74 nitrosyl chloride, reaction with ketones

The progression toward Organlco s commercial production of lactam began in 1958. Initially, cyclododecatriene was epoxidized then hydrogenated to the alcohol. The alcohol was oxidized to the ketone, which was then transformed by reaction with hydroxylamine to the oxime which by Beckmann rearrangement yielded the lactam. They immediately began to work on a method to react nitrosyl chloride directly with dodeca-triene and eliminate some intermediate steps. This program eventually led to the earliest version of the commercial process in 1962. 

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

The catalytic oxidation of cyclohexane is performed in the liquid phase with air as reactant and in the presence of a catalyst. The resulting product is a mixture of alcohol and ketone (Table 1, entry 12) [19]. To limit formation of side-products (adipic, glutaric, and succinic acids) conversion is limited to 10-12 %. In a process developed by To ray a gas mixture containing HC1 and nitrosyl chloride is reacted with cyclohexane, with initiation by light, forming the oxime directly (Table 1, entry 12). The corrosiveness of the nitrosyl chloride causes massive problems, however [20]. The nitration of alkanes (Table 1, entry 13) became important in a liquid-phase reaction producing nitrocyclohexane which was further catalytically hydrated forming the oxime. 

Reaction of nitrosyl chloride with the N = 4 acetylene complex CpW-(CO)(HC=CH)[C(0)Me] produces 20% yields of an alkenyl ketone... 

The reaction has been used in a three-step conversion of olefins into ketones. For example, nitrosyl chloride is added to cyclooctene (1) and the resulting 2-chlorocyclooctanone oxime3 (2) is then acetylated and treated with chromous acetate at 65° for 16 hours. Cyclooctanone (3) is obtained in 88% yield from (2). 

Mononitrosation of cyclohexanone can be effected by reaction with slightly more than 1 eq. of nitrosyl chloride in liquid sulfur dioxide in the presence of an alcohol and 1 eq. of hydrochloric acid at about -10° (equation 1). The product (1) is a 2-alkoxy-3-oximinocycloalkene, the enol ether of ana-oximino ketone. These products can be obtained in yields as high as 40%. 

Ketones having an a-methylene group, that is, —CH2 bound to the carbonyl group, can react with nitrous acid, nitrite esters, or nitrosyl chloride to form nitroso compounds and oximes. These reactions are catalyzed by acids or bases. 

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