Dimethylanilinium

The following rearrangement of N-allyl-i, N-dimethylanilinium ion has been observed. Propose a mechanism. 

By comparison, the recently reported compound bis(N, Y-dimethylanilinium) ditellurium decaiodide [C6H5NH(CH3)2]2Te2Iio provides improved synthetic... 

A 500-ml flask was charged with the step 2 product (0.105 mol), the step 3 product (0.245 mol), and 70 ml of toluene, and then stirred at ambient temperature. Thereafter the solution was treated with bis(2,4-pentanedionato)palladium (0.070 mmol) and tricyclohexylphosphine (0.070 mmol) dissolved in 10 ml of toluene and dimethylanilinium tetrakispentafluorophenyl borate (0.28 mmol) dissolved in 5 ml of CH2C12. The mixture was stirred at 80°C for 1 hour, during which time toluene was suitably added as the viscosity of the reaction solution increased. After the reaction was completed, the solution was diluted with toluene and the mixture precipitated in excess methanol. The precipitate was filtered off and washed with a large amount of methanol, the polymer dried in vacuo at 110°C for 6 hours, and 61.4 g of product isolated. 

On the other hand, instead of an alumoxane compound as activator, N,N-dimethylanilinium tetrakis-perfluorophenylboron has been used with a metallocene catalysts (29). 

It is generally adopted that the catalytically active species in the metallocene-catalysed polymerization is a 14-electron cation. As an example, the mechanism of activation of an unbridged zirconocene catalyst is presented in Fig. 9.5-4, top. In the first two steps the activation by MAO, resulting in the 14-electron cation, is shown. The same cation can be generated by N,N -dimethylanilinium-tetrakis(pentafluorophenyl)borate and methylated metallocenes. As side-products methane and an amine are formed. TiBA can also be involved in the activation, which is not shown in Fig. 9.5-4, bottom. On the other hand, TiBA acts as a scavenger in the polymerization. The above-mentioned reactions take place in the absence of the monomer and are performed before the catalyst is used in the polymerization process. 

Reactions performed under 2 bars of propene with tri isotnitylaliimimiim/dimethylanilinium tetrakisfpenta-... 

Methylaluminoxane-free catalysts, such as cationic complexes derived from TiBz4 and tris(pentafluorophenyl)borane [B(C6F5)3], appear to be much less active, poorly stereospecific catalysts for the polymerisation of styrene. Under analogous conditions, the use of N, yV-dimethylanilinium tetrakis(pentafluor-ophenyl)borate [Me2N(Ph)H]+[B(C6F5)4]- instead of B(C6F5)3 does not yield active catalysts only traces of syndiotactic polystyrene were obtained [70]. 

Fujio et al., unpublished), elimination reactions of p-arylethyl halides and tosylates (Tsuno, 1974 Fujio el al., unpublished), the phenyl ester hydrolyses (Ryan and Humffray, 1966, 1967 Humffray and Ryan, 1967, 1969), pK, values of phenols, thiophenols, anilinium ions and dimethylanilinium ions (Yukawa et al., 1966 Tsuno, 1974) and pK, values of sulphonanilides (Yoshioka et al., 1962). All these correlations are not directly related to the systems involved in the present review and they will be reviewed separately elsewhere. 

Dimethylaminophenyl Tellurium Trichloride Bis[A.A-dimethylanilinium] hexachlorotellurate(lV) or the adduct of tellurium tetrachloride with 2 molecules of dimethylaniline Is refluxed in excess dry methanol under nitrogen until evolution of hydrogen chloride ceases. The resultant solution is concentrated, the precipitate is filtered, and the solid is extracted with acetone. Benzene is added to the acetone solution, the precipitated crystals are collected, washed thoroughly with chloroform, and dried over anhydrous calcium chloride in a vacuum desiccator yield 80% m.p. 90°. 

The first reported rearrangement involving the 2-thienyl moiety was carried out by the action of potassium hydroxide melt on lV-(2-thienyl)-fV,fV-dimethylanilinium chloride60. 

B.L. Knier et al.. Mechanism of Reactions of N-(Methoxy-methyl)-N,N-dimethylanilinium Ions with Nucleophilic Reagents, J. Am. Chem. Soc., 1980,102, 6789. 

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