The pathway for the aqueous chlorinolysis of a series of β-sulfonyl-sulfides is elucidated and the SN2 cleavage step examined. Steric effects in the cleavage of the α-polychloro-oxochloro-sulfonium chloride intermediates are held to be responsible for the suppression of the established nucleophilic competition between water molecules and chloride ions with the result that all cleavage products arise from nucleophilic attack by chloride ions. This report details the second known example of successful SN2 displacement on a carbon atom α to a sulfonyl group.

RICHAKD FRAYCIS L A~G L~K , J u N~. ELL^^ T R~N H O L M , and JOHN S P E~L~K WAS SO^. Can. J. Chem. 58.780 (1980). A reexamination of Linnett's nonpairing spatial orbital theory, as it is qualitatively employed, has led to a number of conclusions. Firstly, in our view the theory has been inconsistently applied to the prediction of molecular geometries and may be ambiguous in dealing with saturated systems. Secondly. it does not provide aguide to chemical reactivity, in contrast to claims made for it. Finally, NPSO theory does provide a useful extension of resonance theory as it is qualitatively employed in organic chemistry, contrary to an existing claim that NPSO theory makes resonance theory obsolete.RICHARD FRANCIS LANGLER. JUNE ELLEN TRENHOLM et JOHN SPENCER WASSON. Can. J. Chem. 58,780 (1980). Une nouvelle etude de la theorie des orbitales spatiales non appariees de Linnett, telle qu'elle est qualitativement employee, a conduit a plusieurs conclusions. Premierement, la theorie est a notre avis utilisee inddment a predire les geometries moleculaires et elle peut &re ambigue dans le cas des systemes satures. Deuxiemement, la theorie ne constitue pas un guide de reactivite chimique contrairement a c e qui aete dit ace sujet. Finalement, la theorie OSNA, loin de rendre desuette la theorie de la resonance telle qu'elle est employee qualitativement en chimie organique, en constitue plut8t un prolongement pratique.[Traduit par le journal]In 1961 Linnett (1) proposed a new structural theory which he named the Nonpairing Spatial Orbital (NPSO) theory but which is much more frequently referred to as Linnett Double Quartet (LDQ) theory. LDQ theory acknowledges the tendency of the elements in the "First Short Period" to achieve octets in formine stable molecules but u presumes that "the importance of the pairing of electrons" has been overemphasized.LDQ octets are not visualized as four spin pairs occupying four regions in space. Instead an octet is regarded as the sum of two tetrahedral quartets of electrons. A auartet contains electrons of the same spin (one quartet for electrons of spin +3 and one quartet for electrons of spin -3). The two quartets are independently oriented.Molecular structures2 are elaborated bv maximizing electronic separations and minimizing electronic repulsions. Priority, it is assumed, must be given to maximizing the separation of electrons having the same spin.Subsequent to the publication of the parent article a substantial number of papers and books have appeared which present and extend LDQ theory (2-25). NPSO theory has been developed as a valence bond approach to the electronic structure of molecules and provides results which are in excelQualitatively, LDQ theory has been applied to predicting bond lengths, bond angles, stabilities of various species, paramagnetism/diamagnetism of molecules, and regioselectivity in Diels-Alder reactions.In previous discussions of 0, (1, 22, 23) three structures3 have been considered i.e., 1-3. The relative stabilities of these structures, as indeed is ...

The successful synthesis and chlorinolysis of α-mercaptodimefhyl sulfone have provided additional support for our contention that Pummerer rearrangements may occur during the chlorinolyses of α-sulfonyl sulfinyl chlorides. Further exploration of chlorinolyses of α-sulfonyl systems has uncovered the first observations of CS bond cleavage during the chlorinolyses of (i) a sulfinyl chloride and (ii) a sulfinate ester.