Patent GB-763041-A (GB)
Title: New pyrimidine derivatives
Inventor: BOON WILLIAM ROBERT
IPC: C07D239/42
Filed: 1952-04-18
Abstract: The invention comprises pyrimidine derivatives of the general formula <FORM:0763041/IV(b)/1> in which Ar is an aryl radical which may optionally bear substituents, X is hydrogen or a lower alkyl radical, Y is a lower alkyl radical or X and Y together with the adjacent nitrogen atom form a heterocyclic ring, and Z is hydroxyl, amino, the group NX1Y1 (wherein X1 is hydrogen or a lower alkyl radical and Y1 is a lower alkyl radical), or the group NH-CRR11-COR1 (wherein R is hydrogen and R11 is hydrogen, phenyl or halophenyl radical and wherein R1 is phenyl or lower alkyl or alkoxy radical), provided that of the groups NXY and Z at least one is the residue of a secondary amine. The terms "lower alkyl" and "alkoxy" include up to 6 and 4 carbon atoms respectively.  They are prepared by reacting a compound of the formula <FORM:0763041/IV(b)/2> with an aryldiazonium salt. The following examples are given: (1) dimethylguanidine sulphate is heated with sodium methoxide and then with diethyl malonate to give 2-dimethylamino-4,6-dihydroxypyrimidine, which is treated with phosphorus oxychloride to give 2-dimethylamino - 4,6 - dichloropyrimidine which, by heating with alcoholic ammonia is converted to 2-dimethylamino - 4 - amino - 6 - chloropyrimidine; the latter compound is then coupled with diazotized p-chloroaniline to yield 2-dimethyl-amino - 4 - amino - 5 - p - chlorobenzeneazo - 6-chloropyrimidine.  (2) 2-Dimethylamino-4-methylamino - 6 - chloropyrimidine obtained by heating 2 - dimethylamino - 4,6 - dichloropyrimidine with alcoholic methylamine is coupled with diazotized p-chloroaniline to yield 2 - dimethylamino - 4 - methylamino - 5 - p-chlorobenzeneazo - 6 - chloropyrimidine.  (3) By a similar process there are obtained 2,4-bis (dimethylamino) - 6 - chloropyrimidine and 2,4-bis(dimethylamino) - 5 - p - chlorobenzeneazo-6-chloropyrimidine.  (4) Desylamine is reacted with trichloropyrimidine to give 2,4 - dichloro-6-desylaminopyrimidine which is heated with alcoholic dimethylamine to give 4-chloro-6-desylamino - 2 - dimethylaminopyrimidine and coupled with diazotized p-chloroaniline to yield 4 - chloro - p - chlorobenzeneazo - 6 - desylamino - 2 - dimethylaminopyrimidine; by similar methods a - (p - chlorophenyl) - a (4-chloro - 5 - p - chlorobenzeneazo - 2 - dimethylamino - 6 - pyrimidylamino) - acetophenone is obtained from a - amino - a  - (p - chlorophenyl)-acetophenone, the latter compound being prepared by treating p-chlorobenzylphenyl ketone with butyl nitrite and acid, and reducing the a  - nitroso - p - chlorobenzylphenyl ketone so formed with hydrogen and palladized charcoal.  In examples there are obtained by similar processes (5) ethyl 4-chloro-5-p-chlorobenzeneazo - 2 - dimethylamino - 6 - pyrimidylaminoacetate from ethyl 4-chloro-2-dimethylamino-6-pyrimidylaminoacetate (obtained by heating 4, 6-dichloro-2-dimethylaminopyrimidine with glycine ethyl ester), (6) 4-chloro-5-p-chlorobenzeneazo - 2 - dimethylamino - 6 - hydroxypyrimidine from 4 - chloro - 2 - dimethylamino - 6 - hydroxypyrimidine (obtained by heating 4-chloro-2-dimethylamino - 6 - methoxypyrimidine with hydrochloric acid); (7) 4 - chloro - 5 - -p chlorobenzeneazo - 2 - diethylamino - 6 - methylaminopyrimidine and 4 - chloro - 5 - p - chlorobenzeneazo - 6 - methylamino - 2 - piperidinopyrimidine; and (8) 4-chloro-5-p-chlorobenzeneazo - 2 - dimethylamino - 6 - pyrimidylaminoacetone starting from trichloropyrimidine and aminoacetone semicarbazone.  The preparation of 2 - dimethylamino - 4 - methylamino - 5 - benzeneazo - 6 - chloropyrimidine, 2 - dimethylamino - 4 - methylamino - 5 - o-methoxybenzeneazo - 6 - chloropyrimidine, 2-dimethylamino - 4 - methylamino - 5 - p - nitrobenzeneazo - 6 - chloropyrimidine and 2 - dimethylamino - 4 - methylamino - 5 - a  - naphthaleneazo - 6 - chloropyrimidine also is described.  Specifications 763,042, 763,044 and 763,120 are referred to.  According to the Provisional Specification the above defined alkyl and alkoxy groups may be replaced by any hydrocarbon groups.