Nitrosyl chloride silver

Dehydrohalogenation Alumina, see Sulfur tetrafluoride. Alumina-Potassium hydroxide. Cesium fluoride. l,5-Diazabicyclo[4.3.0]nonene-5. l,4-Diazabicyclo[2.2.2]octane. 1,5-Diazabicyclo[5.4.0]undecene-5. Dimethylaminotrimethylstannane. Dimethyl sulfoxide. Hexamethylphosphoric triamide. Lithium chloride. Lithium dicyclohexylamide. Magnesium oxide. Potassium r-butoxide. Potassium fluoride. Potassium triethylmethoxide. Pyridine, see Nitrosyl chloride. Silver fluoride. Silver nitrate. Sodium amide. Sodium bicarbonate, see Nitryl iodide. Sodium isopropoxide. Triethylamine, see Sulfur dioxide. 

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)... 

Nitrogen trilluoride, 4336 Nitrogen triodide, 4633 Nitrogen triiodide-silver amide, 4634 Nitrogen triiodide-ammonia, 4635 Nitrosyl chloride, 4023 Nitrosyl fluoride, 4302 Nitryl chloride, 4025 Nitryl fluoride, 4303... 

Nitrosyl cyanide, generated from nitrosyl chloride and silver cyanide in chloroform at — 20 °C, affords unstable products with various dienes, e.g. butadiene and 2,3-di-methyl-1,3-butadiene. With methyl sorbate, compound 182 is produced (equation 103), thebaine (183) gives 184 (equation 104)97 and 9,10-dimethylanthracene yields the stable cycloadduct 185, which decomposes into its components on heating and consequently can serve as a source of nitrosyl cyanide. Thus heating 185 with 1,4-diphenylbuta-1,3-diene gives the dihydrooxazine 186 and dimethylanthracene (equation 105)98. 

Walden concluded that potassium hydrate and phosphorus penta-chloride acted optically normally, i.e. without alteration of the configuration, but that silver oxide, and therefore also nitrous acid and nitrosyl chloride, acted optically abnormally, but as to which of these reactions was really the normal one he was not able to decide. The conclusion was remarkable, since the action of silver oxide takes place in aqueous. solutions at a low temperature and the effect of potash in producing racemisation is well known. Still more curious is the supposition that nitrous acid and nitrosyl chloride act optically abnormally. 

Nitrosyl chloride in carbon tetrachloride reacts with silver thiocyanate to form silver chloride and nitrosyl thiocyanate ... 

Nitrosyl fluoride also can be produced by the action of nitrosyl chloride with silver fluoride ... 

Nitrosyl bromide also added to imines but the yields of a-acetates after the addition of silver acetate were not better than these obtained by the addition of nitrosyl chloride. Because of their high reactivity, it was not possible to isolate a-bromodialkylnitrosamines in either case. Presumably, steric effects may also operate. 

A very unstable series of compounds, many decomposing at well below 0°C. The products formed from iV-sodio triazenes and nitrosyl chloride explode violently on being disturbed with a wooden spatula, and are much more sensitive than those derived from silver triazenes. These exploded under a hammer-blow, or on friction from a metal spatula. 

Nitrosyl cyanide is readily generated by reaction of nitrosyl chloride with dry silver cyanide in chloroform at — 20 "C. This transient compound can be trapped by dimethylanthracene to give the corresponding cycloadduct in 20-30% yield which can be purified by crystallization34. 

When nitrosyl cyanide adduct 1 is reacted with ( , )-l,4-diphenyl-1,3-butadiene in refluxing benzene, the expected cycloadduct 2 is obtained with total diastereoselectivity, whereas by reaction with nitrosyl cyanide itself, prepared from nitrosyl chloride and silver cyanide, only 3-chloro-4-nitro-1,4-diphenyl-l-butene and l-nitro-l,4-diphenyl-l,3-butadiene are recovered in low yield34,35. 

Nitrosyl cyanide (109) has been briefly examined as a dienophile by Kirby et This intermediate can be generated from nitrosyl chloride and silver cyanide (equation 42) and trapped with 9,10-diinethyl-anthracene to yield adduct (110). As with acyl nitroso compounds, this adduct can be used as a stable source of (109) via a retro Diels-Alder reaction. 

The reagent is synthesized from silver p-chlorobenzoatc and nitrosyl chloride and stored as a solution in benzene. ... 

Hydrolysis Cupric sulfate. Hydrobromic acid. Ion-exchange resins. Magnesium sulfate. Morpholine. Nitrosyl chloride. Phosphoric-Acetic acid. Polyphosphoric acid. Potassium r-butoxide. Potassium persulfate. Pyruvic acid (by exchange). Rochelle salt. Silver trifluoro-acetate (gem-dihromides). 

Olefin additions Bromine azide. Bromine chloride. Bromine (chlorine) dipyridine nitrate. N-Bromoacetamine. N-Bromoacetamide-DMSO-Water. N-Bromoacetamide-Hydrogen fluoride. n-Butyllithium. Dichloroketene. Dichloromethyl 2-chloromethyl ether. N,N-Dichlorourethane. Dichlorovinylene carbonate. Difluoramine. Ethyl azidoformate. Ethyl bromoacetate. Iodine azide. Iodine isocyanate. Iodine nitrate, lodobenzene dichloride. 1-lodoheptafluoropropane. Mercuric acetate. Nitrosyl chloride. Nitrosyl fluoride. Nitryl iodide. Rhodium trichloride. Silver fluoride. 

Kirby et al. have examined the [4 + 2] cycloaddition chemistry of nitrosyl cyanide.lc>44 This unstable species, which can be generated from nitrosyl chloride and silver cyanide, can be trapped in situ by conjugated dienes. However, as with acylnitroso compounds it is often cleaner and more convenient to use the 9,10-dimethylanthracene adduct 26 as a latent source of nitrosyl cyanide [Eq. (20)]. 

A Diels-Alder adduct (206) was obtained when thebaine was treated with nitrosyl chloride and silver cyanide, the reactive intermediate probably being nitrosyl cyanide, ONCN. ... 

The ability of chloride to form a chromyl compound is not unique within the halogens. When bromide and iodide are treated with sulfuric acid and dichromate, they are converted into their free halogens. But fluorides will under these conditions form volatile chromyl fluoride, C1O2F2, and therefore give a reaction similar to chloride. The mercury chloride does not respond to the test owing to its low solubility, and the formation of chromyl chloride is limited for lead, silver, antimony, and tin chloride for the same reason. Iodide in 1 15 relative to chloride will give free chlorine. The presence of nitrites and nitrates interferes, as nitrosyl chloride is formed. ... 

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