Universität zu Köln

Thrun, Frauke, Hickmann, Volker ORCID: 0000-0003-2625-0414, Stock, Christoph, Schaefer, Ansgar, Maier, Walter, Breugst, Martin ORCID: 0000-0003-0950-8858, Schloerer, Nils E., Berkesse, Albrecht and Teles, J. Henrique (2019). Technical Synthesis of 1,5,9-Cyclododecatriene Revisited: Surprising Byproducts from a Venerable Industrial Process. J. Org. Chem., 84 (21). S. 13211 - 13221. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-6904

Full text not available from this repository.

Abstract

The synthesis of 1,5,9-cyclododecatriene by selective trimerization of butadiene catalyzed by TiCl4 and ethylaluminum sesquichloride has been commercially used since 1965. Although thoroughly investigated, not all details of the mechanism are completely understood. The recent development of a new process to produce cyclododecanone involving oxidation of 1,5,9-cyclododecatriene with N2O has led to the serendipitous discovery of an array of hitherto unknown byproducts, formed in the trimerization of butadiene: eleven tricyclic C12H20 and one tetracyclic C12H18 hydrocarbons, three of which had never been described before. The identification of these byproducts became possible by using a combination of chemical enrichment, high-resolution distillation, C-13-2D-INADEQUATE NMR, and comparison with ab initio calculated spectra, thus demonstrating the power of these combined techniques. The identification of these byproducts contributes to a better understanding of the mechanism of this centrally important reaction.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Thrun, Frauke UNSPECIFIED UNSPECIFIED UNSPECIFIED Hickmann, Volker UNSPECIFIED orcid.org/0000-0003-2625-0414 UNSPECIFIED Stock, Christoph UNSPECIFIED UNSPECIFIED UNSPECIFIED Schaefer, Ansgar UNSPECIFIED UNSPECIFIED UNSPECIFIED Maier, Walter UNSPECIFIED UNSPECIFIED UNSPECIFIED Breugst, Martin UNSPECIFIED orcid.org/0000-0003-0950-8858 UNSPECIFIED Schloerer, Nils E. UNSPECIFIED UNSPECIFIED UNSPECIFIED Berkesse, Albrecht UNSPECIFIED UNSPECIFIED UNSPECIFIED Teles, J. Henrique UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-129443
DOI:	10.1021/acs.joc.9b01633
Journal or Publication Title:	J. Org. Chem.
Volume:	84
Number:	21
Page Range:	S. 13211 - 13221
Date:	2019
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-6904
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ETHANOADAMANTANE; REARRANGEMENT; CHEMISTRY; ALKENES; OLEFINS Multiple languages Chemistry, Organic Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/12944