Chemistry of Anthracene–Acetylene Oligomers XX: Synthesis, Structures, and Self‐Association of Anthracene–Anthraquinone Cyclic Compounds with Ethynylene Linkers

Iwanaga, Takeshi; Miyamoto, Kazuaki; Tahara, Kazukuni; Inukai, Koji; Okuhata, Satoshi; Tobe, Yoshito; Toyota, Shinji

doi:10.1002/asia.201101000

“…For example, the introduction of alkyl or alkoxy groups at the sterically crowded 9‐positions in 2 and 3 generates separable stereoisomers owing to steric hindrance 6. 7 We also synthesized compound 4 , a monoanthraquinone analogue of 1 , as a small cyclic dimer with polar functional groups and a long alkyl group 8. This compound formed associated species in solution and in the crystalline state owing to attractive intermolecular interactions.…”

Section: Introductionmentioning

confidence: 99%

Chemistry of Anthracene–Acetylene Oligomers XXV: On‐Surface Chirality of a Self‐Assembled Molecular Network of a Fan‐Blade‐Shaped Anthracene–Acetylene Macrocycle with a Long Alkyl Chain

Tsuya

¹

,

Iritani

²

,

Tahara

³

et al. 2015

Chemistry A European J

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An anthracene cyclic dimer with two different linkers and a dodecyl group was synthesized by means of coupling reactions. The calculated structure had a planar macrocyclic π core and a linear alkyl chain. Scanning tunneling microscopy observations at the 1-phenyloctane/graphite interface revealed that the molecules formed a self-assembled monolayer that consisted of linear striped bright and dark bands. In each domain, the molecular network consisted of either Re or Si molecules that differed in the two-dimensional chirality about the macrocyclic faces, which led to a unique conglomerate-type self-assembly. The molecular packing mode and the conformation of the alkyl chains are discussed in terms of the intermolecular interactions and the interactions between the molecules and the graphite surface with the aid of MM3 simulations of a model system.

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“…Second, P2 exhibited a rare case of higher energy emission, which was not observed in P1. Third, of the lot, only P0 was phosphorescent [26,28].…”

Section: Chemical Propertiesmentioning

confidence: 99%

“…Japanese chemists used the Sonogashira reaction to synthesize and study the structures and properties of macrocycles that had anthracene nuclei interconnected by rigid acetylene bridges, 1, as well as the corresponding anthraquinone analogs, 2, (Figure 22) [25,26].…”

Section: Chemical Propertiesmentioning

confidence: 99%

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

Vasilevsky¹,

Stepanov²

2020

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0

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In addition to the reported synthetic routes for the acetylene derivatives of quinones, a detailed analysis of the fundamental chemical, physicochemical, and biological properties of this class of compounds is presented herein. The advantages of Pd- and Cu-catalyzed cross-coupling of terminal alkynes with iodarenes via the Sonogashira reaction to produce new acetylenylquinones with predetermined properties are examined. Here, combining quinoid and acetylene residues into one molecule gives the resulting compounds chemical specificity, as demonstrated by several reported examples of non-trivial transformations. In particular, the presence of the quinoid cycle significantly increases the electrophilicity of the triple bond and determines the range of transformation possibilities. Moreover, acetylenylquinones have heightened sensitivity to both external (such as the reaction temperature and the nature of the solvent) and internal (e.g., the structure of substituents in the nucleus and the acetylene fragment) factors. For example, regioselective cleavage of a strong triple bond under the action of amines is possible in the absence of a metal catalyst. Peri-substituted acetylenyl-9,10-anthraquinones are most suited for the synthetic route because of the proximity of the acetylene and carbonyl groups. Mechanisms of reactions of selective alkynylquinones are described.

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“…Japanese chemists used the Sonogashira reaction to synthesize and study the structures and properties of macrocycles that had anthracene nuclei interconnected by rigid acetylene bridges, 1, as well as the corresponding anthraquinone analogs, 2, (Figure 22) [25,26].…”

Section: Chemical Propertiesmentioning

confidence: 99%

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

Vasilevsky¹,

Stepanov²

2020

REFFIT

0

View full text Add to dashboard Cite

In addition to the reported synthetic routes for the acetylene derivatives of quinones, a detailed analysis of the fundamental chemical, physicochemical, and biological properties of this class of compounds is presented herein. The advantages of Pd- and Cu-catalyzed cross-coupling of terminal alkynes with iodarenes via the Sonogashira reaction to produce new acetylenylquinones with predetermined properties are examined. Here, combining quinoid and acetylene residues into one molecule gives the resulting compounds chemical specificity, as demonstrated by several reported examples of non-trivial transformations. In particular, the presence of the quinoid cycle significantly increases the electrophilicity of the triple bond and determines the range of transformation possibilities. Moreover, acetylenylquinones have heightened sensitivity to both external (such as the reaction temperature and the nature of the solvent) and internal (e.g., the structure of substituents in the nucleus and the acetylene fragment) factors. For example, regioselective cleavage of a strong triple bond under the action of amines is possible in the absence of a metal catalyst. Peri-substituted acetylenyl-9,10-anthraquinones are most suited for the synthetic route because of the proximity of the acetylene and carbonyl groups. Mechanisms of reactions of selective alkynylquinones are described.

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Chemistry of Anthracene–Acetylene Oligomers XX: Synthesis, Structures, and Self‐Association of Anthracene–Anthraquinone Cyclic Compounds with Ethynylene Linkers

Cited by 8 publications

References 63 publications

Chemistry of Anthracene–Acetylene Oligomers XXV: On‐Surface Chirality of a Self‐Assembled Molecular Network of a Fan‐Blade‐Shaped Anthracene–Acetylene Macrocycle with a Long Alkyl Chain

Chemistry of Anthracene–Acetylene Oligomers XXV: On‐Surface Chirality of a Self‐Assembled Molecular Network of a Fan‐Blade‐Shaped Anthracene–Acetylene Macrocycle with a Long Alkyl Chain

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

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