Photochemistry of α,β-unsaturated thiones

Addition to electron-rich olefins from T1

V. Pushkara Rao, Vaidhyanathan Ramamurthy

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

1,1,3-Trimethyl-2-thioxo-l,2-dihydronaphthalene (1) adds to electron-rich olefins upon excitation to either S2 (ππ*) or S1 (nπ*) states. Excitation to S2 level resulted in the same mixture of products, namely thietane and 1,4-dithiane, as on excitation to S1 level. Addition occurs to the thiocarbonyl function and not to the carbon-carbon double bond. The addition is site-specific, and the formation of thietane is regiospecific. The ratio of thietane to 1,4-dithiane in the product mixture is dependent on the concentration of the thioenone. The addition is suggested to originate from the lowest triplet state (T1) and involves diradical intermediates.

Original languageEnglish
Pages (from-to)327-332
Number of pages6
JournalJournal of Organic Chemistry
Volume53
Issue number2
StatePublished - Dec 1 1988
Externally publishedYes

Fingerprint

Thiones
Photochemical reactions
Alkenes
Carbon
Electrons
1,4-dithiane

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Photochemistry of α,β-unsaturated thiones : Addition to electron-rich olefins from T1. / Pushkara Rao, V.; Ramamurthy, Vaidhyanathan.

In: Journal of Organic Chemistry, Vol. 53, No. 2, 01.12.1988, p. 327-332.

Research output: Contribution to journalArticle

@article{08b04432ffb54e278d444b5d3ff3e019,
title = "Photochemistry of α,β-unsaturated thiones: Addition to electron-rich olefins from T1",
abstract = "1,1,3-Trimethyl-2-thioxo-l,2-dihydronaphthalene (1) adds to electron-rich olefins upon excitation to either S2 (ππ*) or S1 (nπ*) states. Excitation to S2 level resulted in the same mixture of products, namely thietane and 1,4-dithiane, as on excitation to S1 level. Addition occurs to the thiocarbonyl function and not to the carbon-carbon double bond. The addition is site-specific, and the formation of thietane is regiospecific. The ratio of thietane to 1,4-dithiane in the product mixture is dependent on the concentration of the thioenone. The addition is suggested to originate from the lowest triplet state (T1) and involves diradical intermediates.",
author = "{Pushkara Rao}, V. and Vaidhyanathan Ramamurthy",
year = "1988",
month = "12",
day = "1",
language = "English",
volume = "53",
pages = "327--332",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Photochemistry of α,β-unsaturated thiones

T2 - Addition to electron-rich olefins from T1

AU - Pushkara Rao, V.

AU - Ramamurthy, Vaidhyanathan

PY - 1988/12/1

Y1 - 1988/12/1

N2 - 1,1,3-Trimethyl-2-thioxo-l,2-dihydronaphthalene (1) adds to electron-rich olefins upon excitation to either S2 (ππ*) or S1 (nπ*) states. Excitation to S2 level resulted in the same mixture of products, namely thietane and 1,4-dithiane, as on excitation to S1 level. Addition occurs to the thiocarbonyl function and not to the carbon-carbon double bond. The addition is site-specific, and the formation of thietane is regiospecific. The ratio of thietane to 1,4-dithiane in the product mixture is dependent on the concentration of the thioenone. The addition is suggested to originate from the lowest triplet state (T1) and involves diradical intermediates.

AB - 1,1,3-Trimethyl-2-thioxo-l,2-dihydronaphthalene (1) adds to electron-rich olefins upon excitation to either S2 (ππ*) or S1 (nπ*) states. Excitation to S2 level resulted in the same mixture of products, namely thietane and 1,4-dithiane, as on excitation to S1 level. Addition occurs to the thiocarbonyl function and not to the carbon-carbon double bond. The addition is site-specific, and the formation of thietane is regiospecific. The ratio of thietane to 1,4-dithiane in the product mixture is dependent on the concentration of the thioenone. The addition is suggested to originate from the lowest triplet state (T1) and involves diradical intermediates.

UR - http://www.scopus.com/inward/record.url?scp=0040050030&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0040050030&partnerID=8YFLogxK

M3 - Article

VL - 53

SP - 327

EP - 332

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -