The Condensation of Certain Aromatic Methyl Ketones

Clapp, Daniel B.; Morton, Avery A.

doi:10.1021/ja01302a025

Cited by 24 publications

(18 citation statements)

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“…Clapp and Morton first synthesized 1 by the cyclotrimerization of 1-acetylnaphthalene in aniline at 175 °C. 10 The crude product was obtained as a tar, which provided 1 in 18% yield after a tedious purification process. Magill's preparation of 1 followed Clapp and Morton's procedure.…”

Section: Synthesismentioning

confidence: 99%

“…11,12 The severe steric congestion that develops during the cyclization of ortho-disubstituted aromatic compounds (and 1-substituted naphthalene derivatives) accounts for the low yields of 1. 10,11,13 We felt that 1 could be prepared cleanly and in high yield using modern synthetic methodology. 14 Metal-mediated crosscoupling reactions of aryl halides or sulfonates with aryl stannanes (Stille coupling), 15 aryl halides with aryl halides (Ullman coupling), 16 and aryl halides with aryl boranes (Suzuki, coupling) 17 all represent viable approaches for the synthesis of 1 and related derivatives.…”

Section: Synthesismentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases: Isomeric 1,3,5-Tris(naphthyl)benzenes

and

McMahon

1996

J. Phys. Chem.

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1,3,5-Tris(1-naphthyl)benzene (1), 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2), and 1-(1-naphthyl)-3,5bis(2-naphthyl)benzene (3) easily supercool and form glasses on cooling from the melt. We synthesized 1, 2, and 3 using Suzuki's conditions to effect the cross-coupling reactions of 1,3,5-tribromobenzene with 1-naphthylboronic acid and/or 2-naphthylboronic acid. Variable-temperature 13 C NMR studies of 1 establish a barrier of ca. 12 kcal/mol for rotation about the aryl-aryl bond; this value displays good agreement with the barrier of 13 kcal/mol computed using molecular mechanics calculations (MM2). This relatively low rotational barrier is inconsistent with the previously held notion that 1,3,5-tris(1-naphthyl)benzene (1) exists as a mixture of noninterconverting rotational isomers (atropisomers) in solution at room temperature. Variabletemperature 13 C NMR studies of 2 establish barriers of ca. 12 kcal/mol for rotation about the 1-naphthylaryl bond and <9 kcal/mol for rotation about the 2-naphthyl-aryl bond. Again, these values display good agreement with the barriers of 14 and 2 kcal/mol computed using molecular mechanics calculations (MM2). Earlier syntheses of 1,3,5-tris(1-naphthyl)benzene (1) provided materials that were poorly characterized by modern standards. 1 H and 13 C NMR spectra of one such material, a sample widely used in studies of glasses and supercooled liquids, establish the structure of the material as 2, not 1. This revised structural assignment necessitates a re-evaluation of the earlier literature. Differential scanning calorimetry (DSC) establishes that tris(naphthyl)benzenes 1, 2, and 3 melt (T m ) 182, 194, and 147 °C, respectively) and form glasses upon cooling (T g ) 81, 77, and 67 °C, respectively). Given its low melting point and glass transition temperature, 1-(1-naphthyl)-3,5-bis(2-naphthyl)benzene ( 3) is an attractive candidate for future studies of molecular dynamics of glassy materials.o-Terphenyl and 1,3,5-tris(1-naphthyl)benzene (1, TRNB) are rare examples of low-molecular weight, nonpolar compounds that spontaneously form stable supercooled liquids. The liquid, supercooled liquid, glassy, and crystalline states of o-terphenyl and 1,3,5-tris(1-naphthyl)benzene (1) are all experimentally

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Section: Synthesismentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases: Isomeric 1,3,5-Tris(naphthyl)benzenes

and

McMahon

1996

J. Phys. Chem.

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“…Consequently, 1,3,5-tri(het)arylbenzenes serve as versatile platforms in the design of organic light emitting diodes (OLEDs), 8,9 dendrimers, 10 polycyclic aromatic hydrocarbons (PAH), 11 bulky ligands 12 and truxenes (derivatives of 10,15-dihydro-5H-diindeno[1,2-a; 1',2'c]fluorene). 13 The classical one-directional convergent synthetic approach, originally developed by Clapps and Morton, 14 is that most frequently reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

Insights into the triple self-condensation reaction of thiophene-based methyl ketones and related compounds

Andicsovà‐Eckstein¹,

Végh²,

Krutošíková³

et al. 2018

Arkivoc

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The acid catalysed triple self-condensation of 1-thien-2-ylethanone (2-acetylthiophene) and five related compounds is presented. Tetrachlorosilane used as the Lewis acid produces dry hydrogen chloride which catalyzes the self-condensation process. Depending on the reaction conditions and the substitution of the carbonyl substrates, the reaction can proceed as a [2+2+2] cyclotrimerization towards C 3 -symmetric 1,3,5trisubstituted benzenes, or as the single-type aldol condensation leading to 1,3-disubstituted (E)-β-methylchalcones. This is important for the design of new aromatic/olefinic compounds beyond the model structures. Synthesis of 4'-fluoro-3,5-di-(2-thienyl)biphenyl through a mixed-type aldol reaction using erbium triflate is discussed. Mechanistic rationale is provided.

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“…Many catalysts such as hydrochloric acid, [8] sodium or potassium pyrosulfate in H 2 SO 4 , [9] aniline hydrochloride, [10] TsOH, [11] amberlyst-15, [12] titanium tetrachloride (TiCl 4 ), [13] SiCl 4 , [14] SmCl 3 ,[15] CuCl 2 , [16] SiCl 4 -methanol, [17] and Cp 2 ZrCl 2 [18] have been reported in the literature. However, except for a few examples, most of these procedures suffer from drawbacks such as use of precious metal catalysts, long reaction times, or harsh operating conditions.…”

Section: Introductionmentioning

confidence: 99%

Efficient One-Step Synthesis ofC₃-Symmetrical Benzenoid Compounds Mediated by SOCl₂/EtOH

Zhao

Kang

et al. 2012

Synthetic Communications

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The Condensation of Certain Aromatic Methyl Ketones

Cited by 24 publications

References 0 publications

Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases: Isomeric 1,3,5-Tris(naphthyl)benzenes

Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases: Isomeric 1,3,5-Tris(naphthyl)benzenes

Insights into the triple self-condensation reaction of thiophene-based methyl ketones and related compounds

Efficient One-Step Synthesis ofC₃-Symmetrical Benzenoid Compounds Mediated by SOCl₂/EtOH

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The Condensation of Certain Aromatic Methyl Ketones

Cited by 24 publications

References 0 publications

Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases: Isomeric 1,3,5-Tris(naphthyl)benzenes

Synthesis and Characterization of Organic Materials with Conveniently Accessible Supercooled Liquid and Glassy Phases: Isomeric 1,3,5-Tris(naphthyl)benzenes

Insights into the triple self-condensation reaction of thiophene-based methyl ketones and related compounds

Efficient One-Step Synthesis ofC3-Symmetrical Benzenoid Compounds Mediated by SOCl2/EtOH

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Efficient One-Step Synthesis ofC₃-Symmetrical Benzenoid Compounds Mediated by SOCl₂/EtOH