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Title: Dimerization of Indanedioneketene to Spiro-oextanone: A Theoretical Study

Abstract

Indanedioneketene, a compound resulting from the thermal degradation of the phenyliodonium ylide of lawsone, dimerises quantitatively to a spiro-oxetanone derivative, a key compound for further transformations. A theoretical DFT study of this unusual for α-oxoketenes [2+2] cyclization reaction both in the gas phase and in dichloromethane solution, provides support for a) a single-step, transitionstate (involving a four-membered cyclic ring) charge controlled, concerted mechanism, and b) a [4+2] cyclization reaction, not observed but studied theoretically in this study. A parallel study of an open chain α,α'-dioxoketene dimerization explains the difference in the stability and reactivity observed experimentally between the cyclic and open chain products.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
988612
Report Number(s):
PNNL-SA-72271
Journal ID: ISSN 0022-3263; JOCEAH; KC0301020; TRN: US201018%%572
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Organic Chemistry
Additional Journal Information:
Journal Volume: 75; Journal Issue: 16; Journal ID: ISSN 0022-3263
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHAINS; CYCLIZATION; DIMERIZATION; METHYLENE CHLORIDE; STABILITY; THERMAL DEGRADATION; TRANSFORMATIONS

Citation Formats

Bakalbassis, Evangelos G, Malamidou-Xenikaki, Elizabeth, Spyroudis, Spyros, and Xantheas, Sotiris S. Dimerization of Indanedioneketene to Spiro-oextanone: A Theoretical Study. United States: N. p., 2010. Web. doi:10.1021/jo100500u.
Bakalbassis, Evangelos G, Malamidou-Xenikaki, Elizabeth, Spyroudis, Spyros, & Xantheas, Sotiris S. Dimerization of Indanedioneketene to Spiro-oextanone: A Theoretical Study. United States. https://doi.org/10.1021/jo100500u
Bakalbassis, Evangelos G, Malamidou-Xenikaki, Elizabeth, Spyroudis, Spyros, and Xantheas, Sotiris S. 2010. "Dimerization of Indanedioneketene to Spiro-oextanone: A Theoretical Study". United States. https://doi.org/10.1021/jo100500u.
@article{osti_988612,
title = {Dimerization of Indanedioneketene to Spiro-oextanone: A Theoretical Study},
author = {Bakalbassis, Evangelos G and Malamidou-Xenikaki, Elizabeth and Spyroudis, Spyros and Xantheas, Sotiris S},
abstractNote = {Indanedioneketene, a compound resulting from the thermal degradation of the phenyliodonium ylide of lawsone, dimerises quantitatively to a spiro-oxetanone derivative, a key compound for further transformations. A theoretical DFT study of this unusual for α-oxoketenes [2+2] cyclization reaction both in the gas phase and in dichloromethane solution, provides support for a) a single-step, transitionstate (involving a four-membered cyclic ring) charge controlled, concerted mechanism, and b) a [4+2] cyclization reaction, not observed but studied theoretically in this study. A parallel study of an open chain α,α'-dioxoketene dimerization explains the difference in the stability and reactivity observed experimentally between the cyclic and open chain products.},
doi = {10.1021/jo100500u},
url = {https://www.osti.gov/biblio/988612}, journal = {Journal of Organic Chemistry},
issn = {0022-3263},
number = 16,
volume = 75,
place = {United States},
year = {Fri Aug 20 00:00:00 EDT 2010},
month = {Fri Aug 20 00:00:00 EDT 2010}
}