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具有混合发色团的双环[2.2.2]辛-5-烯-2-酮光转化过程中形成异常稳定的乙烯酮。

Formation of an exceptionally stable ketene during phototransformations of bicyclo[2.2.2]oct-5-en-2-ones having mixed chromophores.

作者信息

Ghosh Asitanga

机构信息

Deptartment of Chemistry, Hooghly Mohsin College, Chinsurah, Hooghly, West Bengal, 712101, India.

出版信息

Beilstein J Org Chem. 2020 Sep 15;16:2297-2303. doi: 10.3762/bjoc.16.190. eCollection 2020.

DOI:10.3762/bjoc.16.190
PMID:33014169
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7509375/
Abstract

Photochemical reactions of bicyclo[2.2.2]oct-5-en-2-ones having mixed chromophores like a 5,6 dibenzoyl moiety and bulky electron-deficient substituents like phenyl or isopropenyl at the bridgehead position were analyzed for the first time in different solvents and upon irradiation with different wavelengths. In all cases, a regioselective photoinduced 1,5-phenyl migration leading to vinyl ketenes from the more congested site of the molecule to the less congested one has been observed. The ketenes were exceptionally stable both in air and solution. Its stability studies in acetonitrile through time-dependent UV absorption spectra revealed that it remained almost unchanged at least for a couple of weeks.

摘要

首次在不同溶剂中并使用不同波长进行辐照，分析了具有混合发色团（如5,6-二苯甲酰基部分）和桥头位置带有大体积缺电子取代基（如苯基或异丙烯基）的双环[2.2.2]辛-5-烯-2-酮的光化学反应。在所有情况下，均观察到区域选择性光诱导的1,5-苯基迁移，导致乙烯基烯酮从分子中拥挤程度较高的位点迁移至拥挤程度较低的位点。这些烯酮在空气和溶液中都异常稳定。通过时间相关的紫外吸收光谱对其在乙腈中的稳定性研究表明，它至少在几周内几乎保持不变。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/1a06bee3b081/Beilstein_J_Org_Chem-16-2297-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/7ef71db4bef3/Beilstein_J_Org_Chem-16-2297-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/e6700bf8a009/Beilstein_J_Org_Chem-16-2297-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/2bb615da26d3/Beilstein_J_Org_Chem-16-2297-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/f0c9cf2b281e/Beilstein_J_Org_Chem-16-2297-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/cb96d6cfb677/Beilstein_J_Org_Chem-16-2297-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/c5c9f18c612d/Beilstein_J_Org_Chem-16-2297-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/54a808b417a2/Beilstein_J_Org_Chem-16-2297-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/3b0bb09fcd1b/Beilstein_J_Org_Chem-16-2297-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/1a06bee3b081/Beilstein_J_Org_Chem-16-2297-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/7ef71db4bef3/Beilstein_J_Org_Chem-16-2297-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/e6700bf8a009/Beilstein_J_Org_Chem-16-2297-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/2bb615da26d3/Beilstein_J_Org_Chem-16-2297-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/f0c9cf2b281e/Beilstein_J_Org_Chem-16-2297-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/cb96d6cfb677/Beilstein_J_Org_Chem-16-2297-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/c5c9f18c612d/Beilstein_J_Org_Chem-16-2297-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/54a808b417a2/Beilstein_J_Org_Chem-16-2297-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/3b0bb09fcd1b/Beilstein_J_Org_Chem-16-2297-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2273/7509375/1a06bee3b081/Beilstein_J_Org_Chem-16-2297-g010.jpg

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