Thermolysis of Trialkylnitrosoureas: Formation of an Unusual Product

Article abstract of DOI:10.1021/jo00141a007

The thermolysis of four trialkylnitrosoureas, 1,1,3-trimethyl-1-nitrosourea (1), 3,3-diethyl-1-methyl-1-nitrosourea (2), 1-ethyl-3,3-dimethyl-1-nitrosourea (3), and 1,3,3-triethyl-1-nitrosourea (4), was carried out neat, in aprotic and aprotic solvents.When the thermolysis was run neat or in protic solvents, 4 gave as much as 70percent of N,N-diethylalanine ethylester (9).Ethyl N,N-diethylcarbamate (8) (about 10percent) was the only other product isolated.In protic solvent, however, 8 was the principal product.Neat thermolysis of 2 and 3 gave products analogues to those obtained from 4 but in much lower yields.Thermolysis of 1 did not give any product comparable to 9.Tetramethylurea was a major product from the thermolyses of 1 and 3.Decomposition of 3 was faster than any of the other three compounds, studied, but 3 did not give high yields of products.Addition of CuCl to the reaction mixture caused the reaction products to change dramatically.The appropriate dialkylnitrosamine and the denitrosated urea were then the major products.