Robba, Max published the artcileCertain derivatives of diazines. II. Reactions of nitriles of diazines, Related Products of pyrimidines, the publication is Ann. Chim. (Paris) (1960), 414, database is CAplus.
Several thioamides, amidoximes, tetrazoles, imino esters, amidines, and imino ketones containing diazine structures were prepared VII (1 g.) and 14 ml. EtOH saturated at 0° with NH3 then H2S, refrigerated 16 hrs., the precipitate removed, dried, and crystallized from EtOH gave 90% 4-thiocarbamoylpyridazine, m. 214-15°. 3-Thiocarbamoylpyridazine, m. 168°, and 2-, 4-, and 5-thiocarbamoylpyrimidine (XVI), m. 225°, 236°, and 170°, resp., were similarly prepared 3-Hydroxy-4-cyanopyridazine (XVII) (1 g.), 10 ml. C5H5N, and 0.83 g. Et3N saturated at 0° with H2S, the precipitate removed after refrigeration 16 hrs., and a 2nd crop obtained by addition of 15 ml. H2O gave 89% 3-hydroxy-4-thiocarbamoylpyridazine, m. 305°. XV (0.517 g.) in 0.5 ml. H2O at 40° treated with 0.34 g. NH2OH.HCl in 1 ml. H2O and 1.45 g. Na2CO3 in 7 ml. H2O, the mixture heated 1.5 hrs. at 70-5°, and refrigerated 16 hrs. gave 0.51 g. pyrazine-2-amidoxime, m. 185-6°. Pyridazine-3-amidoxine m. 240°, pyridazine-4-amidoxime m. 209°, 3-hydroxypyridazine-4-amidoxime m. 232°, and 4-pyridine-amidoxime m. 186°. Pyrimidine-2-amidoxime, m. 262°, required 2.3 hrs. heating; 3-hydroxypyridazine-4-amidoxime, m. 305°, was recovered after acidification with HOAc. 5-Thiocarbamoyl pyrimidine (XVI) (0.5 g.), 0.25 g. NH2OH.HCl, 1 g. Na2CO3, 15 ml. EtOH, and 8 ml. H2O refluxed 8 hrs., the mixture concentrated, and refrigerated 24 hrs. yielded pyrimidine-5-amidoxime, m. 165°. I (0.9 g.), 0.65 g. NaN3, 1.8 ml. HOAc, and 3 ml. iso-PrOH heated 108 hrs. at 150°, refrigerated 16 hrs., the dried precipitate dissolved in 10 ml. H2O, and acidified with 10% HCl yielded 1.14 g. 3-(5-tetrazolyl)pyridazine (XVIII), m. 307-8°, after sublimation at 210°/0.01 mm. Similarly prepared were: 4-(5-tetrazolyl)pyridazine, m. 237°; 3-hydroxy-4-(5-tetrazolyl)pyridazine, m. 331°; 2-(5-tetrazolyl)pyrimidine, m. 233°; and 4-(5-tetrazolyl)pyrimidine, m. 266°. XII (1 g.), 0.7 g. NaN3, 0.57 g. NH4Cl, and 13 ml. HCONMe2 stirred 7 hrs. at 125-30°, the solvent evacuated, and the residue worked up as for XVIII yielded 0.872 g. 4-(5-tetrazolyl)pyrimidine, m. 257°. XV (1 g.) in 5 ml. EtOH saturated with HCl at 0°, excess HCl and EtOH evacuated, the residue washed with Et2O, suspended in 5 ml. EtOH, saturated with NH3 at -15°, added to 3 ml. saturated NaCl at 0°, extracted with Et2O, and the extract gave 0.84 g. ethyl pyrazinimidate, m. 49-50°, after sublimation. Similarly obtained were: ethyl pyrimidine-4-carboximidate (XIX), m. 29-30°; methyl pyridazine-4-carboximidate, m. 102-3°; methyl pyridazine-3-carboximidate, m. 79-80°; ethyl pyrimidine-5-carboximidate (XX), m. 87°; and ethyl pyrimidine-2-carboximidate hydrochlorides, m. 64-5°. For XIX, the solution was filtered prior to extraction with Et2O. XIII (1 g.) treated similarly to XV, the residue washed with Et2O, and the Et2O evaporated yielded 0.634 g. XX. The residue on crystallization from EtOH yielded 0.607 g. 5-amidinopyrimidine hydrochloride, m. 213°, also obtained by refluxing 1 hr. 0.545 g. XX, 0.19 g. NH4Cl, 9 ml. EtOH, and 1 ml. H2O. For preparation of N-monosubstituted diazinoamidines, 0.0085-0.036 mole nitrile was fused with an equimolar amount of amine at 30-75° (130-150° for XVII), an equimolar amount of AlCl3 added such that a temperature of 140-220° is reached (170-180° for best yields), the mixture cooled, dissolved in H2O at 80°, the solution filtered, the filtrate washed with Et2O, and made alk. with 40% NaOH (Na2CO3 for XVII); the amidine was recovered by filtration or extraction with Et2O or CHCl3 and purified by crystallization or sublimation. The following 2-(N-monosubstituted-amidino)-pyrazines were prepared: phenyl, m. 104°; o-tolyl, m. 131°, p-chlorophenyl, m. 148°; benzyl, m. 118°; α-naphthyl, m. 128°; β-naphthyl, m. 114°; and p-tolyl, m. 137°. 3-(N-Monosubstituted-amidino)pyridazines: phenyl, m. 121°; p-tolyl, m. 133°; benzyl, m. 92°; p-chlorophenyl, m. 152°; β-naphthyl, m. 137-8°. 4-Analogs: phenyl, m. 160; p-tolyl, m. 167°; p-methoxyphenyl, m. 118°; p-chlorophenyl, m. 149°; β-naphthyl, m. 128°. The following pyridazines: 3-hydroxy-4-(phenylamidino), m. 177°; 3-hydroxy-4-(p-tolylamidino), m. 190°; 3-hydroxy-4-(p-methoxyphenylamidino), m. 178°; 3-hydroxy-4-(p-chlorophenyl)amidino, m. 198°; 3-hydroxy-4-(β-naphthyl)amidino, m. 183°; and 3-hydroxy-4-(2-pyridyl)amidino, m. 197°. 2-(Monosubstituted-amidino)pyrimidines: phenyl, m. 117-18°; o-tolyl, m. 92-3°; p-tolyl, m. 128°; p-chlorophenyl, m. 112°; α-naphthyl, m. 154-5°; β-naphthyl, m. 166°; benzyl, m. 80°. 4-Analogs: phenyl, m. 126°; o-tolyl, m. 104°; p-tolyl, m. 134°; benzyl, m. 72°; α-naphthyl, m. 148°; β-naphthyl, m. 152°; and p-chlorophenyl, m. 135°. VII, PhCH2NH2, and AlCl3 gave, in addition to the amidine, 4-(N-benzylcarbamoyl)pyridazine, m. 80-1°, also prepared from 4-carbomethoxypyridazine. AlCl3 (0.0095 mole) added in portions to 0.0095 mole each XIII and amine in 25 ml. CS2, the solution refluxed 3-4 hrs., decomposed in ice-HCl, the product taken up in dilute HCl, and liberated with 20% NaOH at 0-5° gave 10-38% yields of the following pyrimidines: 5-(N-phenylamidino), m. 172°; 5-(p-tolylamidino), m. 190°; 5-(p-methoxyphenylamidino), m. 178-9°; 5-(2-pyridylamidino), m. 151°; and 5-(2-thiazolylamidino), m. 162-3°. MeMgI (0.0283 mole) in 20 ml. Et2O added to 0.0905 mole I in 30 ml. Et2O, the mixture stirred 3 hrs., 15 g. ice and 3 g. NH4Cl added after 16 hrs., the Et2O layer separated, the aqueous layer extracted with Et2O, the Et2O extracts washed with NaCl, dried, and concentrated gave 0.64 g. oil, which chromatographed (Al2O3) gave 3-acetylpyridazine (XXI), m. 87-8°, and VI. The aqueous phase stirred 1 hr. with 20% HCl below 5°, neutralized with 40% NaOH, and the product taken up in Et2O gave addnl. XXI in 27% total yield. 4-Acetylpyrimidine, m. 67°, was obtained similarly. VII (1 g.) in 50 ml. Et2O and 5 ml. C6H6 treated with 0.0283 mole MeMgI and the mixture treated as in the preparation of XXI, yielded 71% 4-(iminoacetyl)pyridazine, m. 78-9°. 5-(Iminoacetyl)pyrimidine, m. 180-1°, was prepared similarly. Et2NH (0.0042 mole) in 5 ml. Et2O added to 0.0142 mole EtMgBr in 12 ml. Et2O, the solution refluxed 20 min., cooled, 1 g. III in 5 ml. Et2O and 2 ml. C6H6 added, the mixture refluxed 2 hrs., and worked up as for XXI then chromatographed gave 0.208 g. 2-(diethylcarbamoyl)pyrimidine, m. 35-6°. XII gave 4-(diethylcarbamoyl)pyrimidine, m. 36-7°, and XI.
Ann. Chim. (Paris) published new progress about 92306-69-9. 92306-69-9 belongs to pyrimidines, auxiliary class Tetrazoles, name is 4-(1H-1,2,3,4-Tetrazol-5-yl)pyrimidine, and the molecular formula is C5H4N6, Related Products of pyrimidines.
Referemce:
https://pubchem.ncbi.nlm.nih.gov/compound/Pyrimidine,
Pyrimidine – Wikipedia