methyl 3-oxo-2,3,9,9a-tetrahydro-1H-fluorene-9a-carboxylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: methyl 3-oxo-2,3,9,9a-tetrahydro-1H-fluorene-9a-carboxylate
• 英文别名: methyl 6-oxo-8,9-dihydro-7H-fluorene-8a-carboxylate
• 化学式: C₁₅H₁₄O₃
• 分子量: 242.274
• InChiKey: RHGTZXHKRGALQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 3-oxo-2,3,9,9a-tetrahydro-1H-fluorene-9a-carboxylate 在 吡啶 、 selenium(IV) oxide 作用下， 以51%的产率得到methyl 3-oxo-9,9a-dihydro-3H-fluorene-9a-carboxylate
  参考文献：
  名称：

  甲氧羰基在3-亚甲基-1,4-环己二烯中的迁移。von Auwers重排的扩展

  摘要：

  加热后，在6位具有烷氧羰基取代基的3-亚甲基-1,4-环己二烯进行重排并伴随芳构化，得到相应的芳基乙酸酯。这种转变代表了冯·奥维尔（von Auwers）重排的一种变型，并通过自由基链机制进行。中间烷氧基羰基基团可以被截获，从而允许进一步有用的合成变化。

  DOI：

  10.1016/j.tet.2016.03.032
• 作为产物：
  描述：

  methyl 1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-indene-2-carboxylate 在 哌啶 、 溶剂黄146 作用下， 以 甲苯 为溶剂， 生成 methyl 3-oxo-2,3,9,9a-tetrahydro-1H-fluorene-9a-carboxylate
  参考文献：
  名称：

  甲氧羰基在3-亚甲基-1,4-环己二烯中的迁移。von Auwers重排的扩展

  摘要：

  加热后，在6位具有烷氧羰基取代基的3-亚甲基-1,4-环己二烯进行重排并伴随芳构化，得到相应的芳基乙酸酯。这种转变代表了冯·奥维尔（von Auwers）重排的一种变型，并通过自由基链机制进行。中间烷氧基羰基基团可以被截获，从而允许进一步有用的合成变化。

  DOI：

  10.1016/j.tet.2016.03.032

文献信息

• An unexpected result in an intramolecular Ritter reaction induced by triflic anhydride
  作者：Valeria Justribó、Marı́a I. Colombo

  DOI：10.1016/j.tetlet.2003.08.107

  日期：2003.10

  The treatment of the methyl 2-(cyanoethyl)-1-hydroxy-2-indane-carboxylate 1b in dichloromethane solution with triflic anhydride at 20°C afforded the tricyclic enone 3 in 65% yield, instead of the expected lactam 2b produced under the ‘classic’ conditions of the Ritter reaction.

  在20℃下用三氟甲磺酸酐处理2-（氰基乙基）-1-羟基-2-茚满-羧酸甲酯1b在二氯甲烷中的溶液，得到65％收率的三环烯酮3，而不是在此条件下产生的预期内酰胺2b。 Ritter反应的“经典”条件。
• Acetylenic cyanoenones as therapeutics for inflammation and carcinogenesis
  申请人：Honda Tadashi

  公开号：US10233146B2

  公开（公告）日：2019-03-19

  The present invention provides a compound having the structure: wherein X is C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, cyano, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenylaryl, alkenylheteroaryl, alkynylaryl, alkynylheteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, heteroaryloxy, acyl, alkylhydroxy, alkylamino, alkenylamino, alkynylamino, amido, carboxyl, or carboxyl ester, or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with Y, Y is H or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with X, or forms an unsubstituted or substituted monocycle with Z; and Z is H or forms an unsubstituted or substituted monocycle with Y; wherein when X and Y are both H, then X is C2 alkenyl or C2 alkynyl, and when Y is H forms a substituted cyclohexyl, cycloheptyl with X, the cyclohexyl is other than a trisubstituted cyclohexyl bearing CH3, i-Pr and (CH2)2CO2CH3 groups or CH3, i-Pr and (CH2)3NH2, or a salt or ester thereof.

  本发明提供了一种具有以下结构的化合物： 其中 X是C1-C12烷基、C2-C12烯基、C2-C12炔基、氰基、芳基、杂芳基、烷芳基、烷基异芳基、烯芳基、烯基异芳基、炔芳基、炔基异芳基、烷氧基、烯氧基、炔氧基、芳氧基、杂芳氧基、酰基、烷基羟基、烷基氨基、烯基氨基、炔基氨基、氨基、羧基或羧基酯，或与 Y 形成未取代或取代的环丁基、环戊基、环己基、环庚基、茚或四萘、 Y 是 H，或与 X 形成未取代或取代的环丁基、环戊基、环己基、环庚基、茚满或四萘，或与 Z 形成未取代或取代的单环；和 Z 是 H，或与 Y 形成未取代或取代的单环； 其中，当 X 和 Y 均为 H 时，则 X 为 C2 烯基或 C2 炔基，而当 Y 为 H 时，则与 X 形成取代的环己基、环庚基，该环己基是三取代的环己基以外的环己基。 当 Y 为 H 与 X 形成取代的环己基、环庚基时，环己基不是含有 CH3、i-Pr 和 (CH2)2CO2 基团或 、i-Pr 和 ( )3NH2 的三取代环己基、 或其盐或酯。
• New Monocyclic, Bicyclic, and Tricyclic Ethynylcyanodienones as Activators of the Keap1/Nrf2/ARE Pathway and Inhibitors of Inducible Nitric Oxide Synthase
  作者：Wei Li、Suqing Zheng、Maureen Higgins、Rocco P. Morra、Anne T. Mendis、Chih-Wei Chien、Iwao Ojima、Dale F. Mierke、Albena T. Dinkova-Kostova、Tadashi Honda

  DOI：10.1021/acs.jmedchem.5b00393

  日期：2015.6.11

  A monocyclic compound 3 (3-ethynyl-3-methyl-6-oxocyclohexa-1,4-dienecarbonitrile) is a highly reactive Michael acceptor leading to reversible adducts with nucleophiles, which displays equal or greater potency than the pentacyclic triterpenoid CDDO in inflammation and carcinogenesis related assays. Recently, reversible covalent drugs, which bind with protein targets but not permanently, have been gaining attention because of their unique features. To explore such reversible covalent drugs, we have synthesized monocyclic, bicyclic, and tricyclic compounds containing 3 as an electrophilic fragment and evaluated them as activators of the Keap1/Nrf2/ARE pathway and inhibitors of iNOS. Notably, these compounds maintain the unique features of the chemical reactivity and biological potency of 3. Among them, a monocyclic compound 5 is the most potent in these assays while a tricyclic compound 14 displays a more robust and specific activation profile compared to 5. In conclusion, we demonstrate that 3 is a useful electrophilic fragment for exploring reversible covalent drugs.
• ACETYLENIC CYANOENONES AS THERAPEUTICS FOR INFLAMMATION AND CARCINOGENESIS
  申请人：Honda Tadashi

  公开号：US20180134654A1

  公开（公告）日：2018-05-17

  The present invention provides a compound having the structure: wherein X is C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, cyano, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenylaryl, alkenylheteroaryl, alkynylaryl, alkynylheteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, heteroaryloxy, acyl, alkylhydroxy, alkylamino, alkenylamino, alkynylamino, amido, carboxyl, or carboxyl ester, or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with Y, Y is H or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with X, or forms an unsubstituted or substituted monocycle with Z; and Z is H or forms an unsubstituted or substituted monocycle with Y; wherein when X and Y are both H, then X is C 2 alkenyl or C 2 alkynyl, and when Y is H forms a substituted cyclohexyl, cycloheptyl with X, the cyclohexyl is other than a trisubstituted cyclohexyl bearing CH 3 , i-Pr and (CH 2 ) 2 CO 2 CH 3 groups or CH 3 , i-Pr and (CH 2 ) 3 NH 2 , or a salt or ester thereof.
• [EN] ACETYLENIC CYANOENONES AS THERAPEUTICS FOR INFLAMMATION AND CARCINOGENESIS<br/>[FR] CYANOÉNONES ACÉTYLÉNIQUES UTILISÉES COMME AGENTS THÉRAPEUTIQUES POUR LE TRAITEMENT D'UNE INFLAMMATION ET DE LA CARCINOGENÈSE
  申请人：UNIV NEW YORK STATE RES FOUND

  公开号：WO2016168450A1

  公开（公告）日：2016-10-20

  The present invention provides a compound having the structure: wherein X is C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, cyano, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenylaryl, alkenylheteroaryl, alkynylaryl, alkynylheteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, heteroaryloxy, acyl, alkylhydroxy, alkylamino, alkenylamino, alkynylamino, amido, carboxyl, or carboxyl ester, or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with Y, Y is H or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with X, or forms an unsubstituted or substituted monocycle with Z; and Z is H or forms an unsubstituted or substituted monocycle with Y; wherein when X and Y are both H, then X is C2 alkenyl or C2 alkynyl, and when Y is H forms a substituted cyclohexyl, cycloheptyl with X, the cyclohexyl is other than a trisubstituted cyclohexyl bearing CH3, i-Pr and (CH2)2CO2CH3 groups or CH3, i-Pr and (CH2)3NH2, or a salt or ester thereof.