Solvolysis of bicyclo[3.2.1]octa-2,6-dienyl and isomeric p-nitrobenzoates

Diaz, A. F.; Sakai, M.; Winstein, S.

doi:10.1021/ja00728a045

Cited by 33 publications

(61 citation statements)

References 4 publications

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“…The unexpected appearance of endo alcohol 23 is in contrast to the behavior of 26, which gives exclusive exo alcohol 22 on solvolysis. 13 A product stability study showed that the exo acetate (precursor to 22) isomerized under the reaction conditions14 to give an identical acetate mixture with that obtained in the solvolysis study.…”

Section: Resultsmentioning

confidence: 86%

Foiled electrocyclic rearrangement of cyclopropyl cations

Creary¹

1975

J. Org. Chem.

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Section: Resultsmentioning

confidence: 86%

Foiled electrocyclic rearrangement of cyclopropyl cations

Creary¹

1975

J. Org. Chem.

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“…22-6,05 (m) 6,45-6,28 6,76-6,55 H-C(4) 5,38-5,22 (m) 5,68-5,52 6,12-5,96 2H-C(9) 4,60 (3) 4,80 (3); 4,78 (s) 5,06; 5,OO H-C(2). -C(7) 1, 80-1.70(m) 2,lO-1,98 2,44-2,32 H3C-C(l), -C (5) 1,23 (s); 1,13 (s) 1,53; 1,42 1,97; 1,86 H3C-C (8) 0,95 (s) 1,53 2,48 HO 1 3 (s) 3,75 7,98 0,179 0,270 0,387 7,lO-6.95 7,58-7,40a) 8,10-7,95 6,64-6,48 7,28-7,12b) 5,35; 5,25 5,72; 5,58 6,17; 5,97 2,84-2,74 3,44-3.24 4,l -3,7c) (25), 129 (18), 128 (43), 127 (II), 119 (lo), 118 (lo), 117 (25), 116 (19). 115 (54), 106 (13), 105 (51), 104 (lo), 103 (17), 102 (lo), 92 (8,5).…”

Section: Experimenteller Teilunclassified

Säurekatalysierte Umlagerungen von 1,5‐Dimethyl‐6‐methyliden‐tricyclo[3.2.1.0^2,7]oct‐3‐en‐8endo‐olen

Mukherjee‐Müller

Gilgen

Zsindely

et al. 1977

Helvetica Chimica Acta

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Acid Catalysed Rearrangement of 1,5-Dimethyl-6-methyliden-tricyclo [3.2.1.~~7Joct-3-en-8endo-ols SummaryThe tricyclic alcohols 2,3,4 and 6 (Scheme I ) are synthesized by the reaction of the tricyclic ketone 1 with sodiumborohydrid or metalloorganic reagents. Their configuration at C (8) is determined by NMR. in the presence of Eu (fod),. The exo-attack of 1 by the nucleophil forming the endo-alcohol is favored, the n-electrons of C (3)=C (4) hindering the endo-attack. On treatment with sulfuric acid in dioxane/water at 25" the tertiary alcohols yield aryl-substituted ketones. 3 gives in 78.5% yield a mixture of the 3-(dimethylphenyl)-2-butanones 12 and 13, in addition to 16.5% of (2,3,4-trimethylphenyl)-2-propanon (14) (Scheme 2). The alcohols 4 and 6 yield mixtures of the 2-(dimethylphenyl)-3-pentanones 19 and 20 (72%), and 2-(dimethylpheny1)-propiophenones 21 and 22 (68%), respectively (Scheme 2). In the case of the secondary alcohol 2 mainly products derived from hydration at the C(6),C(9) double bond are formed, namely the mixture of diols 23 and 24 (21%), and the mixture of the isomeric 2-(dimethylphenyl)propanals 25,26 and 27 (3%) (Scheme 3). -The structures of 12-14, 19/20, 21/22, 23/24 and 25/26/27 were established by spectroscopic data. In the case of 12 and 13 the degradation of their mixture to the known 1-(dimethylpheny1)ethanols 17/18 confirmed the assignment. -The most probable mechanism for the rearrangement of 3 is shown in Schemes 4 and 5. The reaction proceeds from 3 through a, b and g to 12 and 13; 14 is formed via e, f and i. In the case of 4 and 6 only the reaction analogue to 3 + a -. b + g s 12/13 takes place. The isomeric aldehyds 25-27 formed from 2 could have the structures s, t, and v. The former two could be generated in a similar way as 12/13 from 3, the latter one as shown in Scheme 8.

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“…Die weitere Umwandlung von 41 in 43 kann uber 42 verlaufen. Ein Analogiefall zur Umlagerungsstufe 41 --f 42 findet sich bei der Hydrolyse der epimeren #-Nitrobenzoate 55, die neben den Alkoholen 56 auch die epimeren tricyclischen Alkohole 57 geben [30] (Schema 74 Auf ahnliche Weise wie die Bildung von 5 lasst sich auch das Entstehen kleiner Mengen von 2,4,6-Trimethylphenylessigsaure (6) und 2,3,5-Trimethylphenylessigsaure (7) bei der Formolyse von 2 erklaren (Schema 113). Die aus 2 zur Hauptsache gebildete 2,4,5-Trimethylphenylessigsaure (5) verdankt ihre Bildung der Isomerisierung des Carbenium-Ions 40 zum besonders stabilen allylischen Ion 41 unter Wanderung des Zentrums 8 von C ( l ) nach C (2).…”

Section: Synthese Der Anderen Polymethylsubstituierten Phenylessigsauunclassified

“…5'24 ppm) rnit J 3 , , = 8 Hz. -MS.: 192 (At+, 75), 177 (36), 162 (60), 161 (57), 149 (66), 133 (loo), 117 (68), 105 (30), 91 (73), 77 (32).…”

Section: 7mentioning

confidence: 99%

Umwandlung von 6‐Methylen‐tricyclo[3.2.1.0^2,7]oct‐3‐en‐8‐onen mit Ameisensäure in kernmethylierte Phenylessigsäuren

Peter‐Katalinić

Zsindely

Schmid

1974

Helvetica Chimica Acta

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In a preceding communication [5] it was shown that 1,5-dimethy1-6-methylcnetricyclo[3.2.1.02~7]oct-3-en-8-one (2) and related tricyclic ketones are converted by strong acids (CF,COOH, FS0,H) into polymethylatcd tropylium salts with loss of carbon monoxide, e.g. the 1,2,4-trimethyltropylium ion 4 from 2 (Scheme I).Under the influence of neat formic acid at Z O O , 2 gives rise to ring-methylated phenylacetic acids, 2.e. 2,4,5-trimethylphenylacetic acid (5, main product) as well as smaller amounts of 2,4,6and 2,3,5-trimethylphenylacetic acids (6,7 resp.; Scheme 2 ) . -On rearrangement of 2 in HCOOD, ca. 2 D-atoms are incorporated (formula d,-5) into the 2,4,5-trimethylphenylacetic acid.The tricyclic 15, containing 3 methyl groups, gives 2,3,5,6-tetramethylphenylacetic acid (11; Scheme 4 ) with formic acid; the isomeric tricyclic 16, 2,3,4,5-tetramethylphenylacetic acid (12; Scheme 5). From 1,2,4, 5-tetramethyl-6-methylene-tricyclo[3.2.1.02~']~~t-3-en-8-one (17) one obtains pentamethylphenylacetic acid (14; Scheme 6). Similarly from 18, a phenylacetic acid derivative, most probably 4-ethyl-Z.5-dimethyl-phenylacetic acid (19; Scheme 77), has been obtained. -In no case was the formation of a-phenylpropionic acid derivatives obscrved, not evcn from the tricyclic 23 containing six methyl groups.From the tricyclic ketone 2 in 70% formic acid a trimethyl-cyclohepta-2,4,6-triene-lcarboxyclic acid with partial formula 24, besides 2,4,5-trimethylphenylacetic acid (5), is formed. 24 remained practically unchanged on standing in neat formic acid and thus does not represent an intermediate product arising by the rearrangement of 2 in that solvent.On standing in methanolic sulfuric acid, tricyclic 2 furnishes the two stereoisomeric methanoladdition products 2-26 and E-26 (Scheme 70) ; these are converted into the phenylacetic acids 5, 6 and 7 by neat formic acid.The conversion of 2 and related compounds into ring-polymethylated phenylacetic acids, represents a novel and rather complicated reaction. In our opinion the reaction paths represented in Schemes 12 and 78 are responsible for the conversion of 2 into the trimethylphenylacetic acids, compound 40 representing a key intermediate. Analogous reaction paths can be assumed for the other tricyclic ketone transformations.The use of shift reagents in the NMR. spectroscopy and the high-resolution gas-chromatography of the corresponding methyl esters proved particularly important for the analysis of the reaction mixtures. The majority of the polymethylated phenylacetic acids were independently synthesised by means of the Willgerodt-Kindler reaction (chap. 3.2.), whose course is strongly influenced by methyl groups in the ortho-positions of the acetophenone derivatives employed. Schema 4 J 15 11Im NMR.-Spektrum (100 MHz, CCI,) zeigt der Methylester der 2,3,5,6-Tetramethylphenylessigsaure (11) zwei scharfe s bei 2,19 und 2,13 ppm, die je zwei aromat. CH, entsprechen. Auf Zusatz von Tris(dipiva1omethanato) europium(II1) (Eu(dpm),)[lo] werden die zwei s nach 3,05 und 2,64 ppm verschob...

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Solvolysis of bicyclo[3.2.1]octa-2,6-dienyl and isomeric p-nitrobenzoates

Cited by 33 publications

References 4 publications

Foiled electrocyclic rearrangement of cyclopropyl cations

Foiled electrocyclic rearrangement of cyclopropyl cations

Säurekatalysierte Umlagerungen von 1,5‐Dimethyl‐6‐methyliden‐tricyclo[3.2.1.0^2,7]oct‐3‐en‐8endo‐olen

Umwandlung von 6‐Methylen‐tricyclo[3.2.1.0^2,7]oct‐3‐en‐8‐onen mit Ameisensäure in kernmethylierte Phenylessigsäuren

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Solvolysis of bicyclo[3.2.1]octa-2,6-dienyl and isomeric p-nitrobenzoates

Cited by 33 publications

References 4 publications

Foiled electrocyclic rearrangement of cyclopropyl cations

Foiled electrocyclic rearrangement of cyclopropyl cations

Säurekatalysierte Umlagerungen von 1,5‐Dimethyl‐6‐methyliden‐tricyclo[3.2.1.02,7]oct‐3‐en‐8endo‐olen

Umwandlung von 6‐Methylen‐tricyclo[3.2.1.02,7]oct‐3‐en‐8‐onen mit Ameisensäure in kernmethylierte Phenylessigsäuren

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Säurekatalysierte Umlagerungen von 1,5‐Dimethyl‐6‐methyliden‐tricyclo[3.2.1.0^2,7]oct‐3‐en‐8endo‐olen

Umwandlung von 6‐Methylen‐tricyclo[3.2.1.0^2,7]oct‐3‐en‐8‐onen mit Ameisensäure in kernmethylierte Phenylessigsäuren