74 nitrosyl chloride, reaction with acids

Experiments have been carried out with dissolved nitrosyl chloride in non-acidic aqueous solution (pH 6.85) in reaction with primary arylamines and secondary alkylamines (Challis and Shuker, 1979a). The products are, as expected, the diazonium ions or N-nitrosamines, which are formed very rapidly together with nitrite ion by hydrolysis of nitrosyl chloride. Thus nitrosyl chloride is involved in two competitive reactions as shown by (22) and... 

Propanol undergoes reactions characteristic of a secondary —OH group. Oxidation is highly exothermic (43 kcal/mol) but occurs above 300° C (572°F), forming acetone. It reacts with acid chlorides, chlorine, and phosphorus chloride to produce chloroacetones (toxic). It loses water molecules over acid catalysts such as alumina or sulfuric acid, to form diisopropyl ether (flammable) and propylene (flammable, forms an explosive mixture with air). It forms isopropyl acetate (mucous membrane irritant, narcotic) with acetic acid. Treatment with nitrosyl chloride or with sodium... 

In one commercial process, the reaction is carried out by irradiating a mixture of cyclohexane, nitrosyl chloride and hydrochloric acid at —10° to 16°C with... 

In one commercial process, the reaction is carried out by irradiating a mixture of cyclohexane, nitrosyl chloride and hydrochloric acid at -10° to 16°C with light from a mercury vapour lamp. The raw material costs in this process are lower than those in the conventional process and the ammonium sulphate production is about half. 

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). 

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)... 

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... 

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... 

A novel, mild system for the direct nitration of calixarenes has been developed using potassium nitrate and aluminum chloride at low temperature. The side products of decomposition formed under conventional conditions are not observed in this system, and the p-nitro-calixarenes are isolated in 75-89% yields.17 Such Friedel-Crafts-type nitration using nitryl chloride and aluminum chloride affords a convenient system for aromatic nitration.18 Nitryl chloride was previously prepared either by the oxidation of nitrosyl chloride or by the reaction of chlorosulfonic acid with nitric acid. However, these procedures are inconvenient and dangerous. Recently, a mixture of sodium nitrate and trimethysilyl chloride (TMSC1) has been developed as a convenient method for the in situ generation of nitryl chloride (Eq. 2.6). 

The reaction of acylsilanes with acid chlorides in the presence of A1C13 leads to furans (Table 9.41) [45]. In these reactions an acyl cation initiates the addition with ensuing silyl migration yielding an intermediate vinyl cation. Attack of the carbonyl oxygen followed by proton loss affords the observed products (Scheme 9.16). An analogous reaction with nitrosyl fluoroborate provides a route to oxazoles (Table 9.42) [65]. The nitrosyl cation serves as the electrophile in this application. 

Nitration of the amine (139) with mixed acid yields the energetic nitramine (140). The same reaction with sodium nitrite in sulfuric acid, or with nitrosyl fluoride in methylene chloride, yields the nitrosamine (141), which is also an energetic high explosive. ... 

Also, nitrosyl chloride is produced by the action of chlorine on sodium nitrate or by the reaction of nitrosyl sulfuric acid with hydrochloric acid ... 

Potassium nitrate may be produced by several methods. It is made commercially by reacting potassium chloride with nitric acid at high temperature. Nitrosyl chloride, a product obtained in the reaction, is converted into chlorine in this manufacturing process. Also, nitric acid is partly recycled in the process. The reactions are (Dancy, W.B. 1981. Potassium Compounds. In Kirk-Othmer Encyclopedia of Chemical Technology, 3 i ed. Pp. 939-42. New York Whey Interscience) ... 

The conditions under which HC1 formed in acidified sodium chloride droplets would be expected to enter the gas phase have been treated by Clegg and Brimble-combe (1990). Cadle and co-workers (Robbins et al., 1959 Cadle and Robbins, 1960) observed that NaCl aerosols in the presence of 0.1-100 ppm NOz at relative humidities of 50-100% lost chloride ion from the particles. They ascribed this to the formation of nitric acid from NOz, followed by reaction (1). Schroeder and Urone (1974) subsequently suggested that NOz could react directly with NaCl to produce gaseous nitrosyl chloride, C1NO, which they observed using infrared spectroscopy stoichiometrically, this is represented as... 

The main renewable resource for L-carvone is spearmint oil (Mentha spicata), which contains up to 75% of this flavour chemical. There also exists a synthetic process for the manufacturing of L-carvone, which is based on (-t)-limonene, which is available as a by-product of the citrus juice industry as a major component of orange peel oil (Scheme 13.4). The synthesis was developed in the nineteenth century and starts with the reaction of (-t)-limonene and nitrosyl chloride, which ensures the asymmetry of the ring. Treatment with base of the nitrosyl chloride adduct results in elimination of hydrogen chloride and rearrangement of the nitrosyl function to an oxime. Acid treatment of the oxime finally results in l-carvone. 

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