Imai, Kinichi published the artcile< Nucleic acid antagonists. VII. Synthesis and characterization of 1,4,6-triazaindenes (5H-pyrrolo[3,2-d]pyrimidines)>, Synthetic Route of 112-63-0, the main research area is ANTIMETABOLITES; CHEMISTRY, PHARMACEUTICAL; EXPERIMENTAL LAB STUDY; HETEROCYCLIC COMPOUNDS; NUCLEIC ACIDS; PYRIMIDINES; PYRROLES.
2-Carbethoxy-5,7-diethoxy-1,4,6-triazaindene (I) (2 g.) and 10 cc. HCl refluxed 6 h. gave 1.3 g. 2-CO2H derivative (II) of 5,7-dioxo-4,5,6,7-tetrahydro-1,4,6-triazaindene (III), m. above 360° (H2O). II (1 g.) and 100 mg. Cu powder heated at 330-40° until the CO2 evolution ceased gave 600 mg. III, m. above 360° (H2O). I (1 g.) and 500 mg. Cu powder heated 10 min. in vacuo at 220-40° yielded 700 mg. 2-CO2Et derivative (IV) of 4,6-diethyl-5,7-dioxo-4,5,6,7-tetrahydro-1,4,6-triazene (V), m. 205° (aqueous EtOH). IV (840 mg.) in 15 cc. EtOH heated 2 h. on the water bath with 1.5 g. NaOH in 2 cc. H2O gave 700 mg. 2-CO2H derivative (VI) of V, m. 306° (MeOH). VI (150 mg.) heated at 310-20° during 10 min. yielded 100 mg. V, m. 142° (reprecipitated from C6H6 with petr. ether). IV (300 mg.), 5 cc. EtOH, and 3 cc. 28% NH4OH heated 5 h. in a sealed tube at 140-50° gave 200 mg. 2-CONH2 derivative of V, crystal powder, m. 298° (aqueous EtOH). 5-Me derivative (VII) (4.7 g.) of 2-methyl-7-oxo-6,7-dihydro-1,4,6-triazaindene (VIII) refluxed 3 h. with 27 cc. POCl3 yielded 4.8 g. 5-Me derivative (IX) of X, m. 158-60° (AcOEt). VIII (5 g.) and 24 cc. POCl3 gave similarly 4 g. X, m. 178° (decomposition). III (5 g.), 400 cc. POCl3, and 10 cc. Me2NPh refluxed 2 h. gave 2 g. 5,7-dichloro-1,4,6-triazaindene (XI), m. 224° (50% MeOH). III (3 g.) and 24 cc. pyrophosphoryl chloride (upper layer of a mixture prepared by heating POCl3 with 0.5 equivalent H2O 1.5 h.) yielded 2.1 g. XI, m. 226-8° (aqueous MeOH). 7-Oxo-6,7-dihydro-1,4,6-triazaindene (XII) (850 mg.) refluxed 2 h. with 20 cc. POCl3 gave 7-chloro-1,4,6-triazaindene (XIII), m. 186-8° (decomposition) (50% aqueous EtOH). XI (3 g.) and 30 cc. 2N KOH refluxed 4.5 h. yielded 1.6 g. 5-Cl derivative (XIV) of XII, m. 270° (decomposition) (H2O). XI (500 mg.) and 400 mg. CS(NH2)2 in 13 cc. EtOH refluxed 5 h. gave 250 mg. 5,7-dimercapto-1,4,6-triazaindene (XV), pale yellow, m. above 360° (H2O). III (500 mg.), 3 g. P2S5, and 20 cc. Tetralin stirred 1.5 h. at 170-200° and 4 h. at 200-5° gave 150 mg. XV. XV (70 mg.) and 2 cc. 0.5N NaOH shaken with 0.1 cc. Me2SO4 gave the 5,7-di-MeS analog of XV, m. 230° (60% MeOH). XIII (700 mg.) and 350 mg. CS(NH2)2 in 20 cc. EtOH refluxed 4 h. yielded 300 mg. 7-mercapto-1,4,6-triazaindene (XVI), pale yellow needles, m. above 300° (H2O). VII (700 mg.), 3.8 g. P2S5, and 16 cc. Tetralin heated 12 h. at 190-200° gave 2,5-dimethyl-7-mercapto-1,4,6-triazaindene (XVII), crystal powder, m. 314-15° (decomposition) (30% MeOH). IX (1.5 g.), 40 mg. Cu powder, 6.3 cc. alc. NH3, and 2 cc. concentrated NH4OH heated 13 h. in a sealed tube at 160-70° gave 750 mg. 2,5-di-Me derivative of 7-amino-1,4,6-triazaindene (XVIII), needles, m. 300-2° (MeOH). X (400 mg.), 20 mg. Cu powder, 1.8 cc. alc. NH3, and 6 cc. concentrated NH4OH yielded similarly 250 mg. 2-Me derivative (XIX) of XVIII, m. 327-8° (decomposition) (MeOH). XI (3 g.) and 60 cc. alc. NH3 heated 12 h. in an autoclave at 120° yielded 1.6 g. 5-Cl derivative (XX) of XVIII, needles, m. 264° (decomposition) XI (4 g.) and 60 cc. alc. NH3 heated 20 h. in an autoclave at 200° yielded 3.6 g. 5-NH2 derivative of XVIII, needles, m. 285° (decomposition). XIV (4 g.) gave similarly 850 mg. 5-amino-7-oxo-6,7-dihydro-1,4,6-triazaindene, m. above 300° (H2O). IX (2.2 g.) and 1.2 g. MgO in 120 cc. EtOH hydrogenated 2 h. over Pd-C gave 1.3 g. 2,5-dimethyl-1,4,6-triazaindene (XXI), m. 211-12° (AcOEt). X, XIV, and XX gave similarly 66% 2-methyl-1,4,6-triazaindene (XXII), m. 237° (decomposition) (AcOEt), 7-oxo-6,7-dihydro-1,4,6-triazaindene (XXIII), m. above 300° with discoloration from about 290° (H2O), and XVIII, decomposed at 320° with browning from about 280° (H2O), resp. XV (400 mg.) in 30 cc. EtOH refluxed 2 h. with 4 g. Raney Ni and kept overnight gave 210 mg. 1,4,6-triazaindene (XXIV), m. 177° (AcOEt). XI (1 g.) in 80 cc. MeOH hydrogenated over Pd-C gave XXIV, m. 175° (decomposition). XI (3 g.) in 120 cc. MeOH hydrogenated 1.5 h. over Pd-C, and the crude product dissolved in 40 cc. H2O, mixed with 18 cc. 30% KOH, treated dropwise with 11.8 g. K3Fe(CN)6 in 50 cc. hot H2O, and stirred 0.5 h. at room temperature yielded 1.3 g. XXIV, m. 172-4° (AcOEt). I (1.1 g.) in 1.5 cc. AcOH treated 20 min. with cooling with 500 mg. 40% aqueous Me2NH, 1.5 cc. AcOH, and 440 mg. 37% aqueous CH2O and the mixture heated 2 h. on the water bath and kept overnight yielded 500 mg. 3-Me2NCH2 derivative (XXV) of I, needles, m. 103-4° (petr. ether). XXV (200 mg.), 2 cc. EtOH, and 100 mg. MeI gave XXV.MeI, needles, m. 180° (1:2 Me2CO-AcOEt). The UV spectra of I, IV, VIII, XVIII, XXI, XXII, XXIII, XXIV, XXIX, and the dihydro derivative of XXIV.HCl, and the IR spectrum of XXIV were recorded.
Chemical & Pharmaceutical Bulletin published new progress about IR spectra. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Synthetic Route of 112-63-0.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics