tert-butyl-substituted cyclooctatetraenes

Journal Article · Fri May 08 00:00:00 EDT 1981 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00323a001· OSTI ID:6197499

Miller, M J ^[1]; Lyttle, M H; Streitwieser, A Jr

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1. Univ. of California, Berkeley

Reaction of cyclooctatetraene (COT) with tert-butyllithium provides a convenient synthesis of tert-butylcyclooctatetraene, 4. As a byproduct of the reaction mixture, 1,4-di-tert-butylcyclooctatriene has been isolated and converted to 1,4-di-tert-butylcyclooctatetraene, 5, by deprotonation with potassium amide and oxidation with iodine. An independent synthesis of 5 was developed from 9-oxabicyclo(6.1.0)octa-2,4,6-triene (cyclooctatetraene oxide), 9. The highly substituted compound 1,3,5,7-tetra-tert-butylcyclooctatetraene (6) has been prepared in 24% overall yield in four steps. The acetylenic ketone 27, prepared from (tert-butylethynyl)copper and pivaloyl chloride, undergoes condensation with dimethyl malonate to give the pyrone ester 28. This ester undergoes facile hydrolysis and decarboxylation in hot concentrated sulfuric acid to yield 4,6-di-tert-butyl-2H-pyran-2-one (22) which is converted to 6 in one step by photolysis in dilute solution.

• DOE Contract Number: W-7405-ENG-48
• OSTI ID: 6197499
• Journal Information: J. Org. Chem.; (United States), Vol. 46:10
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CYCLOALKENES
CHEMICAL PREPARATION
PHOTOLYSIS
LITHIUM COMPOUNDS
ORGANOMETALLIC COMPOUNDS
ALKALI METAL COMPOUNDS
ALKENES
CHEMICAL REACTIONS
DECOMPOSITION
HYDROCARBONS
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
SYNTHESIS
400500* - Photochemistry
400201 - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)