Nitrosyl chloride, reactions

Mechanism The reaction of and A -steroids with nitrosyl fluoride to form ni trimines is best discussed in conjunction with the nitrosyl chloride reaction leading tothe5a-chloro-6 -nitro steroids (33). Since nitroso alkanes are oxidized with nitrosyl chloride to nitro alkanes it is believed that 5a-chloro-6j5-nitro steroids are formed in this way from an initially formed 5a-chloro-6 -nitroso adduct. The same is true for nitrosyl fluoride up to the stage of the nitroso fluoride (56). Since NOF is a weaker oxidizing agent than NOCl the nitroso fluoride tautomerizes to the fluoro oxime (57) at a rate... 

A similar reaction occurs with chlorine, to give nitrosyl chloride... 

The U.S. domestic commercial potassium nitrate of the 1990s contains 13.9% N, 44.1% I+O, 0—1.8% Cl, 0.1% acid insoluble, and 0.08% moisture. The material is manufactured by Vicksburg Chemical Co. using a process developed by Southwest Potash Division of AMAX Corp. This process uses highly concentrated nitric acid to catalyze the oxidation of by-product nitrosyl chloride and hydrogen chloride to the mote valuable chlorine (68). The much simplified overall reaction is... 

Nitrosyl chloride, a product of the basic reaction, has no commercial value and is converted to salable chlorine and to nitric acid for recycling. 

The reactants are fed separately iato a stUl, from which the product is continuously removed by distillation (qv) (31). Isopropyl nitrate is a valuable engiae-starter fuel and can be used ia explosives (see Explosives and propellants) (32). The nitrite ester, isopropyl nitrite, can be prepared from the reaction of isopropyl alcohol and either nitrosyl chloride or nitrous acid at ambient temperature (33). The ester is used as a jet engine propellant (30). 

Toray. The photonitrosation of cyclohexane or PNC process results in the direct conversion of cyclohexane to cyclohexanone oxime hydrochloride by reaction with nitrosyl chloride in the presence of uv light (15) (see Photochemical technology). Beckmann rearrangement of the cyclohexanone oxime hydrochloride in oleum results in the evolution of HCl, which is recycled to form NOCl by reaction with nitrosylsulfuric acid. The latter is produced by conventional absorption of NO from ammonia oxidation in oleum. Neutralization of the rearrangement mass with ammonia yields 1.7 kg ammonium sulfate per kilogram of caprolactam. Purification is by vacuum distillation. The novel chemistry is as follows ... 

Substitutedisoxazole-3,5-dicarboxylic acids have been prepared from ethyl nitroacetate and an aldehyde (63BCJii50). A related reaction leads to diethyl 4-hydroxyisoxazole-3,5-dicarboxylate (334) and involves the reaction of acetonedicarboxylic acid ester (333) with nitrosyl chloride (78JHC1519). 

Whereas sulfonyl halides have been known for a long time and, especially the chlorides, have become of great synthetic value, sulfonyl cyanides were unknown until 1968. They were first prepared by van Leusen and co-workers from the reaction of sulfonylmethylenephos-phoranes with nitrosyl chloride. The same group also investigated part of their chemistry. Since then, two more, completely different, methods of synthesis were published from sulfinates with cyanogen chloride,and by the oxidation of thiocyanates. ... 

Androst-4-ene-3,17-dione 17a-Hydroxyprogesterone (1 g) is dissolved in 10 ml of pyridine and treated dropwise at —20° with a solution of nitrosyl chloride in pyridine until a permanent blue color develops. The reaction is quenched with 500 ml of ice water, and the resulting nitrite is filtered and... 

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)... 

An a-oximino enamine was formed by the reaction of nitrosyl chloride and triethylamine with morpholinocyclohexene 494). Oxime functions have also been introduced into carbonyl conjugated enamines with isoamyl nitrite or NjOj 495). 

Seel and Nogradi were probably the first to suspect that the formulation of the thiol as azidodithiocarbonic acid was incorrect. In a study of the reaction of nitrosyl chloride with azides they found that... 

The required nitrite esters 1 can easily be obtained by reaction of an appropriate alcohol with nitrosyl chloride (NOCl). The 3-nitroso alcohols 2 formed by the Barton reaction are useful intermediates for further synthetic transformations, and might for example be converted into carbonyl compounds or amines. The most important application for the Barton reaction is its use for the transformation of a non-activated C-H group into a functional group. This has for example been applied for the functionalisation of the non-activated methyl groups C-18 and C-19 in the synthesis of certain steroids. ... 

Nitrosyl chloride reacts with aliphatic hydrocarbons at room temperature under the influence of light to give a complex mixture of substitution products. When the reaction is run on cyclohexane at —25°, however, the pure oxime hydrochloride crystallizes from the reaction mixture with virtually no side products. 

Bicyclo[2.2.1]hepta-2,5-diene, nitrosyl chloride adduct, 46, 74 reaction with acetic acid to yield nortricyclyl acetate, 46, 74 Bicyclohexyl, 46, 61 Bicyclohexylidene, 47, 34 ejSO-e s-BlCYCLO[3.3.0]OCTANE-2-CAR-BOXYLIC ACID, 47, 10 Bicyclopentadienylidene, octa-chloro-, 46,93... 

N-Nitroso N phenylglycine, 46, 96 reaction with acetic anhydride to yield 3 phenylsydnone, 46, 96 Nitrosyl chloride, addition to bicyclo-[2 2 ljhepta 2,5 diene, 46, 75 2,4-Nonanedione, 47, 92 Nonane, 1,1,3 trichloro-, 46,104 Nortricyclanol, 46, 74 oxidation by chromic acid, 46, 78 Nortricyclanone, 46, 77 Nortncj clyl acetate 46, 74 frombicyclo[2 2 ljhepta 2,5 dieneand acetic acid, 46, 74 saponification of, 46, 75... 

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