Photochemical transformations of cis-1,2-dibenzoylalkenes

Journal Article · Tue Jan 01 04:00:00 EST 1980 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo01307a012· OSTI ID:6158336

Lahiri, S; Dabral, V; Chauhan, S M.S.; Chakachery, E; Kumar, C V; Scaiano, J C; George, M V

Photorearrangements of cis-1,2-dibenzoylalkenes such as 2,3-dibenzoylbicyclo(2.2.2)octa-2,5-diene (9), 2.3-dibenzoylbicyclo(2.2.2)oct-2-ene (21), 2,3-dibenzoylbicyclo(2.2.1)hept-2-ene (28), and 2,3-dibenzoylbicyclo-(2.2.1)hepta-2,5-diene (35) are reported. Irradiation of 9 in methanol gives a mixture of isomeric esters 13 (69%) and 14 (1%), whereas in benzene a mixture of carboxylic acids 10 (26%) and 11 (6%) and loctone 12 (23%) is formed. Similar rearrangements have been observed in the case of 21 and 28. Irradiation of 35 in benzene, however, gives mostly the quadricyclane 36. Laser flash-photolysis studies have shown that diradical intermediates such as 18 and 19 may be involved in the transformation of 9 to the different products. Similar diradical intermediates have been postulated in the rearrangements of 21 and 28.

• Research Organization: Indian Inst. of Tech., Notre Dame
• OSTI ID: 6158336
• Journal Information: J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 45; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ALKENES
CARBOXYLIC ACIDS
CHEMISTRY
CYCLOALKENES
DATA
DIENES
ESTERS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
PHOTOCHEMISTRY
POLYENES