Nitroso diethylaniline

NDEA = p-Nitroso-iV,Ar-diethylaniline TDTD = 1,4-trans-Dithiane-l, 4-... 

N itroso-N.N-diethylani line (called N.N-D iathy 1- 4-n itros o-an i Iin, 4-N itros o-d iathy 1-anilin or p-Nitroso-diathylanilin in Ger), ON.C6H4.N(C2H5)2 mw 178 23, N 15.72% grn prisms (from eth), grn Ifts (from acet), or grn prisms having a violet surface shimmer, mp 84°, d 1.24 at 15° sol in ale eth si sol in w can be prepd by nitrosation of diethylaniline in HC1 with NaNQ2 soln and by other methods. It forms cryst salts addn compds (Ref 1). No expl props were reported Refs 1) Beil 12, 684, (338) [365] 2) J.I.G. 

NOTE No higher Nitroso derivs of Diethylaniline were found in Beil or in CA thru 1961 Mononitro-N, N-diethylo n i I i ne,... 

A solution of 42.5 g. (0.35 mole) of dimethylaniline in 212 ml. of hydrochloric acid (sp. gr. 1.1) is cooled in an ice bath and stirred while a solution of 25.5 g. (0.37 mole) of sodium nitrite in 40 ml. of water is added slowly. The precipitated p-nitrosodimethylaniline [cf. Org. Syntheses Coll. Vol. 1, 214 (1941)] is removed by filtration. A mixture of 42.5 g. (0.27 mole) of diethylaniline, 25.5 ml. of 37 aqueous formaldehyde solution (formalin), and 55 ml. of concentrated hydrochloric acid is heated on a water bath for 10 minutes, and to the hot mixture the p-nitrosodimethylaniline is added rapidly with stirring. The mixture is heated for 20 minutes after the addition of the nitroso compound and then diluted with water to a volume of 1 1. The mixture is poured into a solution of excess sodium bicarbonate in ice-cold water. The resulting yellow paste is filtered, and the solid is dissolved in 175 ml. of 50% acetic acid. To the resulting solution... 

It was found that p-nitroso-A,A-dimethyl and -diethylaniline are similarly stabilized133. Using the enthalpy of formation of p-nitroso-A,A-diethylaniline that these authors measured, they noted the near thermoneutrality of the gas-phase reaction 25. It is encouraging,... 

Nitroso compounds are formed as intermediates in this reaction. Yields from sulfonic acids, carboxylic acids, and nitro compounds, amongst others, are poor,424 but those from tertiary amines and phenols are often very good,423,426 although naphthols give only the nitroso derivatives for example, yields are 70% from A,iV-diethylaniline,423 96% from phenol,426 98% from o- or 7W-cresol,426 95% from chlorophenol,426 and 75-85% from o-hydroxybenzene-sulfonic acid 428 the diazonium group enters para to the NR2 or OH group. 

---