Constituents of commercial methoxychlor-III. The mechanism of tetraanisylethylene formation. unsym-Tetraarylethylenes (Ar2C=CAr2′): synthesis from DT class pesticides, and conversion to phenanthrenes and dibenzo[g,p]chrysenes

Mitchell, Reginald H.; Mazuch, Ludvik; Shell, Barry; West, Paul R.

doi:10.1139/v78-207

Cited by 10 publications

(3 citation statements)

References 3 publications

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“…The vinyl chlorides were also prepared from the corresponding ethylene compounds, 1aCl according to ref and 1dCl according to ref . The spectral data of 1-chloro-1,2,2-triphenylethene ( 1aCl ), 1-chloro-1,2,2-tris( p -methoxyphenyl)ethene ( 1dCl ), 1-bromo-1-( p -methoxyphenyl)-2,2-diphenylethene ( 1cBr ), and 1-bromo-1,2,2-tris( p -methoxyphenyl)ethene ( 1dBr ) have been reported.…”

Section: Methodsmentioning

confidence: 99%

Substituent Effects on the Photogeneration and Selectivity of Triaryl Vinyl Cations

Dorp

Lodder

2008

J. Org. Chem.

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The photochemical reactions of a series of triaryl vinyl halides 1X in acetic acid and in acetonitrile have been studied using product analysis as a function of the time of irradiation. The quantum efficiencies of formation of the products derived from the photogenerated vinyl cations 1(+) depend on the alpha-aryl substituent, the beta-aryl substituent, the leaving group X (= bromide or chloride), and the temperature at which the irradiations are carried out. Hammett correlation or noncorrelation of the alpha-aryl substituent effects with (excited-state) substituent constants indicates that the ions 1(+) are formed directly from the excited states of 1X by heterolytic cleavage of the carbon-halogen bond. Homolytic cleavage, yielding radicals 1(*), is a parallel process: the partitioning into ion and radical occurs in the excited state. This conclusion is corroborated by the leaving group effect and the temperature effect. By performing the photochemical reactions of 1X in the presence of HOAc and/or NaOAc as well as the labeled common halide ion (82)Br(-) or (36)Cl(-), the relative reactivities of the cations 1(+) toward these nucleophiles were determined. The selectivities follow the Reactivity-Selectivity Principle. The temperature effect data show that the reactions of the cations with the anionic nucleophiles are (de)solvation controlled and their reactions with the neutral nucleophile activation controlled.

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Section: Methodsmentioning

confidence: 99%

Substituent Effects on the Photogeneration and Selectivity of Triaryl Vinyl Cations

Dorp

Lodder

2008

J. Org. Chem.

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“…This result agrees well with earlier works of Davidson [21] and Mitchell. [22] The latter author reported that the failure of 9,10-diphenylphenanthrene derivatives to undergo a second photocyclization to the corresponding dibenzo [g,p]chrysenes is not due to steric hindrance of the ortho hydrogen atoms. In contrast, under Scholl conditions (AlCl 3 , nitrobenzene) 9,10-diphenylphenanthrenes are clearly converted into the dibenzo [g,p]chrysenes.…”

Section: Photocyclization To Phenanthrene Derivatives 22mentioning

confidence: 99%

Tetraphenylethene‐Derived Columnar Liquid Crystals and Their Oxidative Photocyclization

et al. 2003

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The synthesis of novel tetraphenylethenes 9a−f, 13, and 18a,b bearing ether, biphenyl, and 4-cyanobiphenyl moieties via a McMurry reaction and Suzuki coupling as key steps is described. Mesogenic properties of these compounds were studied by differential scanning calorimetry (DSC), optical polarizing microscopy, and X-ray diffraction. Ether-substituted derivatives 9a,b with chain lengths C 8 or C 9 were nonmesogenic. Compounds 9c−f with longer alkyl chains displayed hexagonal columnar mesophases. Whereas cyanobiphenyl derivative 13 was non-mesogenic, the corresponding biphenyl systems 18a,b with decyloxy and dodecyloxy

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“…This class of congested, twisted aromatic compounds is of considerable interest in the design of organoelectronic devices . We note in passing that 9,10-diarylphenanthrenes are known to give dibenzo[ g , p ]chrysene derivatives under oxidative thermal conditions, which adds to the utility of the present annulation reaction for the synthesis of functional materials. …”

mentioning

confidence: 99%

Phenanthrene Synthesis by Iron-Catalyzed [4 + 2] Benzannulation between Alkyne and Biaryl or 2-Alkenylphenyl Grignard Reagent

2011

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The [4+2] benzannulation reaction of internal or terminal alkynes with 2-biaryl, 2-heteroarylphenyl, or 2-alkenylphenyl Grignard reagents in the presence of Fe(acac)(3), 4,4'-di-tert-butyl-2,2'-bipyridyl, and 1,2-dichloro-2-methylpropane takes place at room temperature in 1 h to give 9-substituted or 9,10-disubstituted phenanthrenes and congeners in moderate to excellent yields. The reaction tolerates sensitive functional groups such as bromide and olefin. When applied to a 1,3-diyne, the annulation reaction takes place on both acetylenic moieties to give a bisphenanthrene derivative.

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Constituents of commercial methoxychlor-III. The mechanism of tetraanisylethylene formation. unsym-Tetraarylethylenes (Ar₂C=CAr₂′): synthesis from DT class pesticides, and conversion to phenanthrenes and dibenzo[g,p]chrysenes

Cited by 10 publications

References 3 publications

Substituent Effects on the Photogeneration and Selectivity of Triaryl Vinyl Cations

Substituent Effects on the Photogeneration and Selectivity of Triaryl Vinyl Cations

Tetraphenylethene‐Derived Columnar Liquid Crystals and Their Oxidative Photocyclization

Phenanthrene Synthesis by Iron-Catalyzed [4 + 2] Benzannulation between Alkyne and Biaryl or 2-Alkenylphenyl Grignard Reagent

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