Arenesulfonyl chloride

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). 

In addition to (461), Dorn has described the imine (463) isolated from 5-amino-l-methylpyrazole and arenesulfonyl chloride (80CHE1). Upon heating, or in the presence of triethylamine, it undergoes rearrangement to the more stable 5-bis(arylsul-fonamido)pyrazoles (464). 5-Iminopyrazolines (461) react with acyl chlorides at the exocyclic nitrogen atom to afford amidopyrazolium salts (B-76MI40402). 

Strong acids or superacid systems generate stable fluorinated carbocations [40, 42] Treatment of tetrafluorobenzbarrelene with arenesulfonyl chlorides in nitro-methane-lithium perchlorate yields a crystalline salt with a rearranged benzo barrelene skeleton [43] Ionization of polycyclic adducts of difluorocarbene and derivatives of bornadiene with antimony pentafluonde in fluorosulfonyl chloride yields stable cations [44, 45]... 

This is one of the steps in the copper-catalyzed redox-transfer chain addition of arenesulfonyl chlorides to styrenes (vide infra). The p-value of + 0.56 indicates the involvement of a simple atom transfer as well as a polar contribution to the transition state. 

The copper-catalyzed additions of sulfonyl chlorides to conjugated dienes and trienes73 as well as to aryl-substituted cyclic olefins74 and substituted styrenes have been described75 for example, arenesulfonyl chlorides add to vinylarenes providing good to excellent yields75 of /J-chlorosulfones ... 

Ardel D-100 bisphenol-A polyarylate, 48 Arenesulfonyl chlorides, 329 Aromatic-aliphatic alternating... 

Arenesulfinate esters are usually prepared from an arenesulfinyl chloride and an alcohol in ether and pyridine. The arenesulfinyl chloride is usually prepared from the sodium arenesulfinate which is made by reduction of the arenesulfonyl chloride, preferably by aqueous sodium sulfite. After the crystalline sulfinate epimer has been removed by filtration, the equilibrium between the epimers remaining in the mother liquor may be reestablished by the addition of hydrogen chloride as shown by Herbrandson and Cusano . In this way the yield of the least soluble diastereomer may be increased beyond that which exists in the original reaction mixture (Scheme 1). Solladie prepared sulfinate ester 19 in 90% yield using this technique and published the details of his procedure. Estep and Tavares also published a convenient recipe for this method, although their yields were somewhat lower than Solladie s. 

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 ... 

As the initiator, a common radical initiator and arenesulfonyl chloride are also used [286,287]. As shown in Table 6, this polymerization has a significantly large polymerization rate, and it is hardly disturbed by impurities such as alcohol and water [288]. ATRP with Cu complex was also applied to the polymerization of acrylates [289,290], methacrylates [290-297], and AN [298] as well as St [288, 297, 299]. Because of the suppressed bimolecular termination, hyperbranched polymers are readily prepared [292], being similar to the polymerization with TEMPO previously described. 

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... 

This procedure represents the most convenient synthesis of 3(5)-aminopyrazole. It employs readily available starting materials and gives excellent yields in all steps.5,6 />-Toluene-sulfonyl chloride can be replaced by other arenesulfonyl chlorides. 3-Imino-l-arylsulfonylpyrazolidines can be alkylated with dimethyl sulfate or with alkyl 7>-toluenesulfonates in dimethyl-formamide to give salts of l-alkyl-2-arylsulfonyl-5-amino-4-... 

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 Phosphoryl chloride. Sulfur dioxide-Copper(I) chloride. 

Anisylcyclohexylmethylphosphine, 31 Anthracyclinones, 254 Anthraquinones, 189-190 Antimetabolitc AT-125, 146 Aphidicolin, 558 Aplasomycin, 57-58 Ara-7-deazaguanosine, 403, 404 Arene ally la t ion, 516 Arenediazonium fluoroborates, 161 Arenesulfonyl chlorides, 429, 495 Arene(tricarbonyl)chroniium complexes, 131-132... 

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. 

Some rather interesting custom made electrophilic resins that have been developed lately as nucleophile scavenging materials are the acid chloride (25) and arenesulfonyl chloride (26) resin shown in Fig. 9. Resin 26 is stable to various reaction conditions over resin 18 and can be used while conducting subsequent chemical steps.62... 

Fig. 9. Acid chloride (25) and arenesulfonyl chloride (26)-based custom made nucleophilic scavenging resins.

Arenesulfonyl Chloride Resin (26). To a suspension of chlorobenzyl Merrifield resin (5.0 g, 4.9 mmole) and anhydrous 4-hydroxybenzenesulfo-nic acid sodium salt (2.94 g, 15 mmole commercial material was dehydrated at 110° in vacuo for 8 h) in A, A-dimethy I acetamide (50 ml) was added NaOMe (0.81 g, 15 mmol), and the mixture was stirred at 90° for 2... 

Diethyl-(2-p-tolyl-ethyl) -amine (30). A solution of 2-(p-tolyl)-ethanol (3-5 mole-equiv.), triethylamine (3-5 mole-equiv.), and arenesulfonyl chloride resin (26) in DCM (10 ml/mmol) was allowed to react at RT for 48 h. The resulting resin (31) was then filtered and washed with DCM (2x), MeOH (2x), and DCM (2x). Upon treatment of resin (31) with excess diethylamine at 60° for 6 h, diethyl-(2-p-tolyl-ethyl)-amine (30) was obtained. 

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