Electrophilic aromatic substitution. 14. [1] A kinetic, NMR, and Raman study of the aluminum chloride-catalyzed reaction ofp-toluene-sulfonyl chloride with benzene and toluene in dichloromethane

DeHaan, Franklin P.; Ahn, Paul Y.; Kemnitz, Carl R.; Steven, K.; Na, Jim; Patel, Bimal R.; Ruiz, Richard; Villahermosa, Randy M.

doi:10.1002/(sici)1097-4601(1998)30:5<367::aid-kin7>3.0.co;2-q

Cited by 3 publications

(1 citation statement)

References 13 publications

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“…Similarly, the AlCl 3 -catalysed reaction of p-CH 3 C 6 H 4 SO 2 Cl with toluene has been reported to give 80% (p-CH 3 C 6 H 4 ) 2 SO 2 and only 20% p-CH 3 C 6 H 4 SO 2 (o-CH 3 C 6 H 4 ). 17 When AlCl 3 was added slowly (piecewise) to the PhCl-SOCl 2 mixture (to keep PhCl in excess over the reactive SOCl 2 -AlCl 3 adduct) at 25 °C, the reaction led to formation of a sole sulfoxide isomer (p-ClC 6 H 4 ) 2 SO (Table 1), showing the -Cl group is essentially only a para-director for formation of the diaryl sulfoxide. No other organosulfur compounds were formed.…”

Section: Substituent Effects On the Alcl 3 -Catalysed Electrophilic Aromatic Substitution Reactions Of Soclmentioning

confidence: 99%

Investigations on the Lewis-Acids-Catalysed Electrophilic Aromatic Substitution Reactions of Thionyl Chloride and Selenyl Chloride, the Substituent Effects, and the Reaction Mechanisms

Sun

Haas

McWilliams

et al. 2013

Journal of Chemical Research

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The previously established aluminium-chloride-(AlCl 3 )-catalysed electrophilic aromatic substitution (EAS) of benzene (PhH) with thionyl chloride (SOCl 2 ) has been extended to toluene (PhCH 3 ), chlorobenzene (PhCl), and phenol (PhOH). -CH 3 was found to be mainly a para-director with a minor ortho-directing effect on the EAS reactions giving diaryl sulfoxides (Ar 2 SO). -Cl was found to be exclusively a para-director for formation of Ar 2 SO. All the -CH 3 , -Cl, and -OH groups were shown to be exclusive para-directors for formation of diaryl sulfides (Ar 2 S) from the EAS reactions. Although the reactions of PhH and PhCH 3 with SOCl 2 in the presence of AlCl 3 gave the major Ar 2 SO and minor Ar 2 S at ambient temperature, the phenol (PhOH) reaction was shown to give only the reduced sulfide (p-HOC 6 H 4 ) 2 S with no sulfoxide (p-HOC 6 H 4 ) 2 SO formed. The mixed diaryl sulfoxides ArSOAr′ (Ar, Ar′=C 6 H 5 , p-CH 3 C 6 H 4 ; C 6 H 5 , o-CH 3 C 6 H 4 ; and C 6 H 5 , p-ClC 6 H 4 ) were produced in the AlCl 3 -catalysed reactions of SOCl 2 with molar 1:1 PhH-PhX mixtures (X=CH 3 and Cl). Efforts to enhance the yield of S-aryl arenesulfonothioates ArSO 2 SAr (Ar=Ph, p-CH 3 C 6 H 4 , and p-ClC 6 H 4 ) from the AlCl 3 -catalysed EAS reactions of SOCl 2 were made, showing that decreasing the molar ratios of ArH/SOCl 2 or lowering the temperature resulted in an increase in the product yield. A detailed mechanism has been proposed to account for the formation of ArSO 2 SAr. The Lewis-acid-MCl 3 -(M=Al and Fe)-catalysed EAS reactions of PhH with selenyl chloride (SeOCl 2 ) were demonstrated to give the reduced diphenyl selenide (Ph 2 Se) and diphenyl diselenide (PhSeSePh) via novel auto-redox processes in selenium of the key EAS intermediates.

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Section: Substituent Effects On the Alcl 3 -Catalysed Electrophilic Aromatic Substitution Reactions Of Soclmentioning

confidence: 99%

Investigations on the Lewis-Acids-Catalysed Electrophilic Aromatic Substitution Reactions of Thionyl Chloride and Selenyl Chloride, the Substituent Effects, and the Reaction Mechanisms

Sun

Haas

McWilliams

et al. 2013

Journal of Chemical Research

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Mechanism and kinetics of catalytic decalin alkylation for the synthesis of high-performance fuel

Lu,

Xue,

Wang

et al. 2024

Chemical Engineering Science

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Formation of Diphenyl Sulfoxide and Diphenyl Sulfide via the Aluminum Chloride–Facilitated Electrophilic Aromatic Substitution of Benzene with Thionyl Chloride, and a Novel Reduction of Sulfur (IV) to Sulfur (II)

Sun

Haas

Sayre

et al. 2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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The aluminum chloride (AlCl 3 )-facilitated electrophilic aromatic substitution (EAS) reaction of benzene (PhH) with thionyl chloride (SOCl 2 ) in the molar ratio of PhH:SOCl 2 :AlCl 3 = 2:1:1 was studied under different conditions. At about 70 • C, adding granular AlCl 3 (equimolar to SOCl 2 ) piecewise to a 2:1 mixture of PhH and SOCl 2 led to formation of a highly pure (99.9%) sole product of diphenyl sulfoxide (Ph 2 SO) in an isolated yield of 85% after aqueous workup. It represents a simple and very efficient synthesis of Ph 2 SO, an important fundamental organic reagent. At about 0 • C, adding PhH (twice the molar quantity of SOCl 2 ) to a 1:1 mixture of SOCl 2 and AlCl 3 gave both diphenyl sulfide Ph 2 S (yield: 37%) and Ph 2 SO (yield: 27%) after aqueous workup, together with a small amount of S-phenyl benzenesulfonothioate PhSO 2 SPh (yield: about 5%) and a trace amount of diphenyl sulfone (Ph 2 SO 2 ). A possible mechanism has been proposed to account for formation of all these products, especially for the formation of Ph 2 S [S (II)] from SOCl 2 [S (IV)], which involves a novel reduction of sulfur in the course of the EAS reaction.

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Electrophilic aromatic substitution. 14. [1] A kinetic, NMR, and Raman study of the aluminum chloride-catalyzed reaction ofp-toluene-sulfonyl chloride with benzene and toluene in dichloromethane

Cited by 3 publications

References 13 publications

Investigations on the Lewis-Acids-Catalysed Electrophilic Aromatic Substitution Reactions of Thionyl Chloride and Selenyl Chloride, the Substituent Effects, and the Reaction Mechanisms

Investigations on the Lewis-Acids-Catalysed Electrophilic Aromatic Substitution Reactions of Thionyl Chloride and Selenyl Chloride, the Substituent Effects, and the Reaction Mechanisms

Mechanism and kinetics of catalytic decalin alkylation for the synthesis of high-performance fuel

Formation of Diphenyl Sulfoxide and Diphenyl Sulfide via the Aluminum Chloride–Facilitated Electrophilic Aromatic Substitution of Benzene with Thionyl Chloride, and a Novel Reduction of Sulfur (IV) to Sulfur (II)

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