Cycloalkanones cyano

The incorporation of the side chain, placed in 2-position of a cycloalkanone, is influenced by strong electron withdrawing groups as Y. There are a number of experiments published, in which the nitro, the phenylsulfonyl, the ketone carbonyl, and the cyano group were used as Y. 

Ring enlargement reactions also take place in 2-oxocycloalkane-l-carbonitri-les substituted in 1-position by an co-alkylester or ketone [17]. The introduction of cyano groups into the a-position of cycloalkanones can be carried out in CH2C12 with C1S02NC0 in dimethylformamide [18]. Two and three carbon atom ring expansion reactions are possible by this method. In most cases the yields are low, which is in contrast with the results of the lactonisation (compare... 

The 2-cyano-cycloalkanones are easy to prepare but only in moderate yields [18]. The introductions of nitro- [6] and sulfone- [5] [116] [117] groups are simpler than the cyano group, and the yields are better. Sulfone and cyano compounds are most suitable for the introduction of the side chain. Beside the Michael reaction [16] [97], and the Pd(O) catalyzed addition [15], and the reactions with alkyl halides [16] [17] proceed in good yields. In contrast to other compounds, 2-nitroketones generally do not undergo nucleophilic substitution with non-activated alkyl halides. However, Michael addition products [2], as well as products synthesized by Pd(O) catalyzed alkylation [118], are well known derivatives of 2-nitrocycloalkanones. 

The ring-opening, occurring with C-3 deprotonation and 0-N fission (see p 139), is utilized for the synthesis of a-cyano ketones, especially with cycloalkanones and in the steroid series. The isoxa-zole ring behaves as an electrophilic cyanide equivalent ... 

TABLE 13. Electroreductive cyclization of 2-[2- and 3-cyano-alkyl] alkanones and cycloalkanones ... 

Curtius reaction, conversion of a pyridine hydrazide to a pyridine amide, 362 Cyanoacetamide, 602, 620 Cyanoacetic acid, 601 Cycloalkano-2-pyridones, preparation from 2- (2-cymo-ethyl) cycloalkanones, 729 a-Cyano-2-butenolc acids, 601... 

A simple synthesis of substituted cyano-anilines has been described. Malononitrile reacts with 4—6 cycloalkanones and aldehydes RCHO to give (150), which with alkali is converted into (151). 

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