Patent GB-483585-A (GB)
Title: Improvements in the manufacture and production of compounds of the pyrimidine and pyrimidone series
Filed: 1936-10-26
Abstract: Compounds of the pyrimidine or pyrimidone series are made by stirring or heating o-aminocyano compounds or amides of o-aminocarboxylic acids in an acid medium with aldehydes or with polymerized aldehydes such as trioxymethylene, paraldehyde, and metaldehyde, or with azomethines, acetals, aldoxines, chloral hydrate or o -dihalogenmethyl compounds.  The o-amino-cyano compounds may be of the benzene, naphthalene, anthraquinone or heterocyclic series, and primary or secondary amines or amides may be used.  Aldehydes specified are formaldehyde, acetaldehyde, dodecyl, octodecyl and octodecenyl aldehydes, dialdehydes such as glyoxal, aldehyde carboxylic acids, acrolein, crotonaldehyde, high molecular aldehydes unsaturated one or more times, aldehydes of the benzene, naphthalene, anthraquinone, pyrene, quinoline, and anthrapyrimidine series.  The reaction may be carried out in presence of sulphuric, hydrochloric, phosphoric, nitric, or acetic acids, heating if necessary.  The dihydropyrimidines first formed may be dehydrogenated by such agents as nitrous gases, thionyl chloride, hydrogen peroxide, ammonium persulphate, pyrolusite, potassium permanganate, potassium ferricyanide, oxygen or air, often without separation, or by heating. When the pyrimidine nucleus contains hydroxyl groups, the said groups may be replaced by halogen by means of phosphorus pentachloride, if desired in one operation with the dehydrogenation.  The products are in part dyes for acetate artificial silk, or vat dyes or pigments and in part intermediates for dyes or medicaments.  In examples: (1) paraformaldehyde is reacted with 1-cyano-2-aminoanthraquinone in concentrated sulphuric acid to give Py.4-hydroxy-Py.1,2-dihydro-2(N).1-pyrimidinoanthraquinone (yellow shades on acetate artificial silk), which may be heated with thionyl chloride to give Py.4-hydroxy-2 (N).1-pyrimidinoanthraquinone, or with phosphorus pentachloride to give Py.4-chlor-2(N).1-pyrimidinoanthraquinone; paraformaldehyde may be replaced by paraldehyde, giving Py.2-methyl-Py.4-hydroxy-Py.1.2-dihydro-2(N) .1-pyrimidinoanthraquinone (yellow shades on acetate artificial silk) or by benzaldehyde, giving Py.2 - phenyl - Py.4 - hydroxy - Py.1,2-dihydro-2(N).1 - pyrimidinoanthraquinone; (2) 1-cyano-2-aminoanthraquinone is heated with p-aminobenzaldehyde in concentrated sulphuric acid to give Py.2(41 - aminophenyl) - Py.4-hydroxy - Py.1,2 - dihydro - 2(N).1 - pyrimidinoanthraquinone (brownish-yellow shades on cotton, pure yellow after benzoylation); if 1-aminoanthraquinone-2-aldehyde is used, a dyestuff dyeing cotton violet-red shades is obtained; from 1,5-dicyano-2,6-diaminoanthraquinone and paraformaldehyde, the corresponding dipyrimidinoanthraquinone is obtained; 5 - amino - 6 - cyano - 1,9 - anthrapyrimidine and p-chlorbenzaldehyde yield the corresponding pyrimidino-1.9-anthrapyrimidine; (3) paraformaldehyde is reacted with 1-amino-2-cyanoanthraquinone in sulphuric acid to give Py.4-hydroxy - Py.1,2 - dihydro - 1(N).2 - pyrimidinoanthraquinone (rose shades on acetate artificial p  silk); (4) paraformaldehyde is reacted with 2-amino-3-cyanoanthraquinone in sulphuric acid to give Py.4 - hydroxy - Py.1,2 - dihydro - 2(N). 3-pyrimidinoanthraquinone, which may be dehydrogenated with thionyl chloride to Py.4-hydroxy - 2(N).3 - pyrimidinoanthraquinone (yellow shades on cotton); (5) 2-amino-3-cyanoanthraquinone is reacted with terephthalic dialdehyde in sulphuric acid to give a compound dyeing cotton yellow shades, which gives a similar dyestuff on treatment with phosphorus pentachloride; the terephthalic dialdehyde may be replaced by phthalic or isophthalic dialdehyde giving yellow dyestuffs or by 1-aminoanthraquinone-2-aldehyde to give a violet red cotton dye which also dyes acetate artificial silk yellow-red shades; (6) 2-amino-3-cyanoanthraquinone is reacted with glyoxal sulphate in sulphuric acid to give a dyestuff dyeing cotton brown-yellow shades; (7) paraformaldehyde is reacted with anthranilic acid amide in sulphuric acid to give 4-hydroxy-1,2-dihydroquinazoline; (8) paraformaldehyde is reacted with 1-methylamino-2-cyanoanthraquinone in sulphuric acid to give Py.4 - hydroxy - Py.1 - methyl - Py.1,2-dihydro - 1(N).2 - pyrimidinoanthraquinone (red shades on acetate artificial silk); the 1-methylamino-2-cyanoanthraquinone may be replaced by 1 - phenylamino - 2 - cyanoanthraquinone, 1-(p-chlorphenylamino)- or 1-(p-methoxyphenylamino) - 2 - cyanoanthraquinone; (9) 2-amino-3-cyanoanthraquinone is reacted with the azomethine from 1-aminoanthraquinone-2-aldehyde and aniline in sulphuric acid to give a dyestuff dyeing cotton violet-red shades and acetate artificial silk yellowish red shades; (10) 1-amino-2-cyanoanthraquinone is reacted with 2-(o -dichlormethyl)-anthraquinone in sulphuric acid to give Py.2-(21-anthraquinonyl)-Py.4-hydroxy - 1(N).2 - pyrimidinoanthraquinone (yellow-brown shades on cotton); (11) 2-amino-3-naphthoic amide is reacted with 1-amino-anthraquinone-2-aldehyde in sulphuric acid to give a dyestuff dyeing cotton brown-red shades; (12) 2-amino-3-cyanoanthraquinone is reacted with terephthalaldehyde acid in sulphuric acid to give Py.2-(p-carboxyphenyl)-Py.4-hydroxy-2(N).3-pyrimidinoanthraquinone (yellow shades on cotton); (13) 2-amino-3-cyanoanthraquinone is reacted with 1 - aminoanthraquinone - 2-aldoxime to give the same product as in (9) above; (14) 1-cyano-2-aminobenzene is reacted with paraformaldehyde in sulphuric acid to give 4-hydroxy-1,2-dihydroquinazoline as in (7) above; (15) 1-cyano-2-aminobenzene is reacted with benzaldehyde in sulphuric acid to give 4 - hydroxy - 2 - phenyl - 1,2 - dihydroquinazoline; (16) 1-cyano-2-amino-4-chlorbenzene is reacted with paraformaldehyde in sulphuric acid to give 4 - hydroxy - 7 - chlor - 1,2 - dihydroquinazoline; if the paraformaldehyde be replaced by acrolein, 4 - hydroxy - 2 - vinyl - 7 - chlor - 1,2 - dihydroquinazoline is obtained; (17) 2-amino-3-cyanoanthraquinone is reacted with N-methyl-a -methyl - b  - dimethyl - a .b  - dihydroindole - 5-aldehyde in sulphuric acid to give a product dyeing cotton brownish yellow; the indolealdehyde may be replaced by furfural, to give a product dyeing cotton yellow shades; (18) 1-amino-2-cyanoanthraquinone is reacted with chloral hydrate in sulphuric acid to give Py.2-carboxy-Py.4-hydroxy-Py.1,2-dihydro-1(N) .2-pyrimidinoanthraquinone, which dyes acetate artificial silk orange-yellow; (19) 1-aminoanthraquinone-2-carboxylic acid methylamide is reacted with paraformaldehyde in sulphuric acid to give Py.3-methyl-Py.1,2-dihydro-anthraquinone - 1(N).2 - pyrimidone (orange red on acetate artificial silk); (20) 5-amino-6-cyano-1.9-anthrapyrimidine is reacted with 1-aminoanthraquinone-2-aldehyde in sulphuric acid giving a product dyeing cotton reddish violet shades; (21) 2-amino-3-cyanoanthraquinone is reacted with diethyl acetal in sulphuric acid to give Py. 4 - hydroxy - Py - 2 - methyl - Py. 1,2- dihydro - 2(N).3 - pyrimidinoanthraquinone (yellow-orange shades on acetate artificial silk); the diethylacetal may be replaced by crotonaldehyde or oleylaldehyde; (22) 4-chlor-2-amino-1-cyanbenzene is reacted with benzaldehyde in phosphoric acid to give 2-phenyl 4 - hydroxy - 7 - chlor - 1,2 - dihydroquinazoline; the 4 - chlor - 2 - amino - 1 - cyanobenzene may be replaced by 4-amino- or 4-methoxy-2-amino-1-cyanobenzene; (23) 2,3-aminonaphthoic amide is reacted with paraformaldehyde in acetic acid to give Py.4-hydroxy-Py.1,2-dihydro - 2(N).3 - pyrimidinonaphthalene; (24) 1,4 - diamino - 2 - cyanoanthraquinone is reacted with paraformaldehyde in sulphuric acid to give a dyestuff dyeing acetate artificial silk blue shades; the paraformaldehyde may be replaced by 1-aminoanthraquinone-2-aldehyde to give a product dyeing cotton blue-violet shades.  5 - Amino - 6 - cyano - 1,9 - anthrapyrimidine is obtained by heating 5-amino-6-brom.-1,9-anthrapyrimidine with cuprous cyanide in pyridine in a pressure-tight vessel.