Lithiation of 2-(chloroaryl)-2-methyl-1,3-dioxolanes and application in synthesis of new ortho -functionalized acetophenone derivatives

Lukács, Gyula; Porcs-Makkay, Márta; Simig, Gyula

doi:10.1016/s0040-4039(03)00391-5

Cited by 19 publications

(15 citation statements)

References 27 publications

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“…For additional identification 12b was saponified with boiling solution of КОН (0.4 g) in a methanol/water mixture (1:1, 20 mL) for 3 h. Methanol was removed, water (5 mL) was added and the reaction mixture was acidified by HCl till р Н < 1. The precipitate of 2-acetyl-5-chlorobenzoic acid ( 12a ) [60] (10 mg) was filtered off and dried; m.p. 121–122 °С; 1 H-NMR: δ = 7.81 (d, J = 2 Hz 1H), 7.64 (br.…”

Section: Methodsmentioning

confidence: 99%

Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes

et al. 2014

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A thorough mechanistic study on cobalt-catalysed direct methoxycarbonylation reactions of chlorobenzenes in the presence of methyl oxirane on a wide range of substrates, including poly-and monochloro derivatives with multiple substituents, is reported. The results demonstrate that the reaction is potentially useful as it proceeds under very mild conditions (t = 62 °C, P CO = 1 bar) and converts aryl chlorides to far more valuable products (especially ortho-substituted benzoic acids and esters) in high yields. This transformation also offers another opportunity for the utilization of environmentally harmful polychlorinated benzenes and biphenyls (PCBs). This study is the first to discover an unexpected universal positive ortho-effect: the proximity of any substituent (including Me, Ph, and MeO groups and halogen atoms) to the reaction centre accelerates the methoxycarbonylation in chlorobenzenes. The effect of the ortho-substituents is discussed in detail and explained in terms of a radical anion reaction mechanism. The advantages of the methoxycarbonylation as a model for the mechanistic study of radical anion reactions are also illustrated.

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Section: Methodsmentioning

confidence: 99%

Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes

et al. 2014

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“…Ketals 8a-e were isolated with 94-98 % yield. Compounds 8a,c were characterized as per the literature [1] , while 8b,d,e are new compounds (see experimental section). 7a-e 8a-e…”

Section: Methodsmentioning

confidence: 99%

“…[1,2] The lithio species 2 thus formed were treated with various electrophiles to give ortho-functionalized acetophenone derivatives 3, which provided precursors of a series of benzannelated heterocyclic systems 4. …”

Section: Introductionmentioning

confidence: 99%

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Microwave assisted synthesis of benzophenone and acetophenone ethylene ketals

Lukács¹,

Porcs-Makkay²,

Komáromi³

et al. 2007

Arkivoc

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Dedicated to Professor Csaba Szántay on the occasion of his 80th birthdayAbstract A simple and convenient synthesis of acetophenone and benzophenone ethylene ketals was elaborated by performing the reaction of ethylene glycol in toluene in the presence of PTSA, under microwave irradiation with simultaneous removal of the water so formed. Under these conditions 100 % conversion and high yields were obtained within short reaction times.

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“…Based on our earlier work dealing with the ortho ‐lithiation of benzaldehydes ( 15 ), acetophenones ( 16 ), and benzophenones ( 17 , Scheme ) protected as 1,3‐dioxolanes ( 18 – 20 ), and subsequent lithium sulfinate formation and chlorination, we were in the position to prepare a broad variety of ortho ‐chlorosulfonyl ketals ( 21 – 23 ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Alkylation and Reduction of 4‐Aryl‐2H‐1,2,3‐benzothiadiazine 1,1‐dioxides

et al. 2019

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ortho‐(2‐Aryl‐1,3‐dioxolan‐2‐yl)benzenesulfonyl chlorides obtained from benzophenone ketals by directed ortho‐lithiation chemistry were cyclized either with hydrazine monohydrate or with acetohydrazide to furnish variously substituted 4‐aryl‐2H‐1,2,3‐benzothiadiazine 1,1‐dioxides. Alkylation of benzothiadiazine dioxides with alkyl iodides under basic conditions was elaborated, revealing significant differences compared to the reactivity of 4‐unsubstituted ones. Hydrogenation of the C=N double bond in the presence of platinum(IV) oxide is also described. Detailed NMR studies and DFT calculations supported the structure elucidation of the compounds.

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Lithiation of 2-(chloroaryl)-2-methyl-1,3-dioxolanes and application in synthesis of new ortho -functionalized acetophenone derivatives

Cited by 19 publications

References 27 publications

Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes

Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes

Microwave assisted synthesis of benzophenone and acetophenone ethylene ketals

Synthesis, Alkylation and Reduction of 4‐Aryl‐2H‐1,2,3‐benzothiadiazine 1,1‐dioxides

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