Aldehydes aroyl cyanides

Aldonitrones, prepared by the condensation of aromatic aldehydes and phenylhydroxylamine, are converted by the action of aqueous potassium cyanide to substituted anils of aroyl cyanides. ... 

Moreover, aryl-oxazoles, -imidazoles [17], or-thiazoles [18], anhydrides [19], and imides [20] are accessible via intramolecular Heck-type carbonylations. In addition to typical acid derivatives, aldehydes [21], ketones [22], aroyl cyanides, aroyl acetylenes, and their derivatives [23] could be synthesized via nucleophilic attack of the acyl metal complex with the corresponding hydrogen or carbon nucleophiles. Even anionic metal complexes like [Co(CO)4] can act as nucleophiles and lead to aroylcobalt complexes as products [24]. 

In the presence of ai compounds are reduced I Aroyl cyanides under) Allylation of carbon toward aldehydes enable system in ring A. Ally. Mn-MejSiCl in THF. Fluorinated homoally bonyl compounds" or tlx... 

Aroyl cyanides undergo reductive coupling to furnish a-diketones in moderate yields. Allylation of carbonyl compounds. The chemoselectivity of allylindium reagents toward aldehydes enables elaboration of the steroid side chain without affecting the enone system in ring A. Allylation is also viable using a catalytic amount of indium and Mn-MejSiClinTHF. o... 

Benzoins. The cross-coupling of aroyl cyanides with aldehydes by aqueous... 

Lakhan and Singh ° described the first direct synthesis of 4-amino-2,5-disub-stituted oxazoles 552 from readily available starting materials. They condensed equimolar amounts of an aroyl cyanide 551 and an aldehyde with anhydrous ammonium acetate to afford 552 in 40-65% yield (Scheme 1.151). The reaction works better for aroyl cyanides containing electron-withdrawing groups. The... 

TABLE 1.38 4-AMINO-2,5-DIARYLOXAZOLES AND 2-ALKYL-4-AMINO-5-ARYLOXAZOLES FROM CONDENSATION OF AROYL CYANIDES, ALDEHYDES, AND AMMONIUM... 

The modifications of this reaction include the reaction between aroyl cyanide and aromatic aldehyde in the presence of HCl gas and the reaction of nitrile with aromatic aldehyde, HCl and SOC. ... 

The reaction of pyrido[2,3-6]pyrazine (1) with various aromatic aldehydes in the presence of cyanide ion affords aryl pyrido[2,3-6]pyrazin-3-yl ketones 13 in low yield. This introduction of aroyl groups actually is not an acylation but rather a benzoin-like condensation with subsequent oxidation of the intermediate a-arylpyrido[2,3-6]pyrazine-3-methanol.78... 

This reaction was initially reported by Reissert in 1905 and extended by Grosheintz and Fischer in 1941 It is the synthesis of aldehyde involving the formation of 1 -acyl-2-cyano-1,2-dihydroquinoline derivatives from acyl chlorides, quinoline, and potassium cyanide and the subsequent hydrolysis of said dihydroquinoline derivatives under acidic conditions to produce quinaldic acid and aldehydes. The original procedure occurs smoothly for aroyl or cinnamoyl chloride in liquid SO2 but not in benzonitrile, ether, dioxane, acetone, or CHCb. However, the modification from Grosheintz and Fischer using hydrogen cyanide and 2 eq. quinoline in absolute benzene is also adaptable for aliphatic acid chlorides. This is one of the methods that converts acyl chlorides into aldehydes and is found to be superior to the normal Rosenmund Reduction. For example, o-nitrobenzoyl chloride has been converted into o-nitrobenzaldehyde in 60% yield by the current reaction, whereas the Rosenmund Reduction is not suitable for such conversion. Therefore, this reaction is referred to as the Grosheintz-Fischer-Reissert aldehyde synthesis or Reissert aldehyde synthesis. ... 

Alternatively, the oxidation may occur by coupling to a suitable reactant. In 1997, Miyashita reported the formation of oxidative aroylation with nitrobenzene (Scheme 14.10)." With the same oxidative reagent, nitrobenzene, benzoin reactions had already been developed in 1982 using cyanide or thiamine." The combination of an aldehyde and nitrosobenzene, in the presence of an N-heterocyclic carbene, led to the formation of iV-phenyl hydroxamic adds in good yields." ... 

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