Synthesis of two crystalline species of the Friedel-Crafts intermediate antimony pentachloride-p-toluoyl chloride. Crystal structures of the donor-acceptor complex and of the ionic salt

Chevrier, Bernard; Carpentier, J. M. Le; Weiss, Raymond

doi:10.1021/ja00771a031

Cited by 41 publications

(20 citation statements)

References 4 publications

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“…La distance celle qui a 6t4 trouv6e dans les ions oxocarbonium de structure connue (Boer, 1968;Chevrier, Le Carpentier & Weiss, 1972). La longueur de la liaison C(2)-C(3) est caract6ris-tique d'une liaison simple carbone-carbone du type sp3-sp 3.…”

Section: Gdomdtrie De L'ion Dthyl Oxocarboniumunclassified

Etude de complexes acide de Lewis–halogénure d'acide. II. Structure cristalline du tétrachlorogallate d'éthyl oxocarbonium et de l'hexachloroantimonate d'isopropyl oxocarbonium

Carpentier¹,

Weiss²

1972

Acta Crystallogr Sect B

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Section: Gdomdtrie De L'ion Dthyl Oxocarboniumunclassified

Etude de complexes acide de Lewis–halogénure d'acide. II. Structure cristalline du tétrachlorogallate d'éthyl oxocarbonium et de l'hexachloroantimonate d'isopropyl oxocarbonium

Carpentier¹,

Weiss²

1972

Acta Crystallogr Sect B

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“…1.13 Å for carbon monoxide) . More recently, Weiss and Kochi have characterized aryl‐substituted systems, [ArCO] + , but to date, heteroatom‐stabilized systems [XCO] + ( VI ), remain extremely rare ,. We postulated that such systems might be of interest not only from a fundamental perspective (i.e.…”

Section: Methodsmentioning

confidence: 99%

Successive Protonation of an N‐Heterocyclic Imine Derived Carbonyl: Superelectrophilic Dication Versus Masked Acylium Ion

et al. 2018

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Carbonyl cations are among the most commonly invoked reactive intermediates in organic synthesis. While Olah pioneered superacids to provide a “stable ion” environment for their study in situ, isolated examples are rare. Here, we disclose successive protonation of an N‐heterocyclic imine (NHI) derived carbonyl compound (IDippN)2CO, 2, to the monocation [(IDippN)(IDippNH) CO]+, [3]+, and the doubly protonated dication [(IDippNH)2CO]2+, [4]2+. [3]+ represents a rare example of an N‐protonated carbonyl cation and [4]2+ the first example of a superelectrophilic carbonyl dication. All three compounds have been characterized by X‐ray crystallography and IR spectroscopy, revealing stepwise strengthening of the C=O bond on protonation. The unique stability of these systems is attributed to the enhanced basicity and steric profile provided by the NHI substituents. In addition, we report the related singly NHI‐stabilized cation [IDippNCO]+, [5]+. Crystallographic and DFT analyses provide insight into the interaction between the carbonyl fragment and the NHI, which reveals that the [CNCO]+ unit (isoelectronic to CCCO) can be described as an acylium cation “masked” as a cumulene.

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“…In our earlier publication [24] on Al 2 Cl 6 -catalyzed FC acylations involving phenyl aromatic compounds, a main pathway was established that identified the key stationary points on the PES with the mechanism that corresponded to the steps known to occur both through experimental [53][54][55][56][57][58][59] and theoretical research [53,[60][61][62][63][64][65][66][67][68]. The obtained mechanism is briefly detailed here and for clarity, repeated in [69][70][71][72][73][74], followed by a distorted t-shape stacking (t) configuration (Int2B), C-C bond formation ([TS3] ‡ , Int3) and ultimately deprotonation ([TS4] ‡ ) yielding Int4 (see Fig.…”

Section: Mechanismmentioning

confidence: 99%

A DFT study of the formation of xanthydrol motifs during electrophilic poly(aryl ether ketone) synthesis

et al. 2015

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The reaction pathway of the cyclization of 2-phenoxybenzophenone into 9-phenyl-9H-xanthen-9-ol in the presence of acid and an excess of AlCl33 was studied using density functional theory. This type of reaction is known to occur during the Friedel-Crafts polycondensation of poly(aryl ether ketones) following the undesired benzoylation of nucleophilic positions ortho- to the growing polymer's ether groups. The formed defect acts as an undesired terminator of the polymer chain, causing severe problems in the polymer's melt state. A branched, multistep mechanism reminiscent of the Friedel-Crafts acylation reaction is discovered; the reaction starts with the protonation of the carbonyl oxygen, followed by intramolecular electrophilic attack on the carbonyl carbon that determines the turnover frequency of the catalytic cycle and ends by deprotonation of the Wheland intermediate.

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Synthesis of two crystalline species of the Friedel-Crafts intermediate antimony pentachloride-p-toluoyl chloride. Crystal structures of the donor-acceptor complex and of the ionic salt

Cited by 41 publications

References 4 publications

Etude de complexes acide de Lewis–halogénure d'acide. II. Structure cristalline du tétrachlorogallate d'éthyl oxocarbonium et de l'hexachloroantimonate d'isopropyl oxocarbonium

Etude de complexes acide de Lewis–halogénure d'acide. II. Structure cristalline du tétrachlorogallate d'éthyl oxocarbonium et de l'hexachloroantimonate d'isopropyl oxocarbonium

Successive Protonation of an N‐Heterocyclic Imine Derived Carbonyl: Superelectrophilic Dication Versus Masked Acylium Ion

A DFT study of the formation of xanthydrol motifs during electrophilic poly(aryl ether ketone) synthesis

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