3-ethoxycarbonyl-1-azaazulen-2-one | 1210-27-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 3-ethoxycarbonyl-1-azaazulen-2-one
• 英文别名: Cyclohepta[b]pyrrole-3-carboxylic acid, 1,2-dihydro-2-oxo-, ethyl ester；ethyl 2-oxo-1H-cyclohepta[b]pyrrole-3-carboxylate
• CAS: 1210-27-1
• 化学式: C₁₂H₁₁NO₃
• 分子量: 217.224
• InChiKey: PJOLVSCMENMWFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 海关编码：
  2933790090

反应信息

• 作为反应物：
  描述：

  3-ethoxycarbonyl-1-azaazulen-2-one 在 三氯氧磷 作用下， 反应 2.0h， 以73%的产率得到ethyl 2-chlorocycloheptapyrrole-3-carboxylate
  参考文献：
  名称：

  Synthesis of 2-Arylamino-1-azaazulenes

  摘要：

  A series of 2-arylamino-l-azaazulenes were synthesized by the Buchwald-Hartwig cross coupling reaction. The resulting compounds were characterized by H-1 NMR, C-13 NMR, HRMS analyses, and elemental analysis. X-Ray crystallographic analysis revealed that 2-(1-naphthylamino)-1-azaazuleneexists in dimeric form with two intermolecular N-H center dot center dot center dot N hydrogen bonds in its crystal structure.

  DOI：

  10.3987/com-16-s(s)48
• 作为产物：
  描述：

  环庚三烯酚酮 在 ammonium hydroxide 、 乙醇 、 sodium 作用下， 以 水 为溶剂， 反应 49.0h， 生成 3-ethoxycarbonyl-1-azaazulen-2-one
  参考文献：
  名称：

  1-氮杂氮烯和氮杂烯组成的线性π共轭分子的合成与性质

  摘要：

  使用Sonogashira-Hagihara交叉偶联反应，然后用浓磷酸脱羧，合成了两种化合物6-（1-（氮杂氮烯-2-基）乙炔基氮杂烯（8）和6-（2-氮杂烯基）乙炔基氮杂烯（10）。化合物8和10的特征在于1 H和13 C核磁共振（NMR）光谱，质谱，紫外可见（UV-Vis）光谱，循环伏安法和密度泛函理论（DFT）计算。根据该结果，证实两种化合物在其整个分子结构中均具有π共轭。化合物8和10的酸响应度使用UV-Vis和1 H NMR光谱进行了评估。发现化合物8对三氟乙酸高度敏感，其1-氮杂氮烯基部分充当碱。当与过量的三氟乙酸混合时，化合物10产生z阳离子。

  DOI：

  10.1016/j.tet.2019.130658

文献信息

• Synthesis and Antiallergic Activity of Novel Azaazulene Derivatives.
  作者：Michiko NAGAHARA、Jun NAKANO、Mitsuo MIMURA、Tsutomu NAKAMURA、Katsuhiro UCHIDA

  DOI：10.1248/cpb.42.2491

  日期：——

  Various azaazulene derivatives were synthesized and their antiallergic activity was examined. The structure-activity relationship among various derivatives modified by introducing substituents at the 1-,2-, or 3-position of the azaazulene ring was investigated. The inhibitory activities on allergic histamine release of the compounds bearing a 5-tetrazolyl group at the 3-position were more potent than

  合成了各种氮杂氮烯衍生物，并检查了它们的抗过敏活性。研究了通过在氮杂氮烯环的1-，2-或3-位引入取代基进行修饰的各种衍生物之间的构效关系。在3-位带有5-四唑基的化合物对过敏性组胺释放的抑制活性比具有其他基团（CN，COOH和CHO）的相应化合物更有效。在2-位被氨基，叠氮化物和羧甲基氨基取代的化合物表现出很强的抑制活性。在1位具有各种苯基烷基的化合物比具有其他取代基的化合物具有更高的活性。在氮杂氮烯环的1-，2-或3-位带有取代基的化合物中，
• Reactions of diethyl azulene-1,3-dicarboxylate derivatives and 1-azaazulene derivatives with Grignard reagents, and alkyl- and aryllithium
  作者：Tadayoshi Morita、Noritaka Abe、Kahei Takase

  DOI：10.1039/b003078n

  日期：——

  Reactions of diethyl azulene-1,3-dicarboxylate (1) and diethyl 2-chloroazulene-1,3-dicarboxylate (11) with Grignard reagents, followed by dehydration with tetrachloro-1,2-benzoquinone, gave 2-, 4,- and 6-substituted addition–oxidation products. Grignards reagents have a tendency to react with 1 at the positions in the order of 2 > 4 > 6, while steric hindrance has a greater influence at the positions in order of 2 > 4 > 6. Reactions of 1 and 11 with phenyllithium and methyllithium gave similar results. On the other hand, on the reaction of diethyl 2-methoxyazulene-1,3-dicarboxylate (15), Grignard reagents attacked preferentially at the methoxy group, and 2-substituted products were obtained. Use of excess molar equivalents of Grignard reagents led to diaryl-substituted products. Reaction of 2-chloro-1-azaazulenes with Grignard reagents also gave similar addition–oxidation products, and reacted at the positions in the order 8 ≫ 4 > 6, whereas reaction of 2-methoxy-1-azaazulene with a Grignard reagent gave 1-azaazulen-2(1H)-one.

  二乙基azulene-1,3-二羧酸酯（1）和二乙基2-氯azulene-1,3-二羧酸酯（11）与格氏试剂反应，随后与四氯-1,2-苯并醌脱水，生成了2-、4-和6-取代的加成-氧化产物。格氏试剂倾向于按照2 > 4 > 6的顺序与1反应，而立体位阻在2 > 4 > 6的位置上有更大的影响。1和11与苯基锂和甲基锂的反应结果相似。另一方面，二乙基2-甲氧基azulene-1,3-二羧酸酯（15）的反应中，格氏试剂优先攻击甲氧基，得到2-取代产物。使用过量的格氏试剂会导致二芳基取代产物的形成。2-氯-1-氮杂azulenes与格氏试剂的反应也生成类似的加成-氧化产物，反应位置的顺序为8 ≫ 4 > 6，而2-甲氧基-1-氮杂azulene与格氏试剂的反应则生成1-氮杂azulen-2(1H)-酮。
• Cyclohepta[b]pyrrole derivatives
  申请人：Ayerst, McKenna & Harrison Inc.

  公开号：US04337265A1

  公开（公告）日：1982-06-29

  Disclosed herein are 1,2-dihydro-2-oxo(or 2-thioxo)cyclohepta[b]-pyrrole-1-acetic acid derivatives having optional substitution at positions 3, on the cycloheptatriene ring and on the acetic acid side chain. The compounds are aldose reductase inhibitors and thus are useful for treating diabetic complications.

  本文披露了具有选择性取代基的1,2-二氢-2-氧(或2-硫)环庚七[b]-吡咯-1-乙酸衍生物，取代基位于环庚三烯环和乙酸侧链上。这些化合物是醛糖还原酶抑制剂，因此可用于治疗糖尿病并发症。
• Studies on Heterocyclic Analogs of Azulene. VIII. Reaction of 2-Alkoxycyclohepta[6]pyrroles with Dimethyl Acetylenedicarboxylate
  作者：Noritaka Abe、Tarozaemon Nishiwaki

  DOI：10.1246/bcsj.54.1277

  日期：1981.4

  2-Alkoxycyclohepta[b] pyrroles reacted with dimethyl acetylenedicarboxylate to give tetramethyl 2-alkoxy-3H-2a-azacyclopenta[ef]heptalene-3,4,5,6-tetracarboxylates in benzene and dialkyl 2-(2-alkoxycyclohepta[b]pyrrol-1-yl)fumarate in alcoholic solvents.

  2-烷氧基环庚 [b] 吡咯与乙炔二羧酸二甲酯反应，在苯中生成 2-烷氧基-3H-2a-氮杂环戊二烯四甲酯 [ef]heptalene-3,4,5,6-tetracarboxylates 和二烷基 2-(2-alkoxycyclohepta[b]醇溶剂中的吡咯-1-基)富马酸酯。
• Palladium-Catalyzed Heteroarylamination of Ethyl 2-Chloro-1-azaazulene-3-carboxylate and Annulation of Heteroarylamino-1-azaazurenes
  作者：Noritaka Abe、Kazuya Koizumi、Noriko Yamauchi、Hiroyuki Fujii、Takeo Konakahara、Kunitaka Shimabara、Aya Takemoto、Shinya Yamazaki、Masaki Kurosawa

  DOI：10.3987/com-08-s(d)6

  日期：——

  The palladium catalyzed heteroarylamination of ethyl 2-chloro-1-azaazulene-3-carboxylate was achieved using a catalyst based on Pd-2(dba)(3) / Xantphos system. Treatment of ethyl 2-(heteroarylamino)-1-azaazulene-3-carboxylates with a PPA-POCl3 mixture gave corresponding annulation products. 2-(2-Benzothiazolylamino)-1-azaazulene (3h) showed anticancer activity against HeLa S3 cells (IC50: 6.5 mu M).