(E)-ethyl 3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylate | 1384519-04-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噁庚英
• 英文名称: (E)-ethyl 3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylate
• 英文别名: Ethyl 3-oxo-1-benzoxepine-4-carboxylate；ethyl 3-oxo-1-benzoxepine-4-carboxylate
• CAS: 1384519-04-3
• 化学式: C₁₃H₁₂O₄
• 分子量: 232.236
• InChiKey: NAHHJMAZSISJJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 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：
  4

反应信息

• 作为反应物：
  描述：

  (E)-ethyl 3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylate 在 盐酸羟胺 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以72%的产率得到3H,10H-benzo[6,7]oxepino[3,4-c]isoxazol-3-one
  参考文献：
  名称：

  Convenient one-pot synthesis, anti-mycobacterial and anticancer activities of novel benzoxepinoisoxazolones and pyrazolones

  摘要：

  Series of new benzoxepinoisoxazolones 4a-d and pyrazolones 6a-t were prepared by the cyclocondensation of substituted (E)-ethyl 3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylates 3a-d with hydroxylamine hydrochloride and phenylhydrazine hydrochlorides 5a-k. Synthesized compounds were screened for their in vitro anti-mycobacterial activity and anticancer activity. Ten compounds displayed good anti-mycobacterial activity, among these; compound 4d and 6b found to be potent when compared to standard drug isoniazid. Eleven compounds displayed good anticancer activity and compounds 4b-d displayed equipotent activity on HeLa cell lines when compared to standard drug doxorubicin. Activation of caspase-3 and caspase-9 has been measured for compounds 4b-d on HeLa cell lines (apoptosis). This is the first report assigning in vitro anti-mycobacterial, anticancer and structure-activity relationship for this new class of benzoxepinoisoxazolones and pyrazolones. (C) 2014 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2014.02.042
• 作为产物：
  描述：

  ethyl 2-(chloromethyl)-2-hydroxy-2H-chromene-3-carboxylate 在 乙氧甲酰基亚乙基三苯基 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以82%的产率得到(E)-ethyl 3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylate
  参考文献：
  名称：

  2-（氯甲基）-2 H -chromen-2-ol衍生物的Wittig同源性：取代的2,3-二氢苯并二甲苯-4-羧酸酯的新合成

  摘要：

  维蒂希的2-（氯甲基）-2同系ħ -苯并吡喃-2-醇衍生物2A -吨与（乙氧基羰基亚甲基）三苯基正膦中提供的2氧代亚乙基-2,3- dihydrobenzoxepine -4-羧基酸酯3A -吨与Ž（顺）的选择性。研究了各种碱性催化剂，用于2-（氯甲基）-2 H-铬-2-醇2a与Wittig试剂的反应，得到化合物3b。2-（氯甲基）-2 H -chromen-2-ol 2a的反应与其他Wittig试剂，例如亚甲基（三亚苯基）膦和（1-乙氧基羰基亚乙基）三苯基膦，提供了酮衍生物4a而不是2-氧代亚乙基衍生物3b。使酮衍生物4a与Wittig试剂（乙氧基羰基亚甲基）三苯基膦烷反应，得到2，3-二氢苯并二甲苯基-4-羧酸酯3b。本方法是新颖的，直接的，并且是首次报道。

  DOI：

  10.1016/j.tet.2012.05.047

文献信息

• Stereospecific Synthesis of 3,4-Dihydro-2<i>H</i>-naphtho-1,4-oxazin-2-ones by Unification of Benzoxepine-4-carboxylates with Chiral Amino Acid Ethyl Esters
  作者：Veera Prasad Kasagani、Siva Hariprasad Kurma、China Raju Bhimapaka

  DOI：10.1021/acs.joc.9b02624

  日期：2020.3.6

  A novel and efficient stereocontrolled method has been developed for the preparation of chiral 3,4-dihydro-2H-naphtho[1,2-b][1,4]oxazin-2-ones by the reaction of benzoxepine-4-carboxylates with chiral amino acid ethyl esters for the first time. The chiral 3,4-dihydro-2H-naphtho-1,4-oxazinones have been achieved in one step by the formation of C-N, C-C, and C-O bonds.

  已开发出一种新颖有效的立体控制方法，该方法可通过苯并氧杂庚酸酯-4-羧酸酯与手性化合物的反应制备手性3,4-二氢-2H-萘并[1,2-b] [1,4]恶嗪-2-酮。首次手性氨基酸乙酯。通过形成CN，CC和CO键，一步即可获得手性的3,4-二氢-2H-萘-1,4-恶嗪酮。
• A Novel Approach for C–C, C–N, and C–O Bond Formation Reactions: A Facile Synthesis of Benzophenazine, Quinoxaline, and Phenoxazine Derivatives via Ring Opening of Benzoxepines
  作者：Bhimapaka China Raju、Kasagani Veera Prasad、Gannerla Saidachary、Balasubramanian Sridhar

  DOI：10.1021/ol4033122

  日期：2014.1.17

  synthesis of benzophenazine, quinoxaline, and phenoxazine derivatives by the reaction of benzoxepine-4-carboxylates with benzene-1,2-diamines, ethane-1,2-diamine, and 2-aminophenols in the presence of Bi(OTf)3 (5 mol %) under mild conditions in very good yields. The present protocol opens a new way for C–C, C–N, and C–O bond-formation reactions in a single-step process. The structural assignment was

  已开发出一种新的一锅操作规程，用于通过苯并氧杂庚酸酯-4-羧酸盐与苯-1,2-二胺，乙烷-1,2-二胺和2-氨基苯酚的反应来合成苯并吩嗪，喹喔啉和苯恶嗪衍生物在温和的条件下在Bi（OTf）3（5 mol％）存在下以非常好的收率。本协议为单步过程中C–C，C–N和C–O键形成反应开辟了一条新途径。通过X射线分析确认了结构分配。
• A facile construction of oxygen heterocycles by the reaction of benzoxepine-4-carboxylates with dihaloalkanes and activated alkynes
  作者：Veera Prasad Kasagani、Siva Hariprasad Kurma、China Raju Bhimapaka

  DOI：10.1039/c9ob00769e

  日期：——

  This manuscript describes the preparation of heterocyclic compounds such as naphtho[1,3]-dioxoles (3a-h), [1,4]-dioxines (4a-h), [1,4]-dioxepines (5a-c), [1,4]-dioxocines (6a-c) and diethyl 2-(2-ethoxy-2-oxoethyl)naphtho[1,3]dioxoles (8a-f). These heterocyclic compounds have been achieved by the reaction of benzoxepine-4-carboxylates (1a-h) with dihaloalkanes (2a-e) and activated alkyne (7a) for the

  该手稿描述了杂环化合物的制备，例如萘并[1,3]-二恶唑（3a-h），[1,4]-二恶英（4a-h），[1,4]-二氧杂庚环（5a-c）， [1，4]-二氧杂环酮（6a-c）和2-（2-乙氧基-2-氧代乙基）萘二乙基[1，3]二恶唑（8a-f）。这些杂环化合物是通过苯并xepine-4-羧酸盐（1a-h）与二卤代烷烃（2a-e）和活化炔烃（7a）的首次反应获得的。这项工作代表了通过一步法形成CC和CO键来构建实用氧杂环的第一个例子。
• Convenient one-pot synthesis, anti-mycobacterial and anticancer activities of novel benzoxepinoisoxazolones and pyrazolones
  作者：G. Saidachary、K. Veera Prasad、D. Divya、Ashita Singh、U. Ramesh、B. Sridhar、B. China Raju

  DOI：10.1016/j.ejmech.2014.02.042

  日期：2014.4

  Series of new benzoxepinoisoxazolones 4a-d and pyrazolones 6a-t were prepared by the cyclocondensation of substituted (E)-ethyl 3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylates 3a-d with hydroxylamine hydrochloride and phenylhydrazine hydrochlorides 5a-k. Synthesized compounds were screened for their in vitro anti-mycobacterial activity and anticancer activity. Ten compounds displayed good anti-mycobacterial activity, among these; compound 4d and 6b found to be potent when compared to standard drug isoniazid. Eleven compounds displayed good anticancer activity and compounds 4b-d displayed equipotent activity on HeLa cell lines when compared to standard drug doxorubicin. Activation of caspase-3 and caspase-9 has been measured for compounds 4b-d on HeLa cell lines (apoptosis). This is the first report assigning in vitro anti-mycobacterial, anticancer and structure-activity relationship for this new class of benzoxepinoisoxazolones and pyrazolones. (C) 2014 Elsevier Masson SAS. All rights reserved.
• Wittig homologation of 2-(chloromethyl)-2H-chromen-2-ol derivatives: a new facile synthesis of substituted 2,3-dihydrobenzoxepine-4-carboxylates
  作者：Bhimapaka China Raju、Gannerla Saidachary、Jaladi Ashok Kumar

  DOI：10.1016/j.tet.2012.05.047

  日期：2012.8

  homologation of 2-(chloromethyl)-2H-chromen-2-ol derivatives 2a–t with (ethoxycarbonylmethylene)triphenylphosphorane provided the 2-oxoethylidene-2,3-dihydrobenzoxepine-4-carboxy-lates 3a–t with Z (cis) selectivity. Various basic catalysts were studied for the reaction of 2-(chloromethyl)-2H-chromen-2-ol 2a with the combination of Wittig reagent to provide compound 3b. The reaction of 2-(chloromethyl)-2H-chromen-2-ol

  维蒂希的2-（氯甲基）-2同系ħ -苯并吡喃-2-醇衍生物2A -吨与（乙氧基羰基亚甲基）三苯基正膦中提供的2氧代亚乙基-2,3- dihydrobenzoxepine -4-羧基酸酯3A -吨与Ž（顺）的选择性。研究了各种碱性催化剂，用于2-（氯甲基）-2 H-铬-2-醇2a与Wittig试剂的反应，得到化合物3b。2-（氯甲基）-2 H -chromen-2-ol 2a的反应与其他Wittig试剂，例如亚甲基（三亚苯基）膦和（1-乙氧基羰基亚乙基）三苯基膦，提供了酮衍生物4a而不是2-氧代亚乙基衍生物3b。使酮衍生物4a与Wittig试剂（乙氧基羰基亚甲基）三苯基膦烷反应，得到2，3-二氢苯并二甲苯基-4-羧酸酯3b。本方法是新颖的，直接的，并且是首次报道。