Untersuchungen zur Sulfochlorierung von Paraffinen. V. Kinetische Untersuchungen über die Sulfochlorierung definierter Alkansulfochloride

Abstract

Studies on Sulphochlorination of Paraffins. V. Kinetic Studies on the Sulphochlorination of Pure Alkanesulphochlorides The mixtures of disulphochlorides formed by sulphochlorination of 1‐alkanesulphochlorides C4C9 may be analyzed gaschromatographically after transformation into the corresponding dimethylamides. The individual peaks could be identified in some cases with the aid of pure isomeric disulphochlorides, in other cases they were identified by analogy. The mixtures formed by sulphochlorination of the isomeric heptane sulphochlorides also could be analyzed after transformation into the dimethylamides; the identification of all peaks was possible by comparison of the mixtures obtained from different heptane sulphochlorides. For the alkane sulphochlorides studied the relative rates of sulphochlorination (with reference to n‐octane) were determined, and therefore the relative reaction rates of the individual CH‐bonds with reference to one primary CH‐bond of n‐octane could be calculated. The results show a geminal or vicinal disubstitution not to take place in noticeable amount. In position 3 or in greater distance the influence of the sulphochloride group on the reactivity of the CH‐bonds is not significant.

Analysis of chlorinated, sulfochlorinated and sulfonamide derivatives of n-tetradecane by gas chromatography/mass spectrometry

“…These compounds were rather analysed by EI-MS after their transformation into sulfonate salts [8][9][10]. Several theoretical and thermodynamic studies highlight the formation of the SO 2 + fragment which characterizes the mass spectra of this kind of compounds [11][12][13], but longchain sulfonyl chlorides can hardly be analysed directly by GC-MS because of their instability and their low volatility, so that their analysis requires their conversion, for example, into esters or sulfonamides [14][15][16][17][18][19]. In fact, long-chain n-alkanesulfonyl chlorides are rather analysed by LC-MS after their transformation into sulfonates or sulfonamides [20].…”

Sulfur Dioxide Mediated One-Pot, Three- and Four-Component Syntheses of Polyfunctional Sulfonamides and Sulfonic Esters: Study of the Stereoselectivity of the Ene Reaction of Sulfur Dioxide

“…Other methods imply the reactions of arenediazonium salts with SO 2 /CuCl 2 , the oxidation of thioesters 12 or sulfenyl chlorides, or the reaction of organolithium 14 or organomagnesium 15 reagents with SO 2 Cl 2 or SO 2 + Cl 2 . Alkanesulfonyl chlorides can be obtained by reaction of the corresponding alkane with SO 2 and Cl 2 under radical conditions . All these methods are relatively harsh (acidic, basic) and cannot be applied to polyfunctional substrates.…”