A New Synthesis of Cycloheptatriene

Dryden, Hugh L.

doi:10.1021/ja01639a076

Cited by 18 publications

(6 citation statements)

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“…The rearrangement of these protonated bi-I cyclic ketones would most reasonably involve cyclopropylcarbinyl and allylcarbinyl intermediates, there being ample precedent for this in the products that have resulted from the io~~ization of related bicyclic systems in nucleophilic media (3,14). As is shown for 3H there are two ways in which the rearrangement of this cation could proceed that differ in the cyclobutane bond invol-ved.…”

Section: Discussionmentioning

confidence: 97%

“…In practice only 4H was found as a product and no cation such as 13 could be detected. The auestion of which of the cvclobutane bonds will be involved in this type of rearrangement has been considered extensively in the solvolysis of related bicyclic systems (3,14) and it has been shown that the stereochemistry of the leaving group plays a major role in deternlining which bond is broken. However, with these long lived hydroxy cations such considerations have little meaning and additional factors nli~st be examined.…”

Section: Discussionmentioning

confidence: 99%

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The formation of cycloheptenone and cycloheptadienones from bicyclo[3.2.0]heptanone derivatives. An acid-catalyzed, two carbon ring expansion reaction

Hine¹,

Childs²

1976

Can. J. Chem.

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In strong acids, such as FSO3H and 96% HzS04, bicyclo[3.2.0]heptan-6-one and bicyclo-[3.2.0]hept-2-en-7-one undergo a clean isomerization to form protonated cyclohept-2-enone and cyclohepta-2,4dienone, respectively. Substituted derivatives undergo comparable ring expansions when dissolved in these strong acids. The seven-membered ring ketones can be recovered on quenching the acid solutions with a NaHCO3-ether mixture. In contrast, bicyclo-[3.2.0]hept-2-en-6-one when dissolved in FSO3H rearranged to give protonated l-acetylcyclopentadiene. The mechanism and synthetic utility of these reactions is discussed. KENNETH E. HINE et RONALD F. CHILDS. Can. J. Chem. 54, 12 (1976).Dans les acicies forts comme FSO3H et HlS04 96y0 la bicyclo[3.2.0]heptanone-6 et la bicyclo[3.2.0]heptkne-2 one-7 subissent des isornerisatio~~s propres conduisant respectivement aux formes protonCes de la cycloheptkne-2 one et de la cycloheptadikne-2,4 one. Des derives portant des substituants subissent des extensions de cycle comparables lorsque dissous dans ces acides forts. On peut rCcupCrer les cCtones cycliques a sept chainons en traitant les solutions acides par un melange NaHCOs-Cther. Par ailleurs le traitement de la bicycIo[3.2.O]heptkne-2 one-6 par FSO3H conduit k la forme protonee de l'acetyl-1 cyclopentadikne. On discute du mecanisme et de l'utilite en synthiese de ces reactions.[Traduit par le journal]There are numerous examples of fused bicyclic ring systems in which one of the rings is a cyclobutanone moiety. Indeed, one common and facile synthetic entry into this type of ring system involves the cycloaddition of a ketene to a cycloalkene (I). If a means could be found of inducing cleavage of the cyclobutanone bond that is conunon to both rings, then combined with this ketene addition, we would have a route t o functionalized monocyclic systems possessing a ring two carbons larger than that of the alkene used in the original cycloaddition. A viable two carbon ring expansion reaction would be of value in general syntheses of medium size rings (2). The well known interconversion of cyclobutyl, cyclopropylcarbinyl, and open chain cationic systems (3) suggested t o us that one method of inducing the desired cleavage of the cyclobutanone bond would be to react this carbonyl function with an electrophile. There are several reports of the isomerization of cyclobutanones upon protonation and it would appear that in nlany of these rearrangements the carbon-carbon bond / 3 to the carbonyl group is cleaved (4). In view of our interest in the chemistry of the monocyclic, unsaturated, seven-membered ring ketones (5), we have examined the effect of protonation on several bicyclo[3.2.0]heptan-6-ones and bicyclo[3.2.0Jheptenones and report here the results of this study. ResultsCareful solution of bicyclo[3.2.0]heptan-6-one, 1, in FS03H at -78 "C yielded a clear yellow solution whose pmr spectrum at +20 "C (

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Section: Discussionmentioning

confidence: 97%

Section: Discussionmentioning

confidence: 99%

The formation of cycloheptenone and cycloheptadienones from bicyclo[3.2.0]heptanone derivatives. An acid-catalyzed, two carbon ring expansion reaction

Hine¹,

Childs²

1976

Can. J. Chem.

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“…Caled, for Ci8H20O: C, 81.2; H, 10.5. Found : C, 80.9; H, 10.7. 1,2,2a,7a-Tetrahydro-2,2-dimethyl-7H-cy clobut [a] inden-1 -one (13).-Under a nitrogen atmosphere, 70.0 g. (1.0 mole) of dimethylketene was added with stirring to a solution of 116.0 g.…”

Section: C4h9 23a 23bmentioning

confidence: 99%

“…h i b i t e d .hydro-2,2-dimethyl-7H-cyclobut[a]inden-l-one(13) in 12% yield. 1,3-Cyclooctadiene and butylethylketene Co + produce a 15% yield of a 1,2…”

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confidence: 99%

Ketenes. V. Reactions of Ketenes with Dienes and Olefins¹

Martin¹,

Gott²,

Goodlett³

et al. 1965

J. Org. Chem.

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“…The infrared spectra of the two compounds, taken in the solid state, showed only minor differences in the fingerprint (800-1300 cm.-1) region which may be ascribed to the different crystal forms existing in the solid phase in the racemic and the optically active forms. 13 When the natural alkenylglycerol was converted into its liquid diacetate, both the n.m.r. and the infrared spectra of this and of the synthetic m-diacetate Vile were completely identical.…”

mentioning

confidence: 99%

Studies Directed toward the Synthesis of Plasmalogens. II. (±)-cis- and -trans-3-(n-Hexadec-1'-enyloxy)-1,2-propanediol¹

Jc¹,

Dp²

1965

J. Org. Chem.

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A New Synthesis of Cycloheptatriene

Cited by 18 publications

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The formation of cycloheptenone and cycloheptadienones from bicyclo[3.2.0]heptanone derivatives. An acid-catalyzed, two carbon ring expansion reaction

The formation of cycloheptenone and cycloheptadienones from bicyclo[3.2.0]heptanone derivatives. An acid-catalyzed, two carbon ring expansion reaction

Ketenes. V. Reactions of Ketenes with Dienes and Olefins¹

Studies Directed toward the Synthesis of Plasmalogens. II. (±)-cis- and -trans-3-(n-Hexadec-1'-enyloxy)-1,2-propanediol¹

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A New Synthesis of Cycloheptatriene

Cited by 18 publications

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The formation of cycloheptenone and cycloheptadienones from bicyclo[3.2.0]heptanone derivatives. An acid-catalyzed, two carbon ring expansion reaction

The formation of cycloheptenone and cycloheptadienones from bicyclo[3.2.0]heptanone derivatives. An acid-catalyzed, two carbon ring expansion reaction

Ketenes. V. Reactions of Ketenes with Dienes and Olefins1

Studies Directed toward the Synthesis of Plasmalogens. II. (±)-cis- and -trans-3-(n-Hexadec-1'-enyloxy)-1,2-propanediol1

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Ketenes. V. Reactions of Ketenes with Dienes and Olefins¹

Studies Directed toward the Synthesis of Plasmalogens. II. (±)-cis- and -trans-3-(n-Hexadec-1'-enyloxy)-1,2-propanediol¹