So you want to do molecular modeling? A consumer's guide to desktop modeling programs for the Macintosh

The title compound 11 was synthesized from acenaphthenequinone in 11 steps with an overall yield of ca. 1.3%. Photochemical desulfurization of the thiacyclophanene 24 afforded the cyclophanene 28. Photochemical isomerization of 28 to the tetrahydropyrene derivative 32 followed by DDQ oxidation gave the desired dihydropyrene 11. Compound 11 is found to sustain only about 85% of the ring current of the parent dihydropyrene 1. On the basis of our results, a significant effect on the diatropicity of the 14π annulene in 11 due to its conjugation with a naphthalene moiety is verified. A correlation between theoretically calculated bond orders and experimentally observed coupling constants for selected bonds in 11 indicates that the inductive effect, relative to the resonance effect, plays a major role in the net effect of conjugation observed in 11. Among several derivatives of dihydropyrene 1, a linear relationship is observed for an empirical correlation between the methyl chemical shifts and the corresponding Dewar resonance energies associated with the benzenoid systems in conjugation with 1. This may serve as a method to estimate the resonance energies of other aromatic systems relative to that of benzene. Compound 11 underwent electrophilic nitration, acetylation, and bromination readily under mild conditions. The electrophiles reacted selectively with the dihydropyrene system in 11 and not the acenaphthylene moiety in conjugation.

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“…Computational Details. The initial geometries were generated using the MMX force field with PCMODEL v4.0 on a personal IRIS computer.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Diatropicity of trans-10b,10c-Dimethylacenaphthyleno[1,2:e]-10b,10c-dihydropyrene: A Model Aromatic Molecule To Verify the Effect of Conjugation on the Diatropicity of an Annulene

1997

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“…Computational Details. The initial geometries were generated using the MMX force field with PCMODEL v4.0 calculations were carried out with the MOPAC system (v6.0) on a personal IRIS computer.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of 2-Aryl-10b,10c-dimethyl-10b,10c-dihydropyrenes and a Study of Their Conjugation Behavior: Linear Relationship between the Degree of Conjugation and the Electronic Nature of Substituents

Lai

Jiang

1997

J. Org. Chem.

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A new Gomberg-Bachmann reaction between 10b,10c-dimethyl-10b,10c-dihydropyrene (3) and an arenediazonium salt under acidic conditions afforded a mixture of mono- and diarylated derivatives of 3. The major product was 2-aryl-10b,10c-dimethyl-10b,10c-dihydropyrene 6. The desired products were obtained only from diazonium salts prepared from anilines with at least one strongly electron-withdrawing substituent. The combined conjugation and electronic effects of the arene substituent on the diatropicity of the dihydropyrene moiety in the monoarylated product is insignificant. The conjugation effect in 6 is, however, readily observed by the color appearance of 6 in the solid state and the significant red shift in the absorption bands between 300 and 520 nm in its electronic spectrum. A linear relationship was in fact obtained when the degree of conjugation (rho band lambda(max) values) is correlated with the electronic nature (sigma(+) values) of the corresponding substituents.

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“…Computational Details. The initial geometries were generated using the MMX force field with PCMODEL v4.0 . The semiempirical PM3 calculations were carried out with the MOPAC system (v6.0) on a personal IRIS computer.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Conformational Study of Isomers of 9-Methyl-2,11-Dithia[3.3](1,4)triphenylenometacyclophane and 2,23-Dithia[3.3](1,4)triphenylenophane

1997

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So you want to do molecular modeling? A consumer's guide to desktop modeling programs for the Macintosh

Abstract: 135. The purpose of this article is to provide a broad overview of five Macintosh software packages. Each provides a tool with which the user can construct and view molecular structures. [Erroneously indicated as 134 in hard copy.]

Cited by 17 publications

References 4 publications

Synthesis and Diatropicity of trans-10b,10c-Dimethylacenaphthyleno[1,2:e]-10b,10c-dihydropyrene: A Model Aromatic Molecule To Verify the Effect of Conjugation on the Diatropicity of an Annulene

Synthesis and Diatropicity of trans-10b,10c-Dimethylacenaphthyleno[1,2:e]-10b,10c-dihydropyrene: A Model Aromatic Molecule To Verify the Effect of Conjugation on the Diatropicity of an Annulene

Synthesis of 2-Aryl-10b,10c-dimethyl-10b,10c-dihydropyrenes and a Study of Their Conjugation Behavior: Linear Relationship between the Degree of Conjugation and the Electronic Nature of Substituents

Synthesis and Conformational Study of Isomers of 9-Methyl-2,11-Dithia[3.3](1,4)triphenylenometacyclophane and 2,23-Dithia[3.3](1,4)triphenylenophane

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