Nickel benzene sulfonate

Nickel benzene sulfonate, 7.5 g/L, and triamine tolylphenyl methane chloride, 5-10 mg/L 212,000 5.0... 

The reactivity of 120 is much less than that of either a normal alkene or a dithioacetal. Attempts to hydrogenolyze (see Section IV,3) or reduce 120 with Raney nickel, to hydrolyze the dithioacetal (see Section IV,1) with mercury(II) chloride (even in the presence of an overwhelming excess of the reagent), and to ozonize the double bond at —78°, produce only the starting material an analytical sample was prepared by extended treatment of the crude product with a concentrated, aqueous, alkaline solution of potassium permanganate at the reflux temperature.20 Acetolysis, ozonolysis, or brominolysis of 120 at room temperature affords diphenyl disulfide, and extended oxidation with hydrogen peroxide in acetone, with peroxypropionic acid, and with peroxyacetic acid, produces benzene-sulfonic acid, methyl phenyl sulfone, and an uncharacterized explosive, respectively the products occur as intractable mixtures, and the yields are invariably low. 

Late transition metal complexes, which are more stable in water, can be used for emulsion polymerization [123-125]. Very small and stable polyethylene particles with diameters of 100 mn are obtained by microemulsion polymerization using nickel(II) complexes and diphenylphosphine benzene sulfonate as cocatalyst [126]. 

Having established an eflflcient catalytic system for the nickel catalyzed Heck reaction, a more in-depth study of the mechanistic details was desired. In order to investigate the role of the leaving group, aryl sulfonates with different electronic properties were prepared from 2-naphthol and various phenylsulfonyl chloride derivatives, using the same procedures as described in Chap. 5 (Table 6.3). Relying on the optimized reaction conditions, the coupling between 2-naphthyl benzene-sulfonate and n-butyl vinyl ether resulted in a 68 % conversion (entry 1). Mixtures of... 

Thioethers (sulfides) can be prepared by treatment of alkyl halides with salts of thiols (thiolate ions).7S2 R may be alkyl or aryl. As in 0-35, RX cannot be a tertiary halide, and sulfuric and sulfonic esters can be used instead of halides. As in the Williamson reaction (0-12), yields are improved by phase-transfer catalysis.753 Instead of RS ions, thiols themselves can be used, if the reaction is run in benzene in the presence of DBU (p. 1023).754 Neopentyl bromide was converted to Me3CCH2SPh in good yield by treatment with PhS in liquid NH3 at -33°C under the influence of light.755 This probably takes place by an SrnI mechanism (see p. 648). Vinylic sulfides can be prepared by treating vinylic bromides with PhS in the presence of a nickel complex,756 and with R3SnPh in the presence of Pd(PPh3)4.757 R can be tertiary if an alcohol is the substrate, e.g,758... 

Kanbara has since generated a family of poly(iminoarene)s by reaction of 1,3-dibromo-benzene, 4,4-dibromodiphenyl ether, 2,6- and 3,5-dibromopyridines, 2,4-dibromothiophene, and l,l -dibromoferrocene with a variety of bifunctional arylamines [229]. In many cases, no polymer was obtained, but for polymerizations involving dibromobenzene and 2,6-dibromopyridine, materials with JVfn values of over 10,000 were obtained. Spectral data were provided for poly(2,6-aminopyridine) and a polymer made from dibromobenzene and a dia-rylamino sulfone. These authors have also investigated nickel catalysts for the polymerization of diamines with dichloroarenes, but the materials generated had molecular weights below 10,000 in most cases [230]. 

Raney nickel is a stronger desulfurizing agent than nickel boride. On the other hand nickel boride, prepared from nickel(II) chloride and sodium borohydride, is more selective since it does not desulfurize aromatic sulfones. An example of such selectivity is desulfurization of p-phenylsulfonylphenyl p-tolyl sulfide (33), which affords diphenyl sulfone in 91% yield and toluene in 84% yield. In contrast. Raney nickel desulfurizes both the sulfide and the sulfone giving a mixture of benzene and toluene (equation 82). 5... 

The additives that go into the nickel bath are almost always proprietary carrier portions may include the sodium salts of benzene disulfonic acid, naphthalene 1,5-disulfonic acid, saccharin, and aHyl sulfonic acid. Generally, these compounds are characterized by a —S02 group. Brightener—leveler... 

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