O-Nitroketones

Alkenes react with nitryl chloride to give jS-nitroalkyl chlorides, jS-chloroalkyl nitrites and vic-dichloroalkane products. Nitryl chloride reacts with enol esters to give o -nitroketones. ... 

Formation of the d bond by the reductive cyclization of a,[Pg.610]

Finally, we must mention a number of reports concerning bis chelates, either mononuclear square planar or trinuclear octahedral, with anionic ligands which bear some resemblance to j8-diketones, namely acetophenone, o -nitroketones, hydroxymethylenecamphor and related ligands. 

The simidtaneous denitradon-deoxygenadon of ct-nitroketones is performed o withTsNUNHj and NaBbb, at 80 C to give alkanes fEq 7 90 ... 

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. 

In this way, starting from o- or m-toluic acid, the o- or m-tolyl-phenyl ketone can be prepared it cannot be obtained by the action of benzoyl chloride on toluene. (4) Substituted add-chlorides like brombenzoyl chloride, nitrobenzoyl chloride, etc., can be used, and thus halogen or nitroketones are obtained ... 

Oxidative cyclization of o-aminoacylbenzenes is a much less common process for the synthesis of anthranils than the reductive cyclizations discussed in the previous section, mainly because the o-aminoketones are in many instances best prepared by reductive ring opening of anthranils (see Section III,C,3). Nevertheless, a few examples have been recorded. Oxidation of o-aminobenzophenones to the nitroketones using peroxytrifluoro-acetic acid, permaleic acid, or persulfuric acid proceed via the 3-phenyl-anthranil which occasionally is isolable.168 Caro s acid is also a useful oxidant.169... 

The nitroketone (465) was converted to the oxime acetate (466) which was treated with diborane to reduce the imine group followed by hydrogen to reduce the nitro group and give the diamine (467). The diamine condensed with triethyl orthoacetate to yield dazepinil (471) Scheme 5.110.) [628]. An improved route began with o-toluidine (468) which was iV-protected to allow the directed metallation of the methyl group. Treatment with the SchifPs base (469) followed by deprotection and exposure to triethyl orthoacetate gave dazepinil in improved yield [629]. This benzodiazepine has antidepressant properties. 

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