<b>3,4-Dimethylenecyclobutene by Thermal Rearrangement of 1,5-Hexadiyne</b>

Huntsman, William D.; Wristers, Harry J.

doi:10.1021/ja00903a065

Cited by 64 publications

(19 citation statements)

References 13 publications

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“…28,29 To synthesize naphthazarin-derived POAs, we utilized diene 9, which can be accessed in two steps according to literature procedures. 16,19,[34][35][36][37][38][39] Diene 9 was reacted with naphthazarin (5) to furnish mono-adduct 10 in 49% yield (Scheme 2).…”

Section: Synthesis Of Naphthazarin Phenylene-containing-oligoacene Comentioning

confidence: 99%

Naphthazarin-Polycyclic Conjugated Hydrocarbons and Iptycenes

et al. 2017

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The synthesis of a set of naphthazarin-containing polycyclic conjugated hydrocarbons is described herein. Sequential Diels-Alder reactions on a tautomerized naphthazarin core were employed to access the final conjugated systems. Complete conjugation across the backbone can be achieved through complexation with BF, as observed by H NMR analysis and UV/vis spectroscopy. Precisesynthetic control over the degree of oxidation of naphthazarin quinone Diels-Alder adduct 10 is additionally demonstrated and enables us to direct its subsequent reactivity. Finally, this work serves to demonstrate the potential for naphthazarin as a building block in the synthesis of novel organic electronic materials.

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Section: Synthesis Of Naphthazarin Phenylene-containing-oligoacene Comentioning

confidence: 99%

Naphthazarin-Polycyclic Conjugated Hydrocarbons and Iptycenes

et al. 2017

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“…The thermochemical parameters of the 2 → 130 cyclization have been determined and the activation parameters ( E a = 29.3 kcal/mol, log A = 13.6) [114–115] clearly speak for a concerted pericyclic process. This is, indeed, corroborated by studying the stereochemistry of the process, the work having been carried out by Huntsman [108–109], Pasto [29,115–116], Skattebøl [117] and others [118]. …”

Section: Reviewmentioning

confidence: 76%

“…Up to the present day this electrocyclization remains the most thoroughly investigated reaction of the conjugated bisallenes. As a matter of fact, these studies also demonstrate that 2 is the most likely intermediate in the thermal interconversion of 1,5-hexadiyne ( 129 ) to 130 , a Cope-type rearrangement that was discovered and discussed thoroughly by Huntsman and co-workers [108–111]. A shock-tube pyrolysis study of 2 in the temperature range of 540 to 1180 K at two nominal pressures (22 and 40 kbar) revealed that 2 plays an important role in the so-called propargyl mechanism, which is of importance in relation to the formation of aromatic compounds from nonaromatic precursors [112].…”

Section: Reviewmentioning

confidence: 83%

The chemistry of bisallenes

Hopf¹,

Μαρκόπουλος²

2012

Beilstein J. Org. Chem.

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SummaryThis review describes the preparation, structural properties and the use of bisallenes in organic synthesis for the first time. All classes of compounds containing at least two allene moieties are considered, starting from simple conjugated bisallenes and ending with allenes in which the two cumulenic units are connected by complex polycyclic ring systems, heteroatoms and/or heteroatom-containing tethers. Preparatively the bisallenes are especially useful in isomerization and cycloaddition reactions of all kinds leading to the respective target molecules with high atom economy and often in high yield. Bisallenes are hence substrates for generating molecular complexity in a small number of steps (high step economy).

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“…The suggested thermodynamic stability and instability are not in agreement with experimental observations. The cyclobutene derivative can be stored under nitrogen in a refrigerator for several days [75]. o-Xylylene photochemically synthesized in rigid glass (−196 °C) dimerizes on melting the glassy solution (ca.…”

Section: Kinetic Stabilitymentioning

confidence: 99%

An Orbital Phase Theory

Inagaki

2009

Orbitals in Chemistry

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Cyclic orbital interactions are contained in non-cyclic conjugation as well as cyclic conjugation. For effective interactions, the orbitals are required to meet simultaneously the phase continuity conditions: (1) out of phase relation between electron-donating orbitals; (2) in phase relation between electron-accepting orbitals and between electron-donating and -accepting orbitals. The orbital phase theory is applicable to diverse chemical phenomena of non-cyclic conjugate systems, e.g., relative stabilities of non-cyclic isomers, and selectivities of the reactions through non-cyclic transition structures. The orbital phase theory also includes the rules for cyclic systems, i.e., the Wooward-Hoffmann rule for stereoselection of organic reactions and the Hueckel 4n + 2p electron rule for aromatic molecules. Derivation and applications of the orbital phase theory are reviewed.

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3,4-Dimethylenecyclobutene by Thermal Rearrangement of 1,5-Hexadiyne

Cited by 64 publications

References 13 publications

Naphthazarin-Polycyclic Conjugated Hydrocarbons and Iptycenes

Naphthazarin-Polycyclic Conjugated Hydrocarbons and Iptycenes

The chemistry of bisallenes

An Orbital Phase Theory

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