Acetanilides acrylates

The diazonium salts 145 are another source of arylpalladium com-plexes[114]. They are the most reactive source of arylpalladium species and the reaction can be carried out at room temperature. In addition, they can be used for alkene insertion in the absence of a phosphine ligand using Pd2(dba)3 as a catalyst. This reaction consists of the indirect substitution reaction of an aromatic nitro group with an alkene. The use of diazonium salts is more convenient and synthetically useful than the use of aryl halides, because many aryl halides are prepared from diazonium salts. Diazotization of the aniline derivative 146 in aqueous solution and subsequent insertion of acrylate catalyzed by Pd(OAc)2 by the addition of MeOH are carried out as a one-pot reaction, affording the cinnamate 147 in good yield[115]. The A-nitroso-jV-arylacetamide 148 is prepared from acetanilides and used as another precursor of arylpalladium intermediate. It is more reactive than aryl iodides and bromides and reacts with alkenes at 40 °C without addition of a phosphine ligandfl 16]. 

Palladium(II) effects orthometalation of acetanilides to form the corresponding palladacycles [185]. De Vries, van Leeuwen, and coworkers exploited this reactivity to achieve regioselective oxidative coupling of acetaniUdes and n-butyl acrylate that proceeds efficiently with BQ as the stoichiometric oxidant (Eq. 46) [ 186], The use of TsOH as an additive and acetic acid as a cosolvent significantly improves the results. Inferior results are observed with hydrogen peroxide or copper(II) acetate as the stoichiometric oxidant, but efforts to use molecular oxygen were not described. 

General Procedure for Coupling Acetanilide Derivatives to n-Butyl Acrylate... 

METHYL SULFOXIDE (67-68-5) CjHjOS (CHjIjSO Combustible liquid [explosion limits in air (vol %) 2.6 to 63.0 flashpoint 203°F/95°C oc autoignition temp 419°F/215°C Fire Rating 2]. Violent or explosive reaction with strong oxidizers, acryl halides, aryl halides and related compounds, alkali metals p-bromobenzoyl acetanilide, boron compounds, especially hydrides iodine pentafluoride, magnesium perchlorate, methyl bromide, perchloric acid, periodic acid, silver fluoride, sodium... 

Acetanilide and maleic acid are condensed to give /3-(p-acetaminobenzoyl)acrylic acid which is hydrogenated to give methyl-7-(p-aminophenyl)butyrate. That is reacted with ethylene oxide and then with phosphorus oxychloride to give the methyl ester which is finally hydrolyzed to give chlorambucil. 

Oxidative Heck reaction of acetanilides with n-butyl acrylates. 

Table 2.6 Oxidative Heck Reaction of Acetanilides With n-Butyl Acrylates ...

Unlike the previously discussed Fujiwara-Moritani reactions, which involve the electrophilic palladation of arenes, another category of Fujiwara-Moritani reactions exists that takes advantage of the directing ability of a neighbouring functional group. De Vries and coworkers [32] have reported a selective palladium(ll)-catalysed oxidative coupling of anilides with alkenes through C-H bond activation at room temperature. It was found that acetanilide (54) reacts with -butyl acrylate (4d) in the presence of 2 mol% Pd(OAc)2,... 

Scheme 2.29 ortfto-Directing CDC reactions of acetanilide and butyl acrylate. 

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