REACTION OF AMINESWITH NITROAND NITROSOCYCLICUREAS
Aug., 1950
[CONTRIBUTION FROM THE
3659
DEPARTMENT OF CHEMISTRY, QUEEN'S UNIVERSITY]
The Reaction of Amines with Nitro and Nitroso Derivatives of Cyclic Ureas and Cyclic Guanidines BY A. F. McKAY,~ W. R. R. PARK AND S. J. VIRON lated. Therefore it appeared desirable to investigate the effect of primary amines on a cyclic nitrosamine derivative, e. g., l-nitroso-2-nitramino-2imidazoline (I). This latter compound was expected to undergo ring opening with a retention of the alkyl residue which is eliminated with the linear 1-alkyl- 1-nitroso - 3-nitroguanidines. This was found to be the case and two new series of compounds were obtained. CHs NO2 The treatment of l-nitroso-2-nitramino-2-imida1 I CH-N zoline (I) with aromatic amines in aqueous eth\C=O 2RNHz ----f anol a t 30' gave l-substituted-2-nitramino-2-imiCH2-N I / dazolines (11) and 1,2-disubstituted-3-nitroguaniI dines (111). Both l-substituted-2-nitramino-2NOn imidazolines and 1,2-disubstituted-3-nitroguaniN02NH-CHa-CH (CHa)-NH-NOa dines on refluxing with the corresponding aroRNH-CO-NHR matic amines were recovered unchanged. Thus it The following substituted ureas were prepared by this reaction, the yields are given in parentheses: must be considered that either one of these types 1,3-dicyclohexyl- (88.5), m. p. 227-228O; 1,3-di- of compounds is not an intermediate in the formabenzyl- (98), m. p. 169-170°3; 1,3-diphenyl- tion of the other under the conditions of the reac(97.3), m. p. 235-23Cio3j4; 1,3-di-o-tolyl- (88.5), m. tion. The l-substituted-2-nitramin0-2-imidazolines p. 245-24606; l13-di-m-tolyl- (94.8), m. p. 216.5217.806; 1,3-di-m-anisyl- (85.0), m. p. 170.8- (11) were converted into the corresponding l-sub171.9' ; 1,3-di-m-phenetyl- (95.5) , m. p. 156.2- stituted-2-imidazolidones (IV) in good yield by 157.5"- and 1,3-di-p-phenetylurea (95.4), m. p. hydrolysis in basic solutions. These imidazolidones (IV) also were prepared by treating oxazoli229-2$0°.7-9 sym-Disubstituted ureas were obtained also by done-2 (V) with amines13 as additional proof of treating 1,3-dinitroso-2-imidazolidonewith am- the identity of these compounds. Oxazolidone-2 (V) was prepared by the method of Homeyerl4 ines. from ethanolamine and ethyl carbonate. YO All of the linear 1,2-disubstituted-3-nitroguaniI dines (111) were colored. Thus the double bonded CHa-N, I C=O f RNHz + nitrogen was assigned the position in conjugation CH~-N/ with the aromatic substituent. In accordance I I with this assumption, the ureas (VI) produced by NO RiXH-CO-NHR other products the alkaline hydrolysis of the 1,2-disubstituted-3Several of the 1,3-disubstituted ureas described nitroguanidines were colorless. Alkaline hydrolyabove were prepared by this method along with sis of these latter compounds also produced a small 1,3-di-p-tolylureaI m. p. 261-262°,4*6J0and 1,3- amount of the corresponding 1-substituted-2-imidazolidones (IV). Since the 1,3-disubstituted di-p-anisylurea, m. p. 235-236O.'.l0 Previously, in the studies"nl2 of the effect of ureas (VI) were found to be stable under these primary amines on 1-alkyl-1-nitroso-3-nitroguani-conditions, the small amounts of l-substituted-2dines only the main reaction products were iso- imidazolidones formed must be derived from the 1,2-disubstituted-3-nitroguanidinesby elimina(1) Defence Research Chemical Laboratories, Ottawa, Ont. tion of both an aromatic amino group and the ni(2) A. F. McKay and D. F. Manchester, THISJOURNAL, 71, 1970 tramino group. (1949). (3) S. M.Mistry and P. C. Guha, J. I n d . Chcm. SOL.,7,793 (1930). The results described above illustrate that 1(4) N. Palit, ibid., 11, 479 (1934). nitroso-2-nitramino-2-imidazoline in the presence ( 5 ) F. Leuthardt and R. Brunner, H d v . Chim. Acto, SO, 958 of aromatic amines enters into both a substitution (1947). and an alkylation reaction. These two types of (6) A. Cossack, Bcr., 19, 1449 (1897). (7) G.V. Jadhav, J. I n d . Chcm. Soc., 7, 669 (1930). reactions would be expected to occur also ( 8 ) E. Wertheim, THISJOURNAL, I S , 200 (1931). when 1-substituted-1-nitroso-3-ni troguanidines are (9) J. K.Thomson and F. J. Wilson, J. Chcm. Soc., 1262 (1933). treated with primary amines. (10) T. N. Ghoch, J. Ind. Chcm. SOL.,93, 27 (1946).
It has been shown2that dinitro cyclic ureas dissolve in ten per cent. sodium hydroxide solution and on acidification in the cold evolve carbon dioxide while the corresponding linear dinitramines are precipitated. If primary amines are used instead of sodium hydroxide solution then sym. disubstituted ureas are obtained along with the linear dinitramines.
+
+
+
SO, 3028 (11) A. F. McKay and G. F. Wright, THISJOURNAL, (1947). (12) A. F. McKay, ibid., 71, 1968 (1949).
(13) S. Gabriel and G. Eschenbach, Bcr., SO, 2495 (1897). (14) A. H. Horneyer, U. S. Patent 2,399,118, C. A . , 40, 4084 (1946).
A. I?. MCKAY,W. I
