The isolation, structure, and stereochemistry of traversiadiene. The precursor hydrocarbon of traversianal biosynthesis

Stoessl, A.; Rock, G. L.; Stothers, J. B.

doi:10.1139/v89-199

Cited by 5 publications

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“…After thorough ether extraction, the aqueous phase was treated with NarSz05 (0.5 g in 10 mL of H20) and then acidified with concentrated HC1 solution. Ether extraction of the acidic aqueous phase afforded 2-isopropylbenzoic acid (0.70 g, 85% yield), mp 60-62°C; '3Cmr (CDC13)6: CH,, 24 '~m r (CDC13)6: 1.50 (d, J = 7 Hz, 3H), 3.67 (s, 3H), 3.71 (q, J = 7 Hz, lH), 7.33 (bs, 5H).…”

Section: -Methyl-25-diphenyl-3-hexanone (3d)mentioning

confidence: 99%

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¹³C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift

Dyllick‐Brenzinger¹,

Patel²,

Rampersad³

et al. 1990

Can. J. Chem.

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. Di-tert-butyl ketone (2a), 5,5,7,7-tetramethyl-6-undecanone (2b), and 2,4-dimethyl-2,4-diphenyl-3-pentanone (2d) have been found to undergo slow rearrangement by P-proton abstraction from the a-methyl groups upon treatment with t-BuO-/t-BuOH/> 185°C. This is in contrast to the absence of such rearrangement in cyclic systems. It is the only significant process observed for 2 a and 2b, whereas with 2 d and its monomethyl analog 22 Haller-Bauer type cleavage and an unprecedented 1,3-acyl shift from sp3 to sp2 carbon accompany the p-enolate rearrangement. The rates of 'H/'H exchange of the methyl protons in 2a, b were found to be similar to those reported for a variety of cyclic systems but this exchange does not occur in 2d, where only aryl proton exchange was observed.Key words: p-enolization, acyclic ketones, acyl shift. On a trouvC que, si on soumet la di-tert-butyl-cCtone (2a), la 5,5,7,7-tttramtthyl-undCcan-6-one (2b) ainsi que la 2,4-dimCthyl-l,4-diphCnyl-pentan-3-one ( 2 4 A un traitement par le tert-BuO-/tert-B~OH/5185~C, il se produit une transposition lente impliquant un enlkvement du proton-P des groupements mtthyles en a. Ce rtsultat est en opposition avec le fait que l'on n'observe pas de telles transpositions dans les systkmes cycliques. Cette transportation est le seul processus qui est observk partir des composCs 2 a et 2 b alors que, avec le produit 2d ainsi que son analogue monomCthylC 22, on observe un clivage de Haller-Bauer et un dCplacement acyle-1,3 sans prCcCdent du carbone sp3 vers le carbone sp2 qui accompagne la transposition de 1'Cnolate P. On a trouvC que les taux d'tchange 'H/'H des protons des groupements mCthyles des composCs 2 a et 2 b sont semblables aceux rapportts antkrieurement pourune variCtC de systkmes cycliques; toutefois, cet Cchange ne se produit pas avec le produit 2 d alors que l'on n'observe que I'Cchange des protons aromatiques.

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Section: -Methyl-25-diphenyl-3-hexanone (3d)mentioning

confidence: 99%

“…Its nmr spectra clearly showed the presence of an isopropyl group 6 1. 24 , and a carboxyl carbon (168.7). The aryl protons gave rise to three multiplets centred at 6 7.20 (m, lH), 7.40 (m, 2H), 7.75 (bd, 3 -8 Hz, 1H).…”

Section: Introductionmentioning

confidence: 99%

¹³C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift

Dyllick‐Brenzinger¹,

Patel²,

Rampersad³

et al. 1990

Can. J. Chem.

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ChemInform Abstract: 13C NMR Studies. Part 141. The Isolation, Structure, and Stereochemistry of Traversiadiene. The Precursor Hydrocarbon of Traversianal Biosynthesis.

Stoessl¹,

Rock²,

Stothers³

1990

ChemInform

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Diterpenoids

Connolly¹,

Hill²

1991

Dictionary of Terpenoids

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The isolation, structure, and stereochemistry of traversiadiene. The precursor hydrocarbon of traversianal biosynthesis

Cited by 5 publications

References 0 publications

¹³C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift

¹³C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift

ChemInform Abstract: 13C NMR Studies. Part 141. The Isolation, Structure, and Stereochemistry of Traversiadiene. The Precursor Hydrocarbon of Traversianal Biosynthesis.

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The isolation, structure, and stereochemistry of traversiadiene. The precursor hydrocarbon of traversianal biosynthesis

Cited by 5 publications

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13C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift

13C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift

ChemInform Abstract: 13C NMR Studies. Part 141. The Isolation, Structure, and Stereochemistry of Traversiadiene. The Precursor Hydrocarbon of Traversianal Biosynthesis.

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¹³C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift

¹³C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller–Bauer cleavage, and an alkyl to aryl acyl shift