Arenesulfonyl chlorides, reaction with

Arenes, polyalkyl, oxidation with per-oxytrifluoroacetic acid and boron trifluoride, 48, 89, 90 Arenesulfonyl chlorides, reaction with 3-amino-3-pyrazoline, 48, 11 Aromatic aldehydes. Mesitalde-HYDE, 47, 1... 

Organoperoxysulfonic acids and their salts have been prepared by the reaction of arenesulfonyl chlorides with calcium, silver, or sodium peroxide treatment of metal salts of organosulfonic acids with hydrogen peroxide hydrolysis of di(organosulfonyl) peroxides, RS(0)2—OO—S(02)R, with hydrogen peroxide and sulfoxidation of saturated, non aromatic hydrocarbons, eg, cyclohexane (44,181). 

Arenesulfonyl chlorides as well as alkenesulfonyl chlorides react with vinylarenes in the presence of RuCl2(PPh3)3 and 1 molar equiv. of EtjN to form a,j8-unsaturated sulfones in 70-90% yields. The reaction mechanism for the ruthenium(II) catalyzed reaction involves a free-radical redox-transfer chain process as outlined below ... 

In what was intended as another experimental probe to ascertain whether a concerted or stepwise mechanism was involved in substitution reactions of arenesulfonyl chlorides, Rogne (1975) measured the enthalpies of transfer from propanol to acetonitrile for the transition states, SAH, for the reaction of imidazole with (a) benzoyl chloride and (b) benzenesulfonyl chloride. He found that SAH was considerably more negative for the reaction involving the sulfonyl chloride than for the one involving benzoyl chloride. This means that the transition state for attack of imidazole on benzenesulfonyl chloride is considerably better solvated by acetonitrile relative to its solvation by propanol... 

Esters of arenesulfonic acids are prepared by reaction of the corresponding alcohol with the arenesulfonyl chloride in the presence of a basic reagent, which has the function of activating the alcohol and binding the hydrogen chloride. The reaction is often carried out with pyridine, which is used as solvent. In the procedure for tosylates of primary aliphatic alcohols, described in A.l. Vogel, A Textbook of Practical Organic Chemistry, an aqueous solution of sodium hydroxide is used. Esters of primary alcohols are formed more easily than secondary-alkyl esters, while tertiary alcohols cannot be esterified under the usual conditions. 

To a solution of ZnF2 (0.03 mol) in pyridine (30 mL) was added the aroyl chloride or the arenesulfonyl chloride (0.03 mol) with stirring at 25 °C. Stirring was continued until the reaction was complete (checked by 19F NMR spectroscopy) then treated by either Method A or B as follows. 

Some radical reactions occur under the control of transition metal templates. The first example of asymmetric creation of an asymmetric carbon with a halogen atom is shown by the a DIOP-Rh(I) complex-catalyzed addition of bromotrichloromethane to styrene, which occurs with 32% enantioselectivity (Scheme 99) (233). Ru(II) complexes with DIOP or BINAP ligands promote addition of arenesulfonyl chlorides to afford the products in 25-40% ee (234). A reaction mechanism involving radical redox transfer chain process has been proposed. 

Extensive studies have been carried out on the reaction of arenesulfonyl chlorides with aniline in methanol at 25 °C. These include various substituted thiophenesulfonyl chlorides. The kinetic data show that the rate-determining step in the reaction is addition of the nucleophile, rather than synchronous attack of amine and displacement of chloride (Scheme 162) (76AHC(20)1>. 

Interestingly, exclusive ipso substitution was observed in the reaction of trialkylarylstannanes with arenesulfonyl chlorides [118]. Diaryl sulfones, with substitution patterns different from those available via electrophilic aromatic substitution, were obtained in good to excellent yields. The... 

Arenesulfonyl chlorides.1 Aryldiazonium chlorides are converted into arenesul-I onyl chlorides by reaction with S02 and CuCl. Yields from the corresponding aniline arc 30 90%, being highest with anilines substituted with electron-withdrawing substituents. 

The reaction of arenesulfonyl chlorides with alcohols to yield sulfonates is relatively slow (if compared, e.g., with the formation of mesylates or sulfonamides), and treatment of diols with tosyl chloride can readily yield the statistically expected amount of monotosylated product [35, 36]. The selectivity of such reactions can sometimes be enhanced by additives such as AgO [37] or Bu2SnO [38]. Deprotonation of the diol can be used to increase its nucleophilicity and thereby reduce the reaction time (Scheme 10.9). This strategy can, however, lead to problems, because the products are sensitive toward strong bases, and may cyclize, oligomerize, or undergo elimination. 

Reaction of the parent heterocycle with arenesulfonyl chlorides in the presence of a suitable base constitutes the only widely applied method for the Marylsul-fonylation of indoles, pyrroles, imidazoles, etc. Three procedures using indoles illustrate the variety of conditions. Typical bases include n-BuLi [Scheme 8.268]515 or a metal hydride [Scheme 8.269]524 in THF, or phase-transfer catalysis using sodium hydroxide in aqueous dichlorome thane [Scheme 8.270].515... 

The reactions of metal substituted carbodiimides 20 with arenesulfonyl chlorides or arene-sulfonyl isocyanates produce metal substituted N-sulfonylcarbodiimides 21 (R3M=Me3Si, Et3Ge, Bu3Sn X=C1, NCO). ... 

If desired, glycidic esters can be derived from a,3-dihydroxy esters, such as (110), by either of two methods. In one method, reaction of the diol with an arenesulfonyl chloride is regioselective, producing the a-arenesulfonate (111) in preference to the 3-sulfbnate. Treatment of (111) with an equivalent of base produces the erythro-glycidic ester (112) in good yield. In the second method, the diol is converted to a bromohydrin (114) via the acetoxy bromide (113). The brotmhydrin (114) affords the threo-g ycidic ester (115) on exposure to potassium caitxHiate in methanol. 

The McFadyen-Stevens aldehyde synthesis - is based on the reaction shown in Scheme 13, in which arenesulfonylhydrazides (40) are decomposed to aldehydes by treatment with base. It is generally presumed that the acylimides (41) are intermediates in the procedure. The arenesulfonylhydrazides can be synthesized either from acid hydrazides and arenesulfonyl chlorides or from acyl chlorides and arene-sulfonylhydrazines. The latter method is somewhat more common in recent work and is reported to give superior yields. ... 

All these reagents, (37)-(40) in Scheme 30, will react with aromatic compounds by Friedel-Crafts-type reactions to give organosulfur compounds, e.g. sulfides (41), sulfoxides (42) and symmetrical sulfones (43) the use of an alkane- or arenesulfonyl chloride (32) similarly affords a mixed sulfone (44) (Scheme 30). 

For the reaction of arenesulfonyl chlorides with pyridine bases, Rogne (13, 14) concluded that the amines function as nucleophilic catalysts, for example, II. 

Rate extremes with systematic variation of substituents are often considered to be evidence of changes in the molecularity of a reaction, but for hydrolyses of arenesulfonyl chlorides, rate extremes are more reasonably ascribed to variations in the extents of S-O bond making and S-Cl bond breaking. Variations in k+/k support this hypothesis (Table VI), and as for hydrolyses of acid chlorides (Table V), bond making seems to be important but introduction of electron-donating groups increases the importance of bond breaking in the transition state. 

---