Photochemical rearrangements of .alpha.-methylene ketones

Cormier, Russell A.; Schreiber, William L.; Agosta, William C.

doi:10.1021/ja00796a019

Cited by 50 publications

(32 citation statements)

References 3 publications

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“…55"/0,08 Torr. C13H24O (196,32) (27), 67 (26) : 0,82-0,97/Signalschar, H3C-C(2') + 2 H3C--C(6') ; 0,90-2,14/m, 2H-C(4) + 13-C(1') + H-C(2') + 2 H--C(3') + 2 H-C(4') + 2 I-I-C(5') ; 2,06/.s, 3 M--C:(l) ; 2,14-2,50/?n, 2 H--C(3). (12), 125 (12), 123 (14), 121 (16), 111 (23), 109 (26), 107 (16) 2,2,6p,nonan-7cr-ol ( 6 5 ) ; Smp.…”

Section: 90-256/m 2 H-c(3) + 2 H-c(4) + 2 H-c(5) + 2 H-c(8) + 2 Hunclassified

“…C13H24O (196,32) (17), 163 (24). 139 (17), 138 (27), 123 (52), 111 (16), 109 (23), 96 (18), 95 (44), 83 (29), 82 (58), 81 (32), 71 (24), 69 (59), 68 (27), 67 (26) 2,6a, 7u-TetrawethyZ-bicyclo[4.3.0]no~zan-7~3-oZ (55). .…”

Section: )mentioning

confidence: 99%

“…C 70,53 H 12,320/:,(kf. C 79,44 H 12,32"/0 MS.: wz/e = 196 (3, M+/C13H240), 181 (3), 178 (4), 163 (15) , 154 ( 2 3 ) , 139 (34), 138 (14), 137 (12), 125 (12), 123 (14), 121 (16), 111 (23), 109 (26), 107 (16) S, 299Os, 2935s, 2880s, 2850nr, 1480m, 1460m, 1135zq 1393s, 1382s, 1370m, 1310w, 1 2 3 5~, 1200w, 1185s, 1120m, 1 0 7 5~2 , 1040ni, 1015zw, 9 9 0~1 , 96.5ze1, 940wz, 915s, 2.6.1. 5.…”

Section: )mentioning

confidence: 99%

“…Ber. (281, 81 (26), 79 (29), 77 (20), 69 (26), 67 (24), 65 (14), 55 (31), 53 (23), 43 (14), 41 (63). ~ I R .…”

Section: Clzh19c10mentioning

confidence: 99%

“…-S u m m w y . The photochemical behaviour of y, 6and 6, &-unsaturated carbonyl compounds of the dihydro-ionone series has been studied, with special attention to the investigation of oxetane formation uevszis hydrogen abstraction.UV.-irradiation of the dihydro-P-ionone compounds with structure A (1, 7, 14, 18, 24, 29) led to isomeric ethers with structures B (2, 8, 15, 19, 25, 30), C (3,9,16, 20,26,31) and D (4, 21, 27), isomeric bicyclic alcohols with structurc E (5, 10, 17, 22, 28), and photoreduction products with structure F (6, 11, 12, 13). Photolysis of dihydro-y-ionone (32) gave a complex mixture containing fragmentation product 35, hydrocarbon 36, P-ambrinol (34), oxctanc 33, as well as dihydro-/-ionone (I) and three of its photoproducts (2, 3, 5).…”

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confidence: 99%

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Photochemische Reaktionen. 83. Mitteilung. Verbindungen der 3,4‐Dihydrojonon‐Reihe als Modelle zur Photochemie γ, δ‐ bzw. δ, ϵ‐ungesättigter Ketone und Aldehyde

Zink

Wolf

Müller

et al. 1976

Helvetica Chimica Acta

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Compounds of the 3,4-dihydro-ionone series a s models for the photochemistry of y , 6-and 6 ,~-unsaturated ketones and aldehydes. -S u m m w y . The photochemical behaviour of y, 6-and 6, &-unsaturated carbonyl compounds of the dihydro-ionone series has been studied, with special attention to the investigation of oxetane formation uevszis hydrogen abstraction.UV.-irradiation of the dihydro-P-ionone compounds with structure A (1, 7, 14, 18, 24, 29) led to isomeric ethers with structures B (2, 8, 15, 19, 25, 30), C (3, 9, 16, 20, 26, 31) and D (4, 21, 27), isomeric bicyclic alcohols with structurc E (5, 10, 17, 22, 28), and photoreduction products with structure F (6, 11, 12, 13). Photolysis of dihydro-y-ionone (32) gave a complex mixture containing fragmentation product 35, hydrocarbon 36, P-ambrinol (34), oxctanc 33, as well as dihydro-/-ionone (I) and three of its photoproducts (2, 3, 5). The dihydro-a-ionone compounds 37 and 40 gave mixtures of fragmentation products and the oxetanes 38 and 41. Irradiation of t h e side-chain homologues 42 and 45 yielded 43, which photo-cpclizes t o 44. I n contrast, 3,4-dihydro-3',4'-dchydro-/3-ionone (46) gave merely the isomeric open-chain trienc-ketone 47.The structures assigned to the ethers 2 , 3 , 3 3 , 3 8 and to the alcohols 5,10,13 could be confirmed by chemical reactions and mutual interconversions. The structure of the ether 21 had to be established by X-ray analysis, details of which are described.A novel intramolecular hydrogen transfer is involved in formation of etlicrs B. The photocyclization A + D probably proceeds by addition of the carbonyl-C atom to the double bond ( A + h ) , followed by methyl (1 + 2)-shift (h + i). Process A --j. h may also be involved in formation of compounds of type C and E. 1. 1) 2)Vgl. M . P. Zink, Diss. ETHZ, Nr. 5498 (197.5); auszugsu-eise vorgctragcn an der Herbstversammlung der Schweizerischen Chemischen Gcsellschaft in Lugano am 19. Oktober 1973 [2].Fur die Numericrung der in dieser Mitteilung bcschriebenen Verbindungen siehc Schema 27.

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Section: 90-256/m 2 H-c(3) + 2 H-c(4) + 2 H-c(5) + 2 H-c(8) + 2 Hunclassified