Abstract
The higher excited-state reactions of sterically encumbered thioketenes 1a-d in solution were investigated. Substituted thiiranes, thio esters, thioacetophenones, and 1,2-diones are formed on photoexcitation of thioketenes in hydroxylic and nonhydroxylic solvents. Thioketenes while unreactive upon excitation to S1 produce thiiranylidene carbene and zwitterionic intermediates upon excitation to S2. The reactive state is identified to be S2 (ππ*). The excited thioketene resists carbon monosulfide elimination but undergoes rearrangement. The photobehavior of thioketenes, established in solution for the first time, differs significantly from that of ketenes, and it cannot be extrapolated from that of structurally analogous ketenes and allenes.
| Original language | English |
|---|---|
| Pages (from-to) | 4799-4805 |
| Number of pages | 7 |
| Journal | Journal of Organic Chemistry |
| Volume | 50 |
| Issue number | 24 |
| State | Published - Dec 1 1985 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Organic Chemistry
Cite this
Photochemical behavior of thioketenes in solution : Reaction from S2. / Singh, Sharat; Nimmesgern, Hildegard; Schaumann, Ernst; Ramamurthy, Vaidhyanathan.
In: Journal of Organic Chemistry, Vol. 50, No. 24, 01.12.1985, p. 4799-4805.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Photochemical behavior of thioketenes in solution
T2 - Reaction from S2
AU - Singh, Sharat
AU - Nimmesgern, Hildegard
AU - Schaumann, Ernst
AU - Ramamurthy, Vaidhyanathan
PY - 1985/12/1
Y1 - 1985/12/1
N2 - The higher excited-state reactions of sterically encumbered thioketenes 1a-d in solution were investigated. Substituted thiiranes, thio esters, thioacetophenones, and 1,2-diones are formed on photoexcitation of thioketenes in hydroxylic and nonhydroxylic solvents. Thioketenes while unreactive upon excitation to S1 produce thiiranylidene carbene and zwitterionic intermediates upon excitation to S2. The reactive state is identified to be S2 (ππ*). The excited thioketene resists carbon monosulfide elimination but undergoes rearrangement. The photobehavior of thioketenes, established in solution for the first time, differs significantly from that of ketenes, and it cannot be extrapolated from that of structurally analogous ketenes and allenes.
AB - The higher excited-state reactions of sterically encumbered thioketenes 1a-d in solution were investigated. Substituted thiiranes, thio esters, thioacetophenones, and 1,2-diones are formed on photoexcitation of thioketenes in hydroxylic and nonhydroxylic solvents. Thioketenes while unreactive upon excitation to S1 produce thiiranylidene carbene and zwitterionic intermediates upon excitation to S2. The reactive state is identified to be S2 (ππ*). The excited thioketene resists carbon monosulfide elimination but undergoes rearrangement. The photobehavior of thioketenes, established in solution for the first time, differs significantly from that of ketenes, and it cannot be extrapolated from that of structurally analogous ketenes and allenes.
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M3 - Article
AN - SCOPUS:33845379703
VL - 50
SP - 4799
EP - 4805
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 24
ER -