The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F22%3A00126427" target="_blank" >RIV/00216224:14310/22:00126427 - isvavai.cz</a>

Alternative codes found

RIV/00216275:25310/22:39918915

Result on the web

<a href="https://link.springer.com/article/10.1007/s43630-022-00238-8" target="_blank" >https://link.springer.com/article/10.1007/s43630-022-00238-8</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1007/s43630-022-00238-8" target="_blank" >10.1007/s43630-022-00238-8</a>

Result language

angličtina

Original language name

The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol

Original language description

Irradiation of coumarin-3-carboxylic acid in acetonitrile and methanol solutions at 355 nm results in complex multistep photochemical transformations, strongly dependent on the solvent properties and oxygen content. A number of reaction intermediates, which themselves undergo further (photo)chemical reactions, were identified by steady-state and transient absorption spectroscopy, mass spectrometry, and NMR and product analyses. The triplet excited compound in acetonitrile undergoes decarboxylation to give a 3-coumarinyl radical that traps molecular oxygen to form 3-hydroxycoumarin as the major but chemically reactive intermediate. This compound is oxygenated by singlet oxygen, produced by coumarin-3-carboxylic acid sensitization, followed by a pyrone ring-opening reaction to give an oxalic acid derivative. The subsequent steps lead to the production of salicylaldehyde, carbon monoxide, and carbon dioxide as the final products. When 3-coumarinyl radical is not trapped by oxygen in degassed acetonitrile, it abstracts hydrogen from the solvent and undergoes triplet-sensitized [2 + 2] cycloaddition. The reaction of 3-coumarinyl radical with oxygen is largely suppressed in aerated methanol as a better H-atom donor, and coumarin is obtained as the primary product in good yields. Because coumarin derivatives are used in many photophysical and photochemical applications, this work provides detailed and sometimes surprising insights into their complex phototransformations.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2022

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

PHOTOCHEMICAL &amp; PHOTOBIOLOGICAL SCIENCES

ISSN

1474-905X

e-ISSN

—

Volume of the periodical

21

Issue of the periodical within the volume

8

Country of publishing house

GB - UNITED KINGDOM

Number of pages

15

Pages from-to

1481-1495

UT code for WoS article

000796316200001

EID of the result in the Scopus database

2-s2.0-85130102295