Bridged Polycyclic Compounds. XLV. Synthesis and Some Properties of 5,5a,6,11,11a,12-Hexahydro-5,12:6,11-di-<i>o</i>-benzenonaphthacene (Janusene)

Cristol, Stanley J.; Lewis, David

doi:10.1021/ja00982a035

Cited by 52 publications

(20 citation statements)

References 3 publications

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“…One such system is a molecule called “janusene”, which has a tropylium ring in place of one of the phenyl rings at the facing position ( 13 , Figure ). Cation 13 and its reference cation 14 with the tropylium ring at the lateral position were synthesized from neutral janusene in around 20 to 30% yield each, as yellow powder .…”

Section: Stabilization Of the Tropylium Ion By Intramolecular Charge‐mentioning

confidence: 99%

Professor Tetsuo Nozoe and My Tropylium Ion Chemistry

Komatsu

2014

The Chemical Record

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Needless to say, the discovery of hinokitiol with its "unconventional" aromaticity by Professor Tetsuo Nozoe is one of the most important achievements in organic chemistry in the last century. The essence of this "non-benzenoid" aromaticity in hinokitiol is of course that of tropolone, and it is further related to the aromaticity of tropone and the tropylium ion, i.e., the cycloheptatrienyl cation. In this account, details of the study conducted by the author's group, particularly on the synthesis and properties of tropylium ion derivatives with various unique structures pursuing the ultimately high carbocation stability, are described.

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Section: Stabilization Of the Tropylium Ion By Intramolecular Charge‐mentioning

confidence: 99%

Professor Tetsuo Nozoe and My Tropylium Ion Chemistry

Komatsu

2014

The Chemical Record

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“…Precursors 2b and 3b are prepared through remarkably selective and high-yielding Diels-Alder cycloadditions with anthracene. 11 Their structures were confirmed via single-crystal X-ray crystallography. Surprisingly, 2b and 3b are the only isolated products even though other isomers are possible.…”

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confidence: 94%

Conjugated Polymers in an Arene Sandwich

et al. 2006

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A series of poly(p-arylene butadiynylene)s containing zero, one, and two co-facial pi-pi interactions per repeat unit were synthesized and characterized. A surprisingly selective and high-yielding Diels-Alder cycloaddition of anthracene and nonsymmetric, sterically hindered anhydrides proved essential to generating the cofacial arene-containing monomers. Single-crystal X-ray structures display nearly parallel cofacial arenes that are within the van der Waals contact distances. The precursor molecules with cofacial arenes undergo reversible one- and two-electron oxidations to the radical cation and dication in CH2Cl2. The anhydrides were converted to N-alkyl imides to increase the solubility. High-molecular weight poly(p-arylene butadiynylene)s were prepared via Pd/Cu(I)/benzoquinone oxidative coupling of the diacetylene monomers. The resulting polymers are highly emissive in solution and thin films. The ionization potentials were measured using ultraviolet photoelectron spectroscopy with thin films. Last, fluorescence measurements of polymer thin films during continuous irradiation indicate that the most hindered polymer is more resistant to photobleaching.

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“…[8][9][10][11][12] These interactions have a pivotal influence on the electronic properties, and consequently on the reactivity of such systems. 13,14 Janusene (1), C 30 H 22 , named in allusion to the roman god Janus, was first synthesized by Cristol in 1967 by the [4p+2p] cycloaddition reaction between anthracene and dibenzobarrelene, and its synthesis was later optimized by Cantrell and Filler 15,16 (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

“…Such proximity between these aromatic portions enables janusene to exhibit peculiar electronic properties, which have been evidenced from both experimental and theoretical perspectives. 15,[17][18][19][20][21][22] Experiments have shown that the reactivity of the janusene is critically influenced by the proximity of the facial rings. Regarding electrophilic aromatic substitutions, they occur preferentially on the beta carbons of the facial rings, F b , 15,19 due to transannular interactions that destabilize the ground state (GS) through p-repulsion and stabilize the transition state (TS) through p-delocalization.…”

Section: Introductionmentioning

confidence: 99%