Arenesulfonyl halides

Amino-5-nitrothiazole, on treatment with arenesulfonyl halides and dimethylformamide at 140 C, gives (5-nitro-2-thiazolyl)amidme (274) (Scheme 168) (507, 508). The condensation products of the reaction of 2-aminothiazole derivatives with various aldehydes are grouped in Tables... 

The ring contraction of 3//-azepines is also promoted by acylating agents,54 35 and by arenesulfonyl halides.34 For example, in refluxing acetic anhydride A,-phenyl-3//-azepin-2-amine yields 2-acetamidodiphenylamine (22% mp 121-122°C),34 whereas A,A,-diethyl-3/7-azepin-2-amine (30) with 4-nitrobenzoyl chloride in pyridine yields the benzanilide 31.35... 

Sulfur dioxide and carbon monoxide react with aryl radicals. The adducts formed are converted to the final products, arenecarboxylic halides and arenesulfonyl halides, by ligand transfer with the corresponding cupric halides (Schemes 10-36 and 10-37). 

The three steps 32-34 have been suggested77 to be equilibria, and the overall equilibrium must lie far to the left because no adduct 23 is found in the reaction mixture when the reaction of sulfonyl chloride with olefin is carried out in the absence of a tertiary amine. A second possible mechanism involving oxidative addition of the arenesulfonyl halide to form a ruthenium(IV) complex and subsequent reductive elimination of the ruthenium complex hydrochloride, [HRulvCl], was considered to be much less likely. 

The synthesis of sulfones included electrophilic substitution, specifically, Frie-del-Crafts catalysis by A1C13, FeCl3, SbCl5, AlBr3 and BF3, and so on, which are efficient catalysts for the sulfonylation by arenesulfonyl halides.1 22... 

The ability to conduct radical reactions without the use of tin reagents is important. Allylic triflones have been used to conduct allylation reactions on a range of substrates (39) as a replacement for allyltributylstannane (Scheme 28). The main limitation was that unactivated or trisubstituted triflones failed to undergo reactions. In other nontin radical methods, arenesulfonyl halides have been used as functional initiators in the CuCl/4,4 -dinonyl-2, 2 -bipyridine-catalysed living atom-transfer polymerization of styrenes, methacrylates, and acrylates.The kinetics of initiation and propagation were examined with a range of substituted arylsulfonyl halides with initiator efficiency measured at 100%. 

The last decades have witnessed the emergence of new living Vcontrolled polymerizations based on radical chemistry [81, 82]. Two main approaches have been investigated the first involves mediation of the free radical process by stable nitroxyl radicals, such as TEMPO while the second relies upon a Kharash-type reaction mediated by metal complexes such as copper(I) bromide ligated with 2,2 -bipyridine. In the latter case, the polymerization is initiated by alkyl halides or arenesulfonyl halides. Nitroxide-based initiators are efficient for styrene and styrene derivatives, while the metal-mediated polymerization system, the so called ATRP (Atom Transfer Radical Polymerization) seems the most robust since it can be successfully applied to the living Vcontrolled polymerization of styrenes, acrylates, methacrylates, acrylonitrile, and isobutene. Significantly, both TEMPO and metal-mediated polymerization systems allow molec-... 

A study was reported on the desulfination of some arenesulfonyl halides, RSOaX, using Ru(PPh3)3Cla 15). 

The catalytic desulfination of several arenesulfonyl halides has been studied using Rh(PPh3)aCl and Rh(CO)(PPh3)aCl (15). 

Arenesulfonyl halides can add to alkenes with the assistance of a metal catalyst. Several types of catalysts have been employed with varying degrees of success. Substituted phenyl vinyl sulfones, althou only the ( )-isomers have been prepared finom styrenes, benzenesulfonyl chlorides and a ruthenium catalyst in g< yield.This same reaction has been tried with chiral ruthenium catalysts with modest success (20-40% ). ... 

The Friedel-Crafts sulfonylation of aromatics with alkane- and arenesulfonyl halides and anhydrides has been studied (Eq. 9) [23]. In the reaction of pentafluorobenzenesul-fonyl fluoride with pentafluorobenzene, decafluorodiphenyl sulfone is formed with deca-fluorodiphenyl [23c]. Certain phenylacetylenes react with SO2 and benzene in the presence of SbFs to form benzothiophene 5-oxide [24]. (Eq. 10). Sulfinyl fluoride reacts similarly with arenes under SbFs catalysis to give sulfoxides (Eq. 11) [25]. 

Sulfonyl halides, particularly arenesulfonyl halides, can afford radical species much faster than carbon halides by the assistance of a metal complex and efficiently add to olefins with little dimerization of sulfonyl radicals in comparison to carbon-centered radicals. Another feature of the compounds is that there is little effect of the substituents on the rate of addition to an olefin. These properties make sulfonyl halides an efficient and universal series of initiators for the metal-catalyzed living radical polymerizations of various monomers including methacrylates, acrylates, and styrenes (Figure g). 52.175-177... 

Arenesulfonyl halides 1-32 were first employed for the CuCl/L-1 -catalyzed polymerization of styrene in the bulk at 130 °C to give polymers with controlled molecular weights and relatively narrow MWDs [MJ Mn = 1.4—1.8).152 No significant effects were observed with different ring substituents. 

The use of arenesulfonyl halides was also investigated for the ruthenium-catalyzed polymerization of MMA.180 Living polymers are indeed attained, where the a-end group (/, 1.0) and the MWDs are controlled (MJMn = 1.2—1.5), whereas the Mn values were higher than the calculated values due to low initiation efficiency (f,.n 0.4). 

In addition to the carbon-centered radical initiators, arenesulfonyl halides are simple and efficient functionalized initiators by introducing a variety of functional termini conjugation between the aryl and the sulfonyl groups is absent (FI-51 to FI-58 Figure 14).175 Typically, a series of monosubstituted derivatives (FI-51) are commercially available and afford hydroxyl, carboxyl, nitro, and halo groups in living... 

Percec, V., Barboiu, B., and Kim, H. J. (1998). Arenesulfonyl halides a universal class of functional initiators for metal-catalyzed living radical polymerization of styrene(s), methacrylates, and acrylates. J. Am. Chem. Soc., 120(2) 305-316. 

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