The Configuration of Sulfoxides. Mixed Crystals of Sulfoxides with Sulfones

Rheinboldt, Heinrich; Giesbrecht, Ernesto

doi:10.1021/ja01210a019

Cited by 35 publications

(10 citation statements)

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“…Diphenyl sulphoxide, 4,4-dibromo-, 4,4-dichloro-, 4,4-difluoro-, 4,4-dimethoxy-and 4,4-dimethyl-diphenyl sulphoxides were prepared by Friedel-Crafts reaction of thionyl chloride with the corresponding monosubstituted benzene in the presence of aluminium chloride. 4 All the 4-substituted diphenyl sulphoxides, 4-methoxy-4'-nitro-, 4-methyl-4'-nitro-and 4,4-diacetyldiphenyl sulphoxides were prepared by oxidation of the appropriate sulphide with potassium dichromate' (one third molar equivalent) in acetic acid at 40°C for 24 h. 4-Bromo-4'-nitro-, 4-chloro-4'-nitro-and 4-fluoro-4-nitro-diphenyl sulphoxides were prepared by the oxidation of the sulphides with potassium peroxydisulphate6 (1 : 1 molar ratio) in aqueous acetonitrile. 4,4-Dinitrodiphenyl sulphoxide was obtained from the sulphide by oxidation with potassium peroxydisulphate in aqueous acetic acid containing ca.…”

Section: Methodsmentioning

confidence: 99%

NMR study of substituent effects in 4‐substituted and 4,4′‐disubstituted diphenyl sulphoxides and sulphones

Chandrasekaran

Perumal

Wilson

1989

Magnetic Reson in Chemistry

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The proton and carbon NMR spectra of nine 4-Xdiphenyl sulphoxides, seven 4-X-4'-N02diphenyl sulphoxides, eight 4,4'-X,diphenyl sulphoxides, eight 4X-diphenyl sulphones, seven 4-X4'-N02diphenyl sulphones and eight 4,4'-X,diphenyl sulphones have been obtained. Correlation of the ' ' C chemical shifts with the appropriate substituent chemical shifts (SCS) for monosubstituted benzenes (Lynch plots) does not show the enhancement of substituent effect at C-1 (para to the substituent) that was a feature of the corresponding sulphides studied earlier. Dual substituent parameter (DSP) correlations of the I3C chemical shifts with al/aao are excellent for carbons meta (C-2,6) and para (C-1) to the substituent. The trends for the series sulphides, sulpboxides, sulphones, where a decreasing response to the change of substituent is the general observation, are discussed. Changes of molecular conformation may also influence the transmission of electronic effects to the ring not carrying the variable substituent X.

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Section: Methodsmentioning

confidence: 99%

NMR study of substituent effects in 4‐substituted and 4,4′‐disubstituted diphenyl sulphoxides and sulphones

Chandrasekaran

Perumal

Wilson

1989

Magnetic Reson in Chemistry

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“…To a refluxing solution of ditolyldisulphide (3 g, 0.012 mol, Aldrich Chemical Company Inc.), chloroform (25 mL), and methanol (25 mL) in a 250-mL three-neck flask, lead tetraacetate (25 g) in chloroform (100 mL) was added dropwise over a 1-h period. The solution was allowed to reflux for an additional 24 h. Most of the solvent (100 mL) was distilled from the reaction flask, and water (20 For personal use only. mL) was added.…”

Section: Methyl(4-tolylsulphinare)mentioning

confidence: 99%

Substituent effects on benzyl radical hyperfine coupling constants. Part 2. The effect of sulphur substituents

Wayner¹,

Arnold²

1984

Can. J. Chem.

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Several 4-substituted benzyl radicals of the general form R(0,,)SC6H4CH2. ( 1 7 = 0. 1, 2; R = Me, Ph, Tol. COCH,, OCH,) have been investigated by electron spin resonance (esr) spectroscopy. In general, the ability to delocalize spin density onto the substituent decreases as n increases. The effect of R on the spin density depends on the oxidation state of the sulphur. These trends are explained by considering the sulphur to be either a spin donor or a spin acceptor, depending on the oxidation state. Faisant appel B la resonance paramagnttique Clectronique (rpe), on a CtudiC plusieurs radicaux benzyles substituCs en position 4, de structure gCnCrale R(0,,)SC6H4CH2. ( 1 1 = 0, 1, 2; R = Me, Ph, Tol, COCH,, OCH1). D'une fason gCnCrale, la facilitk B dClocaliser la densitk de spin sur le substituant diminue avec une augmentation de n. L'effet de R sur la densitd, de spin dkpend de I'Ctat d'oxydation du soufre. On peut expliquer ces tendances en considerant le soufre comme Ctant soit un donneur dc spin ou un accepteur de spin dependant de son Ctat d'oxydation. On a determink les valeurs u',,.

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“…[PtCI2py2], the appropriate nucleophile, and silver sulfoxide with zinc in acetic acid (16). para-toluenesulfonate (silver tosylate) were allowed to 4-Chlorodiphenyl Sulfide This nucleophile was isolated from the reaction of sodium thiophenolate with para-dichlorobenzene in D M F (17), b.p.…”

Section: 4'-dichlorodiphet~yl Sulfide Reaction Products Stoichiomementioning

confidence: 99%

Nucleophilic Reactivity of 4,4′-Disubstituted Diphenyl Sulfides Towards trans-Dichlorobis(pyridine)platinum(II)

Gaylor¹,

Senoff²

1971

Can. J. Chem.

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The kinetics of the reaction of trans-[PtC12py2] with a series of 4,4'-disubstituted diphenyl sulfides, XC6H4SC6H4Y, have been studied at 30° in methanol. A linear free energy correlation has been obtained between the logarithm of the second order rate constant and the sum of the Hamrnett substituent parameters for X and Y. This result is consistent with the notion that bond making is the driving force when divalent sulfur functions as a nucleophile towards platinum(I1) substrates and is consistent with the inability of 4,4'-dinitrodiphenyl sulfide to coordinate to platinum(I1).Les cinttiques des rtactions entre le [PtC12py2]-trans et une strie de diphtnylsulfures disubstituks en -4,4', XC6H4SC6H4Y, ont kt6 etudites i 30 "C dans le mtthanol. Une corrklation lineaire de l'tnergie libre a ttk obtenue entre le logarithme de la constante de vitesse du second ordre et la sornme des parametres de Harnrnett pour les substituants X et Y. Ce rtsultat est consistant avec la notion d'apres laquelle I'ttablissement d'une liaison est la force directive lorsqu'un soufre divalent fonctionne en tant que nucltophile envers le platine(I1); ce rtsultat est Bgalement cohtrent avec le fait que le dinitro-4,4' diphknylsulfure ne se coordonne pas avec le platine(I1).Canadian Journal of Chemistry, 49, 2390Chemistry, 49, (1971 Substitution reactions of square planar dB metal complexes, especially those of platinum(I1) have been well documented (1-3). Previous investigations have utilized trans-[PtCl,py,] as a representative substrate in order to investigate the reactivity of a variety of nucleophiles towards platinum(I1) complexes (4, 5). As part of a general interest in the donor properties of ligands containing a sulfur donor atom, we have undertaken a kinetic study of reaction 1 where Ar,S = a 4,4'-disubstituted diphenyl sulfide and py = pyridine. It was also anticipated that this study [ I ] would provide a quantitative indication of the ability of divalent sulfur in a diary1 sulfide to transmit the electronic effect of a para-substituent. The results of this study are reported at this time. Results and DiscussionThe rates of reaction between trans- [PtCl,py,] and XC6H4SC6H4Y ( = Ar,S) follow the usual two term rate law which is common to substitution reactions of square planar platinum(I1) complexes, viz. eq. 2, where k, is a first order rate The experimental pseudo first order rate constants, k,,,, are related to k , and k, by 151.Typical plots of k,,, us. [XC,H4SC6H4Y] are shown in Fig. 1. The slopes of these linear plots correspond to the various k,'s and the common intercept to k,. The kinetic data are tabulated in Table 1 together with the calculated values of the nucleophilic reactivity constant, nPt0, and the sum of the Hammett substituent parameters for each nucleophile. The nucleophilic reactivity constant has been defined by eq. 6. In order to For personal use only.

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The Configuration of Sulfoxides. Mixed Crystals of Sulfoxides with Sulfones

Cited by 35 publications

References 0 publications

NMR study of substituent effects in 4‐substituted and 4,4′‐disubstituted diphenyl sulphoxides and sulphones

NMR study of substituent effects in 4‐substituted and 4,4′‐disubstituted diphenyl sulphoxides and sulphones

Substituent effects on benzyl radical hyperfine coupling constants. Part 2. The effect of sulphur substituents

Nucleophilic Reactivity of 4,4′-Disubstituted Diphenyl Sulfides Towards trans-Dichlorobis(pyridine)platinum(II)

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