Synthesis of 2-Amino-4-arylazulenes from 8-Aryl-2H-cyclohepta[b]furan-2-ones and Transformation into 6-Aryl-7H-naphth[3,2,1-cd]azulen-7-ones.

IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC
The Journal of Organic Chemistry Pub Date : 2024-11-15 Epub Date: 2024-11-04 DOI:10.1021/acs.joc.4c01394
Taku Shoji, Daichi Ando, Masayuki Iwabuchi, Atom Hamasaki, Shigeki Mori, Tetsuo Okujima, Ryuta Sekiguchi, Shunji Ito
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引用次数: 0

Abstract

2-Amino-4-arylazulene derivatives were prepared from 8-aryl-2H-cyclohepta[b]furan-2-ones, which were converted into 6-aryl-7H-naphth[3,2,1-cd]azulen-7-ones through a several step process. The reaction of 8-aryl-2H-cyclohepta[b]furan-2-ones bearing an ester group at the 3-position with malononitrile in the presence of triethylamine afforded 2-amino-4-arylazulenes. The prepared 2-amino-4-arylazulenes were converted to the corresponding 2-chloro derivatives by the Sandmeyer reaction, which were subsequently transformed into 2,4-diarylazulenes by Suzuki-Miyaura coupling with various aryl boronic acids. 2,4-Diarylazulenes underwent intramolecular cyclization between aryl and cyano groups by Brønsted acid to give 6-aryl-7H-naphth[3,2,1-cd]azulen-7-ones. UV/vis spectral analysis revealed that 6-aryl-7H-naphth[3,2,1-cd]azulen-7-one with a N,N-dimethylaminophenyl group at the 6-position exhibited a broad and strong absorption band in the visible region due to intramolecular charge transfer. Furthermore, 6-aryl-7H-naphth[3,2,1-cd]azulen-7-ones exhibited halochromism in 30% CF3CO2H/CH2Cl2. Although fluorescence was not observed in solution, 8-aryl-2H-cyclohepta[b]furan-2-ones with an ester function were found to fluoresce in the solid state. 6-Aryl-7H-naphth[3,2,1-cd]azulen-7-ones also displayed spectral changes with good reversibility under the electrochemical redox conditions.

Abstract Image

从 8-芳基-2H-环庚烷并[b]呋喃-2-酮合成 2-氨基-4-芳基偶氮烯并转化为 6-芳基-7H-萘并[3,2,1-cd]偶氮烯-7-酮。
2-Amino-4-arylazulene 衍生物由 8-芳基-2H-环庚烷并[b]呋喃-2-酮制备而成,通过几个步骤将其转化为 6-芳基-7H-萘并[3,2,1-cd]氮杂烯-7-酮。在三乙胺存在下,8-芳基-2H-环庚烷并[b]呋喃-2-酮的 3 位上带有酯基,与丙二腈反应生成 2-氨基-4-芳基偶氮烯。制备的 2-氨基-4-芳基唑烯通过桑德迈耶反应转化为相应的 2-氯衍生物,然后通过与各种芳基硼酸的铃木-宫浦偶联转化为 2,4-二芳基唑烯。在布氏酸的作用下,2,4-二芳基唑烯在芳基和氰基之间发生分子内环化反应,生成 6-芳基-7H-萘并[3,2,1-cd]氮杂烯-7-酮。紫外/可见光谱分析显示,6-芳基-7H-萘并[3,2,1-cd]氮杂烯-7-酮的 6 位上带有 N,N-二甲基氨基苯基,由于分子内电荷转移,在可见光区域显示出宽而强的吸收带。此外,6-芳基-7H-萘并[3,2,1-cd]氮杂烯-7-酮在 30% CF3CO2H/CH2Cl2 中显示出晕色。虽然在溶液中未观察到荧光,但发现具有酯功能的 8-芳基-2H-环庚烷并[b]呋喃-2-酮在固态下会发出荧光。在电化学氧化还原条件下,6-芳基-7H-萘并[3,2,1-cd]氮杂烯-7-酮也显示出具有良好可逆性的光谱变化。
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来源期刊
The Journal of Organic Chemistry
The Journal of Organic Chemistry 化学-有机化学
CiteScore
6.20
自引率
11.10%
发文量
1467
审稿时长
2 months
期刊介绍: The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.
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