluorinated Benzothiazol-2-yl Substituted Phenoxide and Enolate Ligands
  作者：Zhe Li、Ahmed Dellali、Jahangir Malik、Majid Motevalli、Roger M. Nix、Toyin Olukoya、Yu Peng、Huanqing Ye、William P. Gillin、Ignacio Hernández、Peter B. Wyatt

  DOI：10.1021/ic302063u

  日期：2013.2.4

  Zn(II) complexes of the following new, fluorine-containing, benzothiazole-derived ligands have been synthesized and characterized crystallographically: 2-(3,3,3-trifluoro-2oxopropyl)benzothiazole (3), 4,5,6,7-tetrafluoro-2-(3,3,3-trifluoro-2-oxopropyl)benzothiazole (4), 4,5,6,7-tetrafluoro-2-(2hydroxyphenyl)benzothiazole (12), 2-(3,4,5,6-tetrafluoro-2-hydroxypheny1)-4,5,6,7-tetrafluorobenzothiazole (13), and 2(3,4,5,6-tetrafluoro-2-hydroxyphenyObenzothiazole (16); the Cu(II) complex of ligand 4 is also reported. These are analogs of the important photo- and electroluminescent material [Zn(BTZ)(2)](2), where H-BTZ = 2-(2-hydroxyphenyObenzothiazole. DFT calculations indicate that HOMO and LUMO energy levels in these materials are substantially lowered by fluorination. The fluorinated ZnL2 complexes are mononuclear (in contrast to the dinudear, nonfluorinated material [Zn(BTZ)(2)](2)). They easily sublime and show broad visible photoluminescence. A common crystallographic feature is the existence of pairs of fluorinated ZnL2 molecules related by inversion centers, with their pi systems facing one another.