Electrochemical Synthesis of Alkyl Nitroaromatic Compounds

Gallardo, Iluminada; Guirado, Gonzalo; Marquet, Jacques

doi:10.1021/jo025898k

Cited by 22 publications

(19 citation statements)

References 17 publications

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“…The electrochemistry of Meisenheimer complexes in solution has been exhaustively studied. [56,57] In accordance with these studies, electrodes modified with zeolite NaY incorporating Meisenheimer complex exhibit an oxidation peak in the presence of NaClO 4 as electrolyte in DMF. When size-excluded tetrabutylammonium perchlorate was used as electrolyte, the electrochemical response disappeared, since under these conditions only the external surface can be probed due to the impossibility of the bulky electrolyte diffusing inside the pores.…”

Section: Wwwchemeurjorgsupporting

confidence: 76%

Anionic Organic Guests Incorporated in Zeolites: Adsorption and Reactivity of a Meisenheimer Complex in Faujasites

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Doménech

et al. 2005

Chemistry A European J

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Zeolites are suitable microporous hosts for positively charged organic species, but it is believed that they cannot adsorb organic anions. Pure Meisenheimer complex, derived from reduction of 2,4-dinitroaniline with NaBH4, was adsorbed inside faujasite cavities. Evidence for the internal incorporation of this negatively charged reaction intermediate comes from 1) XPS elemental analysis as a function of the depth of penetration into the particle, 2) the remarkable blue shift in lambda(max) of the Meisenheimer complex adsorbed on zeolite (ca. 470 nm) as compared to that in acetonitrile (580 nm) and 3) from the lack of reactivity with size-excluded hydride-acceptor reagents. Evidence is provided in support of an adsorption mechanism in which a neutral ion pair (alkali metal ion + Meisenheimer anion) is the actual species being adsorbed. In fact it appears that there is remarkable increase in the association constant for the ion-pair complex within the zeolite cavities as compared to DMF solution. Although this mechanism of adsorption as an ion-pair complex has precedents in the adsorption of some inorganic salts, what is novel is the notable increase in the stability and persistence of the Meisenheimer anion (a anionic reaction intermediate) as a result of zeolite inclusion. Adsorbed Meisenheimer complex exhibits much lower reactivity towards electron acceptors, oxygen, and water. Cyclic voltammetry of zeolite-modified electrodes reveals for the Meisenheimer complex adsorbed on LiY a reversible redox peak that is not observed in solution and has been interpreted as arising from site isolation and stabilisation of the electrochemically generated species.

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Section: Wwwchemeurjorgsupporting

confidence: 76%

Anionic Organic Guests Incorporated in Zeolites: Adsorption and Reactivity of a Meisenheimer Complex in Faujasites

Herance

Concepción

Doménech

et al. 2005

Chemistry A European J

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“…Alkylation of nitroaromatic compounds through C−C cross-coupling is achieved by utilizing pyrophoric organometallic reagents such as butyllithium. 43 C−S cross-coupling allows a more desirable way to produce the alkyl thiolated nitroaromatic compounds. We have employed alkyl and benzyl thiols for alkyl thiolation of 1bromo-4-nitrobenzene, obtaining yields of 91−98%.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Nitroaromatic compounds are useful building blocks for nucleophilic aromatic substitution. Alkylation of nitroaromatic compounds through C–C cross-coupling is achieved by utilizing pyrophoric organometallic reagents such as butyllithium . C–S cross-coupling allows a more desirable way to produce the alkyl thiolated nitroaromatic compounds.…”

Section: Resultsmentioning

confidence: 99%

Mono- and Dinuclear α-Diimine Nickel(II) and Palladium(II) Complexes in C–S Cross-Coupling

et al. 2020

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The usefulness of transition metal catalytic systems in C–S cross-coupling reactions is significantly reduced by air and moisture sensitivity, as well as harsh reaction conditions. Herein, we report four highly air- and moisture-stable well-defined mononuclear and bridged dinuclear α-diimine Ni(II) and Pd(II) complexes for C–S cross-coupling. Various ligand frameworks, including acenaphthene- and iminopyridine-based ligands, were employed, and the resulting steric properties of the catalysts were evaluated and correlated with reaction outcomes. Under aerobic conditions and low temperatures, both Ni and Pd systems exhibited broader substrate scope and functional group tolerance than previously reported catalysts. Over 40 compounds were synthesized from thiols containing alkyl, benzyl, and heteroaryl groups. Also, pharmaceutically active heteroaryl moieties are incorporated from thiol and halide sources. Notably, the bridged dinuclear five-coordinate Ni complex has outperformed the remaining three mono four- or six-coordinate complexes by giving almost quantitative yields across a broad substrate scope.

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“…Analysis of the cyclic voltammogram of the mixture enabled us to determine the percentage of 10 remaining in solution, that is, the extent of the nucleophilic attack (by determining the current value of the cathodic peak of 10 when an initial cathodic scan is recorded), the type(s) of substitution product(s), that is, trinitrocyclohexadienyl σ H complexes or σ X complexes, for which E pa is expected to be between 0.5 and 1.7 V, [5,10] and the type(s) of product(s) obtained after the oxidation of the complex [NASH or NASX product (which in this case would be reactant 10) can be identified by growing a reduction wave in a second cycle after the oxidation of the σ H complex or after thorough controlled-potential electrolysis of the sample]. Figure 2 shows the absence of electroactive species 10 in the first cathodic cycle, which means that the percentage of the nucleophilic attack is 100 %.…”

Section: Electrochemical Behavior Of Phosphorus σ H Complexesmentioning

confidence: 99%

Electrochemical Synthesis of Organophosphorus Compounds through Nucleophilic Aromatic Substitution: Mechanistic Investigations and Synthetic Scope

2011

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Advantages of the electrochemical approach in the nucleophilic aromatic substitution reaction, such as (a) low cost and ready availability of reagents, (b) atom economy, and (c) high yields (approaching 100 %), are applied to rationalize the (polar or radical) mechanism and to develop new greener synthetic routes for the synthesis of substituted nitroaromatic organophosphorus compounds. The nucleophiles used to study the feasibility and viability of the reaction are the classical tervalent phosphorus nucleophiles: trimethylphos-

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Electrochemical Synthesis of Alkyl Nitroaromatic Compounds

Cited by 22 publications

References 17 publications

Anionic Organic Guests Incorporated in Zeolites: Adsorption and Reactivity of a Meisenheimer Complex in Faujasites

Anionic Organic Guests Incorporated in Zeolites: Adsorption and Reactivity of a Meisenheimer Complex in Faujasites

Mono- and Dinuclear α-Diimine Nickel(II) and Palladium(II) Complexes in C–S Cross-Coupling

Electrochemical Synthesis of Organophosphorus Compounds through Nucleophilic Aromatic Substitution: Mechanistic Investigations and Synthetic Scope

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