REACTIONS OF ALKYLTRIPHENYLPHOSPHONIUM HALIDES WITH ARENESULFONIC ACID

Abstract

The reaction of equimolar amounts of alkyltriphenylphosphonium bromides with 1-naphthalenesulfonic, 2,4-dinitrobenzenesulfonic, and sulfosalicylic acids in water leads to the formation of ionic alkyltriphenylphosphonium arenesulfonates [Ph3PR][OSO2Ar], R = CH2OMe, Ar = Naft-1 (I); R = CH=СHPPh3, Ar = C6H3(NO2)2-2,4 (II); R = (CH2)2Br (III), R = C6H11-cyclo (IV), Ar = C6H3(COOH-3)(OH-4). Structures of complexes I‒IV have been established by X-ray diffraction analysis. Complexes I–IV are air-stable transparent crystals, readily soluble in arenes, ethanol, chloroform, acetonitrile, tetrahydrofuran, carbon tetrachloride, diethyl ether, and poorly soluble in water at room temperature. Phosphorus atoms in alkyltriphenylphosphonium cations I–IV have tetrahedral coordination, arenesulfonate anions have the usual geometry with a tetrahedral sulfur atom. Compound II crystallizes as a hydrate. The P–C bond lengths vary in the range 1.240(3)–1.827(3) Å, which is less than the sum of the covalent radii of partner atoms (1.83 Å). CPC bond angles vary within 103.77(9)°−112.80(12)°; S–C distances in sulfonate anions are 1.768(3)‒1.807(3) Å. The S–O bond lengths are close to each other and take the values 1.427(3)‒1.4710(17) Å. The bond angles OSO (111.56(10)°−115.74(18)°) are larger than the OSC angles (103.02(12)°−107.26(9)°). Cations and anions in complexes I‒IV are connected by short contacts of S=O∙∙∙Н(Рh) type [2.350‒2.717 Å] (the sum of Van der Waals partner atoms O···Н is 2.62 Å). In crystal II, short contacts of the N=O∙∙∙H(Ph) type [2.448–2.699 Å] are also observed. Crystal structures of I, III, IV contain CH∙∙∙π interactions (2.658‒2.898 Å). Moreover, the spatial structure of crystals II, III is formed with the participation of π–π interactions. (3.276‒3.359 Å). For citation: Sharutin V.V., Sharutina O.K., Mekhanoshina E.S. Reactions of alkyltriphenylphosphonium halides with arenesulfonic acid. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 3. P. 18-26. DOI: 10.6060/ivkkt.20236603.6724.