Nitriles ketone hydrazones

The imides, primaiy and secondary nitro compounds, oximes and sulphon amides of Solubility Group III are weakly acidic nitrogen compounds they cannot be titrated satisfactorily with a standard alkaU nor do they exhibit the reactions characteristic of phenols. The neutral nitrogen compounds of Solubility Group VII include tertiary nitro compounds amides (simple and substituted) derivatives of aldehydes and ketones (hydrazones, semlcarb-azones, ete.) nitriles nitroso, azo, hydrazo and other Intermediate reduction products of aromatic nitro compounds. All the above nitrogen compounds, and also the sulphonamides of Solubility Group VII, respond, with few exceptions, to the same classification reactions (reduction and hydrolysis) and hence will be considered together. 

Ketones - Nitriles/ Ketones can be converted into nitriles by way of the tosyl-hydrazones. Thus the tosylhydrazone of cyclohexanone (I) on treatment with potassium cyanide in methanol acetic acid at room temperature followed by addition o( 2N... 

Nickel peroxide, an undefined black oxide of nickel, is prepared from nickel sulfate hexahydrate by oxidation in alkaline medium with an ozone-oxygen mixture [929] or with sodium hypochlorite [930, 931, 932, 933]. Its main applications are the oxidation of aromatic side chains to carboxyls [933], of allylic and benzylic alcohols to aldehydes in organic solvents [929, 932] or to acids in aqueous alkaline solutions [929, 930, 932], and of aldehydes to acids [934, the conversion of aldehyde or ketone hydrazones into diazo compounds [935] the dehydrogenative coupling of ketones in the a positions with respect to carbonyl groups [931] and the dehydrogenation of primary amines to nitriles or azo compounds [936]. 

Potassium salts of hydrazones are also available by other procedures. Potassium amide has been used to generate potassium salts of monoaryl ketone hydrazones. The reactive intermediate generated in these cases is a dianion. Highly dispersed forms of potassium have also been reported to generate potassium salts from N.N-dimethylhydrazones at -60 C. The use of K/AI2O3 in metalation of aldehyde hydrazone anions produces modest yields of alkylated products in THF suspension. In hexane suspension, side reactions believed to include nitrile formation lead to lower synthetic yields of hydrazone pr ucts. 

Most solid-phase syntheses of pyrazoles are based on the cyclocondensation of hydrazines with suitable 1,3-dielectrophiles. The reported examples include the reaction of hydrazines with support-bound a,(3-unsaturated ketones, 1,3-diketones, 3-keto esters, a-(cyano)carbonyl compounds, and a, 3-unsaturated nitriles (Table 15.19). Pyrazoles have also been prepared from polystyrene-bound 3-(hydrazino)esters, which are generated by the addition of ester enolates to hydrazones (Entry 7, Table 15.19 see also Section 10.3). Benzopyrazoles can be prepared from support-bound hydra-zones using the reaction sequence outlined in Figure 15.11. Oxidation of a polystyrene-bound benzophenone hydrazone yields an a-(acyloxy)azo compound. Upon treatment with a Lewis acid, this intermediate is converted into a 1,2-diazaallyl cation,... 

SCHMIDT REACTION. Acid catalyzed addition of hydrazonic acid to carboxylic acids, aldehydes, and ketones to give amines, nitriles, and amides, respectively. 

Reaction of cyanide ion with an alkyl halide is often the most convenient route to a nitrile, but in those cases where the corresponding aldehyde or ketone is more readily available than the alkyl halide, the following procedure is very convenient. The carbonyl compound is first converted into its 2,4,6-triisopropyl-benzenesulphonyl hydrazone (1) (Expt 6.42 gives the method for the preparation of the reagent, TBSH), which without isolation is then reacted with potassium cyanide under gentle reflux.169... 

Tosylhydrazones can be silylated with (fert-bufyldimethylsilyl)trifluoromethanesulfonate (Me2teriBuSi03SCF3) on the sulfonamide nitrogen. This is how the starting material for a broadly applicable alkane synthesis is produced ( Figure 1.49). Due to their ability to undergo reductive cyanization (Figure 17.69) mesitylene sulfonyl hydrazones allow for a two-step synthesis of nitriles from ketones. 

By the reaction with hydrogen cyanide, HCN, forming cyan-hydrines, which are acid nitriles, with hydroxyl amine, H2NOH, forming oximes, and with phenyl hydrazine, H2N—NH—CeHs, forming hydrazones, all of which reactions are characteristic of the carbonyl group, carbohydrates in water solution are aldehyde or ketone compounds. 

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