74 nitrosyl chloride, reaction with amines

Reaction with a cyclic amine in the presence of a base and at ambient temperature forms alkene. Thus, nitrosyl chloride reacts with aziridine to form ethylene and nitrous oxide ... 

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. ... 

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. ... 

The key reaction, based on a method for removing glutamate residues in peptides, involves the conversion of the sole primary amine in the molecule to a diazo function. The most expeditious method consists of reacting (18-1) with nitrosyl chloride. The resulting diazo function in the product (18-2) can be displaced formally by oxygen from the enol form of the amide at the 7 position to form the iminolactone (18-3) the reaction may involve a spontaneous loss of nitrogen followed by capture of the resulting carbocation. Hydrolysis of the imine function in the product the leads to one of the key intermediates in this series, 7-ACA (18-4) [22]. 

Among the preparative routes to the octalin mixtures, the acid-catalyzed dehydration of 2-decalol3 and the metal-amine reduction of naphthalene4 appear most satisfactory. Apart from the purification method described in this preparation, pure A9,10-octalin has also been obtained by reaction of the octalin mixture with nitrosyl chloride. After separation of the adducts by fractional crystallization, the pure A9,10-octalin has been regenerated from its nitrosyl chloride adduct.3,5... 

The cis addition of nitrosyl chloride to cyclic unconjugated polyenes was observed in dichloromethane28. From cyclooctadiene a single diastereomeric dimer 3 (either meso or dl) was produced due to conformational factors associated with the cis configuration. This product underwent transannular electrophilic reaction to give 4. From (Z,Z,Z)-l,5,9-cyclododecatriene the chloro nitroso adduct 5 was obtained as a mixture of the meso and dl forms and was converted to -chloro amine 6 by lithium aluminum hydride/aluminum trichloride reduction 6 was converted to the corresponding aziridine. 13C-NMR spectroscopy was extremely useful in determining the diastereomeric composition of the nitroso dimers. 

Related reactions include the formation of the 2-cyano compounds (190) when 1,2-dimethyl-5-nitroimidazole is heated with nitrosyl chloride or an AT-oxide, and when 2-methyl-l-(o-nitrophenyl)imidazoles (191) cyclize under the influence of iron(II) oxalate (Scheme 98) (74JCS(P1)1970). The last reaction product is contaminated by a large amount of amine reduction product ( 64%) but there is also some cyclization with the 4-methyl isomer of (191). In the presence of trimethylamine, 2-cyanomethylbenzimidazole condenses with acetone to give the unsaturated derivative (192 Scheme 99) (77CPB3087). Neither 2-methylimidazole nor 2-methylbenzimidazole reacts with formamide in the presence of phosphoryl chloride. 

Incompatible with strong oxidizers acids, water (slowly decomposes, forming amine and carbon disulfide). Reaction with nitrosating compounds (i.e., nitrogen oxides, nitrosyl chloride, nitrite esters, metal nitrates and nitroso compounds, etc.) can cause the formation of carcinogenic N-nitrosodiethylamine. 

With nitrosyl chloride or ethyl nitrite in place of nitrous acid, the same holds except for Cl or OC2H5 instead of OH. The nitrous acid in this reaction corresponds to the base, and the amine to the acid. This formulation also shows how general a classification may be developed from a simple scheme and that although the reactions of organic chemistry appear to be most complex and different, in reality a great many conform to simple fundamental principles and changes. If A = CeHs, then the reaction corresponds to the formation of nitrosobenzene, etc. 

Nitrosamines. Nitrosamines are usually prepared by reaction of rec-amines with nitrous acid in water. They can also be prepared by conversion of tbe amine into the sodium amide (NaH, THF) followed by reaction with nitrosyl chloride. jcc-Amines also react directly with nitrosyl chloride in THF if pyridine is added as base. Yields by either method are fair to good. - R. E. Lyle, J. E. Saavedra, and G. G. Lyle, Synthesis, 462 (1976). 

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