Ketones formation from nitriles

The addition of Grignard reagents to aldehydes, ketones, and esters is the basis for the synthesis of a wide variety of alcohols, and several examples are given in Scheme 7.3. Primary alcohols can be made from formaldehyde (Entry 1) or, with addition of two carbons, from ethylene oxide (Entry 2). Secondary alcohols are obtained from aldehydes (Entries 3 to 6) or formate esters (Entry 7). Tertiary alcohols can be made from esters (Entries 8 and 9) or ketones (Entry 10). Lactones give diols (Entry 11). Aldehydes can be prepared from trialkyl orthoformate esters (Entries 12 and 13). Ketones can be made from nitriles (Entries 14 and 15), pyridine-2-thiol esters (Entry 16), N-methoxy-A-methyl carboxamides (Entries 17 and 18), or anhydrides (Entry 19). Carboxylic acids are available by reaction with C02 (Entries 20 to 22). Amines can be prepared from imines (Entry 23). Two-step procedures that involve formation and dehydration of alcohols provide routes to certain alkenes (Entries 24 and 25). 

Base-promoted aminothiophene formation from ketone, a-active methylene nitrile and elemental sulfur. 

By far one of the most important reactions through the S l mechanism is formation of a C—C bond by the reaction of aryl halides with carbanions derived from hydrocarbons, ketones, esters, amides, nitriles and even, with some limitations, from aldehydes. The reactions of cyanide ions and carbonyl complexes of Co and Fe also form a new C—C bond. 

Simple distillation cannot separate aromatics from noD -aromatic, because the relative volatilities are very low, and many azeotropes are formed. Azeotropic distillation is based on the formation of an azeotrope betu een the non-aromatic hydrocarbons and a low boiling polar solveat It is select among the hrst terms of the series of alcohols, ketones, aldehydes and nitriles, and is employed pure or mixed with water. If the solvent forms a hetero-azeotrope, its recovery is accordbgly facilitated. The )aeld is not limited in principle. The impurity content of the feedstock and the composition of the azeotrope determine the amount of solvent required. Cuts rich in aromatics can be treated in this way fairly economically. However, any variation in the type of impurity to be removed, and consequently in the composition of the azeotrope, may lead to less perfect purification. Furthermore, this method can be applied only to a narrow cut which contains... 

The generation of imidoyl chlorides from nitriles and hydrogen halides in the presence of a suitable Lewis acid accounts for the formation of ketones in the Houben-Hoesch reaction (see Section IVD). 

Victor Merz (Odessa, 12 December 1839-Ziirich, 25 May 1904) was associate professor (1869) and professor (1871) in the university of Zurich. He worked first on inorganic chemistry. He synthesised ketones from acid chlorides and hydrocarbons, sodium formate from carbon monoxide, and oxalic acid by heating alkali formates. He prepared aromatic carboxylic acids by distilling sulphonates with potassium cyanide and hydrolysing the nitriles produced, discovered a- and j8-naphthoic acids, and prepared j8-naphthyl-amine from j8-naphthol by the action of ammonia and zinc chloride. ... 

The production of optically active cyanohydrins, with nitrile and alcohol functional groups that can each be readily derivatized, is an increasingly significant organic synthesis method. Hydroxynitrile lyase (HNL) enzymes have been shown to be very effective biocatalysts for the formation of these compounds from a variety of aldehyde and aliphatic ketone starting materials.Recent work has also expanded the application of HNLs to the asymmetric production of cyanohydrins from aromatic ketones. In particular, commercially available preparations of these enzymes have been utilized for high ee (5)-cyanohydrin synthesis from phenylacetones with a variety of different aromatic substitutions (Figure 8.1). 

Another type of reductive amination is shown in Figure 13-18. This reaction illustrates the formation of an amine from a ketone through the formation of an intermediate oxime. Figure 13-19 shows the conversion of a nitrile to an amine. (The nitrile can be formed by the action of cyanide ion, CN", on a halide via an Sf 2 mechanism.)... 

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