Dérivés Du Triméthyl-1,8,8 Bicyclo[3,2,1]octane: I. La Réaction Du Diazométhane Avec La Camphoquinone

Favre, H.; Marinier, Bernard; Richer, J-C.

doi:10.1139/v56-169

Cited by 10 publications

(2 citation statements)

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“…A monoenol ether of type 17 resulted however, possibly arising by an acid-catalysed cleavage of the product envisaged as intermediate. 21 and 22 have been reported previously [I 11.…”

Section: ")mentioning

confidence: 55%

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Photochemical Reactions. Part 64 [1]. The photochemistry of 3‐alkyl‐cyclopent‐2‐en‐ones

Reinfried

Belluš

Schaffner

1971

Helvetica Chimica Acta

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SociCtC suisse de chimie, B%le ~ Societa svizzera di chimica, Basilea Nachdruck verboten -Tous droits reserves -Printed by Birkhauser AG., Basel, Switzerland Erscheint 9mal jahrlich -Parait 9 fois par an Photochemical ReactionsThe Photochemistry of 3-Alkyl-cyclopent-2-en-ones by R. Reinfriedla), D. BelluLlb), and K. Schaffnerlc) Summary. On ultraviolet irradiation in toluene, cyclopent-2-en-one (la) and 3-methylcyclopent-2-en-one (lb) undergo dimerisation (+ 3 a, b, 4 b), whereas 3-l-butyl-cyclopent-2-en-one (le) and the bicyclo[3.2.l]octenone 2a only react with the solvent (+ 5e-7e, 8-10). The 3-ethyl-(lc) and 3-isopropyl-cyclopent-2-en-ones (Id) afford by dimerisation products 3c, d, 4c and by reaction with the solvent 5c,d, 6c,d, 7d. The p-methoxy-enones If and 2b are unreactive under comparable irradiation conditions. The head-to-head cyclobutane dimer 3 b ( H H ) by separate irradiation at < 3400 in toluene, is reconverted to Ib. By similar irradiation each of the head-totail dimers 3b (anti-and syn-HT) and also the unsaturated dimer 4 b give a new isomer of unknown structure besides small amounts of monomer l b and relatively large amounts of insoluble material.The photoreactions of lb-e can be quenched by naphthalene. Stern-Volmer plots ior the quenching of the dimers of lb, l c , and Id, and of 3-t-butylcyclopentanone (5e) and the dihydro dimer 7e are linear and within each experiment, the slopes satisfactorily coincide, whereas the slope for the a-benzyl ketone 6c is distinctly greater than that for the dimers 3c. A similar differentiation, although less pronounced, is found between the benzyl ketones 6d and b e and the respective accompanying products.We have previously shown that triplet-excited cyclohexenones, such as 10-methyld1~g-octal-2-one and testosterone, readily add toluene to form a-benzyl ketones [3]. In preliminary experiments, the formation of similar products and of dihydro dimers and bibenzyl was observed when 3-t-butyl-cyclopent-2-en-one (1 e) and 5,8, S-trimethylbicyclo[3.2.l]oct-3-en-2-one (2 a) were irradiated in toluene solution 2). A recent paper by Mark et al. [4] on the photodimerisation of 3-methyl-cyclopent-2-en-one now prompts us to report our results on the photochemistry of the cyclopentenones la-f and the bicyclo~3.2.l]octenones 2a and 2b in toluene solution. Irradiation of Cyclopentenones la-f and of Bicyclo[3.2. lloctenones 2 a and2b in Toluene Solution. The Table summarises the approximate percentages of products obtained in representative photolyses (n --f n* excitation) of the six enones la-e and 2a in toluene solution (cf. also Chart 1). Cyclopent-2-en-one (la) gave only the anti-HH and anti-HT cyclobutane dimers3), as previously reported by Eaton [S] 2,Cf. [3b], footnote 14. for the photodimerisation of l a in other solvents, and no products due to reaction with the solvent could be observed. Similarly, the 3-methyl-enone l b formed only dimers, whereas the 3-t-butyl-enone 1 e did not undergo dimerisation but afforded the dihydro (5e) and benzyl ketone (6e) d...

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“…A monoenol ether of type 17 resulted however, possibly arising by an acid-catalysed cleavage of the product envisaged as intermediate. 21 and 22 have been reported previously [I 11.…”

Section: ")mentioning

confidence: 55%

“…?-Methoxy-cyclopent-Z-en-one (If) and (&)-5,8,8- Trinzethyl-4-lnethoxyy-bicyclo[3.2. l]oct-3-en-2one (2b) [21] [23j. 0 .…”

mentioning

confidence: 99%