Itai, Takanobu; Kamiya, Shozo published the artcile< Potential anticancer agents. XI. Synthesis of 4- and 5-azidopyridazine 1-oxide>, Product Details of C4H5N3, the main research area is .
The reaction of NaOMe with 3,4,5-trichloropyridazine (I) was studied. 4-Azidopyridazine 1-oxide (II) and 5-azidopyridazine 1-oxide (III) were synthesized from the corresponding hydrazino compounds 4-hydrazinopyridazine 1-oxide (IV) and 5-hydrazinopyridazine 1-oxide (V) with HNO2; II was also derived from 4-chloropyridazine 1-oxide (VI). I (4.88 g.) kept 1 hr. at 0-5° with 0.61 g. Na in 50 ml. MeOH, then 3 hrs. at room temperature, refluxed 1 hr., the filtrate evaporated, and the product crystallized gave 1.6 g. 5-methoxy-3,4-dichloropyridazine (VII), m. 101-2°. VII (1 g.) in 20 ml. MeOH treated with H and Pd-C gave quant. 4-methoxypyridazine, m. 143-4°. VII (1.4 g.) refluxed 3 hrs. with 0.18 g. Na in 20 ml. MeOH gave 0.57 g. 4-chloro-3,5-dimethoxypyridazine (VIII), m. 161-2°. The mother liquors afforded 0.36 g. 3-chloro-4,5-dimethoxypyridazine (IX), m. 91-2°. VIII was dehalogenated by catalytic hydrogenation in the presence of concentrated NH4OH to give 74% 3,5-dimethoxypyridazine, m. 73-5°. Similarly, IX gave 4,5-dimethoxypyridazine, m. 98-100°; picrate m. 165°. I (5.22 g.) similarly treated with 2 equimolar amounts of MeONa gave 25% VIII and 41% IX. VI (1.042 g.) heated 2 hrs. with 0.19 g. Na in 40 ml. MeOH gave 0.97 g. 4-methoxypyridazine 1-oxide (X), m. 124-5°. X (0.97 g.), 5 ml. 80% N2H4.H2O, and 5 ml. alc. refluxed 3 hrs. gave 0.42 g. IV, m. 192-3° (decomposition); benzylidene derivative m. 252° (decomposition); isopropylidene derivative m. 218°; cyclohexylidene derivative m. 196-9°. IV (0.1 g.) in 5 ml. 5% HCl treated dropwise with 55 mg. NaNO2 in 2 ml. H2O, kept 20 min., and basified gave 52 mg. II, m. 123° (decomposition). VI (0.6 g.), 0.6 g. NaN3, 2 ml. H2O, and 8 ml. alc. heated 5 hrs. in a sealed tube gave 51% II. The aqueous layer afforded 4% 4-aminopyridazine 1-oxide. II (0.25 g.) in 10 ml. CHCl3, refluxed 2 hrs. with 0.7 g. PCl3, evaporated, the residue left with 5 ml. ice-H2O, basified, and extracted with CHCl3 gave 0.16 g. 4-azidopyridazine (XI), m. 62-4°. XI (30 mg.) in 5 ml. MeOH shaken 5 min. with Pd-C and H gave 4-aminopyridazine, m. 129-30°. IV (0.2 g.), 0.24 g. acetylacetone, and 30 ml. alc. refluxed 3 hrs. gave 0.23 g. 4-(3,5-dimethyl-1-pyrazolyl)pyridazine 1-oxide (XIa), m. 155-6°. 5-Methoxypyridazine 1-oxide (0.55 g.), 5 ml. alc., and 2.5 ml. 80% N2H4.H2O refluxed 1 hr. gave 0.3 g. V, m. 188° (decomposition); benzylidene derivative m. 280° (decomposition). V (0.2 g.) in 5 ml. 5% HCl treated 20 min. with 0.12 g. NaNO2 in H2O gave 0.16 g. III, m. 100-2° (decomposition). 3-Azidopyridine (3.1 g.), 40 ml. AcOH, and 7 ml. 30% H2O2 heated 3 hrs. at 75°, then 3 hrs. with 4 ml. more 30% H2O2, and the product separated gave 2.25 g. 3-azidopyridine 1-oxide (XII) m. 99-103°. XII refluxed 2 hrs. with Na in MeOH gave 90% starting material. II (0.1 g.) refluxed 1 hr. with 17 mg. Na in 10 ml. MeOH, evaporated, the residue extracted with hot CHCl3, evaporated, and crystallized gave 74% X. II similarly treated with PhCH2ONa gave 71% 4-benzyloxypyridazine 1-oxide, m. 140-1°. III (0.12 g.) heated 1 hr. with Na in anhydrous PhCH2OH gave 51% 5-benzyloxypyridazine 1-oxide, m. 100-2°. Similar treatment of XIa with MeONa gave 63% 5-methoxypyridazine 1-oxide, m. 106-9°.
Chemical & Pharmaceutical Bulletin published new progress about Neoplasm. 20744-39-2 belongs to class pyridazine, and the molecular formula is C4H5N3, Product Details of C4H5N3.
Referemce:
Pyridazine – Wikipedia,
Pyridazine | C4H4N2 – PubChem