Dichlorination of β-Keto Esters and 1,3-Diketones Mediated by Oxone/Aluminum Trichloride Mixture in Aqueous Medium

Smonou, Ioulia; Giannopoulos, Vasileios; Katsoulakis, Nikolaos

doi:10.1055/s-0041-1737412

Cited by 3 publications

(1 citation statement)

References 31 publications

(41 reference statements)

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“…In the event, we found that our product was completely identical with an authentical sample prepared by chlorination of tert-butyl acetoacetate (15) with AlCl 3 /oxone (Scheme 3). [12] It should be noted that using 2.5 equiv. of 1, a 38 % yield of 16 was achieved under the same reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

The Surprising Reactivity of Chloromethyl Chlorosulfate with Active Methylene Compounds

Buchy,

Desmaële

2024

ChemistrySelect

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Condensation of chloromethyl chlorosulfate (1) with alkyl 1,3‐keto esters under phase‐transfer catalysis (PTC) conditions led to methylene bridged bis‐acetoacetates through a sequential chloromethylation‐β‐elimination‐Michael addition process. The latter compounds further evolved towards polyfunctional dihydrofuran and tetrahydropyran derivatives by competitive chloromethylation/chlorination reaction. In aprotic organic solvent, chlorination of the methylene active group is the main process and proceeded by reaction of the enolate of acetoacetate with the chlorine atom bound to the sulfonyl group of 1. The reactivity of some other active methylene compounds under PTC conditions was investigated. Acetylacetone reacted similarly to ethyl acetoacetate providing O‐heterocycles while ethyl cyanoacetate gave diethyl 2,4‐dicyanoglutaric acid diethyl ester together with 2‐diethyl 1,2‐dicyanocyclopropane‐1,2‐dicarboxylate. A plausible reaction mechanism is proposed whose the key feature is the competitive halogenation/chloromethylation of the intermediate methylene bridge dimeric active methylene compounds followed by intramolecular cyclization.

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Section: Resultsmentioning

confidence: 99%

The Surprising Reactivity of Chloromethyl Chlorosulfate with Active Methylene Compounds

Buchy,

Desmaële

2024

ChemistrySelect

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KI‐Mediated Chlorine Gas‐Free Synthesis of 3,3‐Dichloro‐2‐oxindole Derivatives

Wang

et al. 2023

Eur J Org Chem

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An efficient and environmentally friendly methodology for 3,3‐dichlorination and 2‐oxidation of indole derivatives is described. Using KI as promotor, MCl (M=K, Na) as chlorine source, and oxone as oxidant, the reaction proceeds smoothly affording various functionalized 3,3‐dichloro‐2‐oxindoles in moderate to excellent yields. This strategy can also be extended to 3‐substituted indoles. With a broad substrate scope, it is a practical approach to 3,3‐disubstituted‐2‐oxindoles.

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Product Selectivity Control under Acidic and Basic Conditions on Oxidative Transformation of 1,3-Dicarbonyls Using Sodium Hypochlorite Pentahydrate

Kirihara,

Takizawa,

Sakamoto

et al. 2024

Synthesis

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In this study, we reported that the reactivity of 1,3-dicarbonyls with sodium hypochlorite pentahydrate (NaOCl・5H2O) as an easy-to-handle oxidant, alters greatly depending on the pH value. The reaction of NaOCl・5H2O under weakly basic conditions (pH 12) gives the corresponding carboxylic acids in up to 97% yield. Upon addition of AcOH (pH 5), chlorination of active methylene sites proceeds efficiently to afford dichlorinated products in high yields.

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Dichlorination of β-Keto Esters and 1,3-Diketones Mediated by Oxone/Aluminum Trichloride Mixture in Aqueous Medium

Cited by 3 publications

References 31 publications

The Surprising Reactivity of Chloromethyl Chlorosulfate with Active Methylene Compounds

The Surprising Reactivity of Chloromethyl Chlorosulfate with Active Methylene Compounds

KI‐Mediated Chlorine Gas‐Free Synthesis of 3,3‐Dichloro‐2‐oxindole Derivatives

Product Selectivity Control under Acidic and Basic Conditions on Oxidative Transformation of 1,3-Dicarbonyls Using Sodium Hypochlorite Pentahydrate

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