Reaction of phenylacetonitriles with

Effects of polymer structure on reaction of phenylacetonitrile with excess 1-bromo-butane and 50% NaOH have been studied under conditions of constant particle size and 500 rpm stirring to prevent mass transfer limitations I03). All experiments used benzyltrimethylammonium ion catalysts 2 and addition of phenylacetonitrile before addition of 1-bromobutane as described earlier. With 16-17% RS the rate constant with a 10 % CL polymer was 0.033 times that with a 2 % CL polymer. Comparisons of 2 % CL catalysts with different % RS and Amberlyst macroporous ion exchange resins are in Table 6. The catalysts with at least 40% RS were more active that with 16 % RS, opposite to the relative activities in most nucleophilic displacement reactions. If the macroporous ion exchange resins were available in small particle sizes, they might be the most active catalysts available for alkylation of phenylacetonitrile. 

N 11.76% crysts (from ale), mp 70—72° was prepd by reaction of phenylacetonitrile with 4-chloro-l-nitrobenzene St KOH in pyridine with exclusion of air (Ref 2). No expl props are reported... 

Additionally, the use of metal halides has been shown to accelerate alkane elimination and product formation, for example, the reaction of phenylacetonitrile with InMes. The introduction of CsF has been perceived to act as a catalyst by forming intermediate metalates of the types [XMMes]" and [MesMXMMes]-. ... 

Indeed a reaction of phenylacetonitrile with CCl leads to trans-dicyanostilbene via the initially formed phenylchloroacetoni-trile(8). On the other hand phenylacetonitrile derivatives undergo simple halogenation... 

The phenylchloroacetonitrile anion, generated in the reaction of phenylacetonitrile with CCl, can also be trapped by acrylonitrile. In this case, however, the main product is 1-phenyl-l,2-dicyano-2-chlorocyclopropane along with the expected phenyldicyanocyclopro-pane. 

Figure 8. Reaction of phenylacetonitriles with lithium dimethylaminoborohydride.

Preparation by reaction of phenylacetonitrile with phloroglucinol (Hoesch reaction),... 

Obtained by reaction of phenylacetonitrile with 2,6-di-hydroxy-4-methoxytoluene (Hoe-sch reaction) (52%) [5353]. 

Obtained by reaction of phenylacetonitrile with 4-hexyl-resorcinol in the presence of zinc chloride (17%) (Hoesch reaction) [6225], m.p. 210-211° [6225]. 

Several papers report on the synthesis of interesting thioketones by less common routes. Trost and his co-workers isolated bis-(l,2,3-triphenylcyclo-propenyl) thioketone (49) from the reaction mixture resulting from the addition of thiophenylcyclopropenium bromide to a solution of dimethylsul-phonium methylide in THF. The thione (50) was obtained as a by-product in the reaction of phenylacetonitrile with diethyl sulphite (affording 4,5-diphenylisothiazol-3-ol as the main product). ... 

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