Photochemical valence isomerization of oxobicyclic analogs of norbornadiene

Payo, E.; Cortés, Luis Eduardo López; Mantecon, Joaquin; Rivas, Carlos; Pinto, Gladys León de

doi:10.1016/s0040-4039(00)71618-2

Cited by 6 publications

(1 citation statement)

References 3 publications

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“…The substituent migrations which occur in the transformation of 1 to 2, although not particularly new from a chemical standpoint, are nevertheless the first to be reported in the direct formation of benzene derivatives from DielsAlder adducts. High yields of 2 and the possibility of increasing the number of types of substituents ;References in parentheses give parameters for dimethyl ester and diacid of l b (27,28,30), l c (28,30), and 2b. r (30), as well as dimethyl ester of l a (26 suggests that our procedure should prove generally useful for the synthesis of a large number of benzene derivatives which would be difficult by more conventional routes.…”

Section: Introductionmentioning

confidence: 99%

Influence of Lewis acids on the Diels–Alder reaction. II. Rearrangement of 1- and 1,4-substituted diethyl 7-oxabicyclo[2•2•1]2,5-heptadiene-2,3-dicarboxylate adducts to 4- and 4,6-substituted diethyl 3-hydroxyphthalates

Mcculloch¹,

Stanovnik²,

Smith³

et al. 1969

Can. J. Chem.

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Direct formation of 4-or 4,6-alkyl and aryl substituted diethyl 3-hydroxyphthalates from the correspondingly substituted Diels-Alder adducts of 2-or 2,5-substituted fi~rans and diethyl acetylenedicarboxylate is pronloted by AICI, in CH2C12 at room temperature. The first adduct of 2,5-diphenylfuran to be isolated has been obtained from the same reaction at -20'. The aromatic compounds can be obtained alternatively by treating the adducts with BF, or H2S04: where the adducts can be prepared by conventional means this two-step procedure has resulted in greatly improved yields. Adducts of furan and furfuryl alcohol are similarly converted to substituted phenols. HCI effected conversion only in the case of adducts carrying a bridgehead aryl substituent; in all other cases HCI added to the substituted double bond. The mechanism of the adduct rearrangement is discussed.

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Section: Introductionmentioning

confidence: 99%

Influence of Lewis acids on the Diels–Alder reaction. II. Rearrangement of 1- and 1,4-substituted diethyl 7-oxabicyclo[2•2•1]2,5-heptadiene-2,3-dicarboxylate adducts to 4- and 4,6-substituted diethyl 3-hydroxyphthalates

Mcculloch¹,

Stanovnik²,

Smith³

et al. 1969

Can. J. Chem.

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Phenylsubstituierte Quadricyclanester Synthese, Thermolyse, Cycloadditionen

Prinzbach

Thyes

1971

Chem. Ber.

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H Die 1.4-und 1.5-Diphenyl-norbornadienester 6a, b und 9a, b sowie einige Dihydroderivate (18, 19) werden synthetisiert. Durch direkfe Lichtanregung erhalt man die entsprechenden Quadricyclane 7a, b und 10a, b, deren thermische Bestandigkeit je nach der Stellung der Phenylreste betrachtlich variiert (Pyrolyseverlauf und angenaherte Halbwertszeiten werden bestimmt). Die durch Aceton sensihilisierte Photolyse von 6a, b liefert die Tricyclo[3.2.0.02J]hepten-Derivate 31 bzw. 25,27. Nach vorliiufigen Befunden ist die Di-x-Methan-Umlagerung auch im Falle von 9a, b bevorzugt. Bei der Umsetzung von 7a, lob mit Acetylendicarbonsatire-dimethylester oder Propiolsaure-methylester werden die I : I -Addukte 33a, b hzw. 38 erhalten. Phenyl Substituted Quadricyclane Esters -Synthesis, Thermolysis, Cycloadditions The 1.4-and I .5-diphenyl substituted norbornadiene esters 6a, b, 9a, b and some dihydro derivatives (18,19) are synthesized. The corresponding quadricyclanes 7a, b, 10a, bare obtained upon direct irradiation. Depending on the position of the phenyl substituents the thermal stability of the quadricyclanes varies considerably; the course of their pyrolysis reaction and approximate half-lives are determined. The sensitized (acetone) photolysis of 6a, b leads to the tricyclo[3.2.0.02.~]heptene derivatives 31 and 25, 27, resp. Judged by preliminary results the di-7r-methane transformation is also the favorite pathway in the case of 9a, b. Cycloaddition reactions between 7a, lob, and dimethyl acetylenedicarboxylate or methyl propiolate yield the 1 : 1 adducts 33a, h and 38. Leichtigkeit und Kichtung thermischer lsomerisierungsreaktionen in tetracyclischen Verbindungen des Typs 2 --in groBer Vielfalt durch [27c + 27c]-Photocycloadditionen aus Norbornadienderivaten 1 zuganglich 2) -werden entscheidend durch die Art der Brucke X bestimmt. Der lsocyclus 2a (R --H)3) sowie alle bisher untersuchten Deri-11 44. Mitteil. in der Reihe J'hotochemische Urnwandlungen"; 43. Mitteil. I M. KIuus und H. Prinzbuch, Angew. Prinzbach und Thyes Jdhrg. 104 vate4) liefern beim Erhitzen unter Spaltung der Bindungen A die Ausgangsdiene zuruck. Die Oxa-(2b)s) u n d Azaheterocyclen (2c)6) hingegen lagern sichfast aus-nahmslos7)In die Heterotropilidene 3b bzw. 3c um, ohne daR sich tricyclische Zwischenprodukte (z. B. 4b, c) nachweisen lieBen Die Erwartung, dd8 in den Methylenquadricyclanen 2d die Methylenfunktion die Allylbindungen B soweit schwachte, um die Thermolyse wie be1 den Heterocyclen 2b, c bevorzugt Jm Sinne voii 2 --f 3 ablaufen zu ldssenso dd8 uber die Sequenz 1 +-2 + 3 also Heptafulvene aus Fulvenen zugdnghch wurden . hat sich nicht bestatigt. Ndch den bisherigen Befunden beurteilt, reicht diese Aktivierung nicht aus, um den energetischen Vorteil einer Spaltung der Dreiring/Vierrmgbindungen A kompensieren zu konnens).In dieser Arbeit 9) gehen wir der Frage nach, ob Phenylsubstituenten in den Positionen 2/4 bzw. 2/6 der Quadricyclanester (2a) die lsomerisierung in die Tropilidenreihe 1 enken. 7) Mit der zusatzlichen Aktivierung der Vierring...

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Diels-Alder adducts of furan derivatives in the synthesis of carro- and heterocyclic systems (review)

Adamskaya

Oleinik

1985

Chem Heterocycl Compd

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Photochemical valence isomerization of oxobicyclic analogs of norbornadiene

Cited by 6 publications

References 3 publications

Influence of Lewis acids on the Diels–Alder reaction. II. Rearrangement of 1- and 1,4-substituted diethyl 7-oxabicyclo[2•2•1]2,5-heptadiene-2,3-dicarboxylate adducts to 4- and 4,6-substituted diethyl 3-hydroxyphthalates

Influence of Lewis acids on the Diels–Alder reaction. II. Rearrangement of 1- and 1,4-substituted diethyl 7-oxabicyclo[2•2•1]2,5-heptadiene-2,3-dicarboxylate adducts to 4- and 4,6-substituted diethyl 3-hydroxyphthalates

Phenylsubstituierte Quadricyclanester Synthese, Thermolyse, Cycloadditionen

Diels-Alder adducts of furan derivatives in the synthesis of carro- and heterocyclic systems (review)

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