A Convenient Synthetic Route to Benz[cd]azulenes: Versatile Ligands with the Potential To Bind Metals in an η5, η6, or η7 Fashion

Balduzzi, Sonya; Müller‐Bunz, Helge; McGlinchey, Michael J.

doi:10.1002/chem.200400425

Cited by 17 publications

(18 citation statements)

References 27 publications

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“…In this latter case, the presence of the bulky substituents renders the molecule reasonably stable but, upon prolonged exposure to air, oxidative dehydrogenation leads to the formation of 27. 18 In 1966, Galantay reported the formation of 2Hdibenz[cd,h]azulen-2-one, 28, via the Friedel-Crafts cyclisation of the acid chloride, 29 (see Scheme 9). Moreover, it was suggested that the favoured resonance structure would be zwitterionic whereby the ring system behaved as a dibenz[cd,h]azulenium cation.…”

Section: Synthesis Of 2-phenyl-11bh-dibenz[cdh]azulenementioning

confidence: 99%

Syntheses, X-ray crystal structures and reactivity of fluorenylidene- and dibenzosuberenylidene-allenes: convenient precursors to dispirotetracenes, di-indenotetracenes and 2-phenyl-11bH-dibenz[cd,h]azulene

et al. 2010

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3,3-(Biphenyl-2,2'-diyl)-1-alpha,alpha,alpha-trifluoro-p-tolyl-allene, 9, sequentially forms head-to-tail, 12, cis-tail-to-tail, 13, and trans tail-to-tail, 14, 1,2-dialkylidene-cyclobutane dimers, each of which has been characterised by X-ray crystallography. Thermolysis at 180 degrees C yields the dispirotetracene, 15, and di-indenotetracene, 16; the latter compound forms an air-stable Diels-Alder adduct, 17, with N-methylmaleimide. In contrast, the dibenzo[a,d]cycloheptenylidene-allenes, (C(14)H(10))C=C=C(Br)Ph, 20a, and (C(14)H(10))C=C=C(H)Ph, 21a, do not dimerise under relatively mild conditions. However, protonation of the bromo-allene, 20a, and subsequent addition of hydride, provide a facile entry to the difficultly accessible bowl-shaped dibenz[cd,h]azulene framework, as in 30, that had not previously been structurally characterised. Among others, the X-ray crystal structures of 12, 13, 14, 17, 20a, 21a and 30 are reported.

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Section: Synthesis Of 2-phenyl-11bh-dibenz[cdh]azulenementioning

confidence: 99%

Syntheses, X-ray crystal structures and reactivity of fluorenylidene- and dibenzosuberenylidene-allenes: convenient precursors to dispirotetracenes, di-indenotetracenes and 2-phenyl-11bH-dibenz[cd,h]azulene

et al. 2010

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“…The ready availability of the dibenzosuberenylidene-bromoallene, 51, raised the possibility of developing a simple route to the benz[c,d]azulene skeleton, a hitherto relatively inaccessible ring system [34][35][36]. As shown in Scheme 17, protonation of 51 with HBF 4 at 0°C occurs at the central allene carbon, resulting in Nazarov cyclization, elimination of HBr, and generation of the tropylium-type cation, 53; subsequent reduction with triethylsilane delivers the dibenz[c,d,h]azulene, 54, the X-ray crystal structure of which reveals a non-planar geometry [32].…”

Section: -Phenyl-12h-dibenz[cdh]azulenementioning

confidence: 99%

From allenes to tetracenes: Syntheses, structures, and reactivity of the intermediates

Banide

Oulié

McGlinchey

2009

Pure and Applied Chemistry

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Each step of the conversion of a series of 9-alkynyl-9H-fluorenes into the corresponding fluorenylidene-allenes that dimerize and proceed sequentially via head-to-tail and tail-to-tail dialkylidene-cyclobutanes, en route to electroluminescent tetracenes, has been characterized X-ray crystallographically. Allenes possessing substituents of very different electronic and steric character, such as aryl, halogeno, silyl, phosphino, and ferrocenyl, exhibit novel and unexpected reactivity patterns. The silyl-allenes dimerize to yield 1,2-bis(fluorenylidene)cyclobutanes of intrinsic C 2 symmetry as a result of the overlapping fluorenylidenes with their large wingspans. Thermal rearrangement of a bis(fluorenyl)bis(trimethylsilyl)-diallene generates the tetrabenzo-quatercyclopentadiene, C 60 H 36 , which represents 60 % of the C 60 framework. An attempt to isolate a "push-pull" allene, whose central carbon possesses carbene character, was made by incorporating a cation-stabilizing substituent (ferrocenyl) and an aromatic anionic moiety (fluorenide) at the termini. However, the allene underwent facile dimerization to the very heavily congested 3,4-di(spirofluorenyl)-1,2-bis(ferrocenyl-chloromethylene)cyclobutane that exhibits a very long (1.65 Å) C(3)-C(4) bond. Extension of this chemistry to dibenzosuberenylidene-allenes led to a straightforward route to the hitherto difficultly available dibenz[c,d,h]azulene system. Moreover, the reaction of 5-phenylethynyl-5H-dibenzo[a,d]cyclohepten-5-ol with dicobalt octacarbonyl yielded, surprisingly, the first isolated example of a (µ-alkyne)Co 2 (CO) 5 (η 2 -alkene)complex, the long-sought first intermediate in the proposed mechanism of the Pauson-Khand reaction (PKR).

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“…Our approach was to extend the guaiazulene carbon framework through nucleophilic addition of the resonance-stabilized anion 2to propargyl bromide, yielding the propargyl-GA 4. It is well known that, due to the hyperconjugation of methyl at the 4-positions of a GA 2, the Cα protons of the alkyl groups can be removed using a strong base such as LDA (Balduzzi et al, 2004). Typically, the resulting azulene carbanions are quite stable due to the presence of an aromatic cyclopentadienyl anionic moiety in their resonance forms.…”

Section: Synthesismentioning

confidence: 99%

“…Typically, the resulting azulene carbanions are quite stable due to the presence of an aromatic cyclopentadienyl anionic moiety in their resonance forms. In the literature, the carbanion 2has a limited number of nucleophilic addition reactions with electrophilic centers (Kurokawa, 1983;Razus et al, 2008;Balduzzi et al, 2004;Aumüller et al, 2011;Woodward et al, 2016). The GA 2, which was commercially available, became the key structure that allowed us to prepare propargyl-GA 4.…”

Section: Synthesismentioning

confidence: 99%

Facile One-pot Synthesis of A Novel Propargyl-Azulene Hybrid Derivative: Cycloaddition Reaction and Some Spectroscopic Properties

Erdoğan

2020

Iğdır Üniversitesi Fen Bilimleri Enstitüsü Dergisi

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Guaiazulene, 1,-isopropylazulene, is one of the non-benzenoid aromatic compounds consisting of fused of the seven-and the five-membered ring. Guaiazulene is an important natural product and having great potential due to its unique optical and electronic properties. In this study, a method for propargyl insertion into the C-4 methyl group of the guaiazulene is developed. A one-pot reaction of the guaiazulene, LDA, and propargyl bromide in THF affords the corresponding a new propargyl-azulene hybrid derivative. Additionally, Diels-Alder cycloaddition reaction between the propargyl-GA and tetraphenylcyclopentadienone was performed, and the cycloadduct was obtained with excellent yield. The structures of new compounds were elucidated on the basis of extensive spectroscopic (IR, NMR, and UV-vis) data analysis. This approach may be potentially useful for the development of the new azulene derivatives.

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A Convenient Synthetic Route to Benz[cd]azulenes: Versatile Ligands with the Potential To Bind Metals in an η⁵, η⁶, or η⁷ Fashion

Cited by 17 publications

References 27 publications

Syntheses, X-ray crystal structures and reactivity of fluorenylidene- and dibenzosuberenylidene-allenes: convenient precursors to dispirotetracenes, di-indenotetracenes and 2-phenyl-11bH-dibenz[cd,h]azulene

Syntheses, X-ray crystal structures and reactivity of fluorenylidene- and dibenzosuberenylidene-allenes: convenient precursors to dispirotetracenes, di-indenotetracenes and 2-phenyl-11bH-dibenz[cd,h]azulene

From allenes to tetracenes: Syntheses, structures, and reactivity of the intermediates

Facile One-pot Synthesis of A Novel Propargyl-Azulene Hybrid Derivative: Cycloaddition Reaction and Some Spectroscopic Properties

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