Landquist, Justus K. published the artcile< Quinoxaline N-oxides. I. The oxidation of quinoxaline and its Bz-substituted derivatives>, Recommanded Product: 6-Quinoxalinecarbonitrile, the main research area is .
Quinoxaline (I) and its Bz-substituted-alkyl, alkoxy, halo, and acylamino derivatives are oxidized to 1- and 1,4-dioxides by organic peroxy acids. Resistance to N-oxidation is encountered in 5- and 8-substituted I. Reduction of 2,3-(O2N)2C6H3OEt with H and Raney Ni gave 3,1,2-EtOC6H3(NH2)2, oil (picrate, m. 210-12°). 2,4-Br(O2N)C6H3Me nitrated with HNO3 and H2SO4 at 40-5° gave 2,4,5-Br(O2N)2C6H2Me, m. 94-5°, which, treated with NH3 in alc. 5 h. at 120° and then reduced with Zn dust and NaOH in EtOH, yielded the 4,5-(H2N)2 analog, m. 140-1°. The following general procedure for preparation of I derivatives was used: (CHO.NaHSO3)2, an ο-phenylenediamine, and H2O were stirred 3 h. at 60°, then made alk. with KOH, and the I derivative was filtered off. The following derivatives were prepared (substituent, m.p., m.p. of 1-oxide, m.p. of 1,4-dioxide): 5-Me, 20-1°, b15, 120°, 131-2°, 192-4°; 5-EtO, 63-4°, b18 165-6°, 114-16°, -; 5-Cl (II), 60-2°, 177-9°, -; 6-iodo, 114-15°, -, -; 6-NC (III), 176-8°, -, -; 6,7-Me2, 100-1°, -, 220°; 6,7-benzo, 125-6°, -, -; 6,7-ClMe (IV), 120-2°, 166-8°, 227°; 6,7-BrMe (V), 127-8°, 167-8°, 222-4°; 6,7-Cl2 (VI), 210°, -, 206-8°; 5,8-Cl2 (VII), 205-7°, -, -; 6-Br (VIII)(prepared by the Sandmeyer reaction from the 6-NH2 compound), 48-9°, b18 146-9°, -, 223-5°; 6-AcNH (prepared from the 6-NH2 compound with Ac2O), 196.5°, -, 245-7°; 5-AcNH, -, 175-8°, 230-2° (insufficient for anal.). The following N-oxides were also prepared (substituent, m.p. 1-oxide, m.p. 1,4-dioxide): 6-Me (IX), -, 218-19°; 5,6-benzo, 158-9°, 215-16°; 5,6:7,8-dibenzo, 243-4°, -; 5-MeO, -, 222°; 6-MeO, -, 227-8°; 6-EtO, -, 192-4°; 5,6-(MeO)2, 138-40°, 220-2°; 6,7-(MeO)2, -, 264-5°; 2-Cl, 150-2°, -; 6-Cl (X), 151-2°, 211-12°. I is oxidized with equimolar AcO2H to quinoxaline 1-oxide, m. 122-3° (XI) while excess peroxy acid yields quinoxaline 1,4-dioxide, m. 241-3° (XII). Simultaneous with N-oxide formation there were obtained 2,3-dihydroxyquinoxalines which are listed below: (substituent, % yield, m.p.): IX, 1, 112°; II, 30, 142-3°; X, 15-30, 144°; VIII, 28, 132°; VII, 65, 160-1°; VI, 43, 170-70.5°; IV, 10, 172-3°; V, 12-6, 160-1°; III, 50, -; 6-O2N, 60, 150°. XI and MeI in MeCN set aside in the dark 36 h., precipitated 1-methylquinoxalinium iodide 4-oxide, m. 188-9°. XI was added cautiously to POCl3, and the mixture boiled 15 min. after the reaction subsided, poured on ice, made alk. with KOH, extracted with Et2O, and concentrated to yield 2-chloroquinoxaline, m. 46-8°. Under similar conditions XII yielded 2,3-dichloroquinoxaline; 5-methylquinoxaline 1-oxide gave 2-chloro-5-methylquinoxaline, m. 95°; and 5,6-benzoquinoxaline 1-oxide yielded 2-chloro-5,6-benzoquinoxaline, m. 120.5°. 2-C10H7NHCH2CO2Et dissolved treated in EtOH with PhN2Cl yielded 1,2-Ph2NC10H6NHCH2CO2Et, m. 135-6°, hydrogenated with Raney Ni at 60° and 50 atm. to 1,2,3,4-tetrahydro-2-oxo-7,8-benzoquinoxaline (XIII), m. 197-8°. XIII with alk. H2O2 gave 2-hydroxy-7,8-benzoquinoxaline, isolated as the hydrate, m. 275-5.5°, which was converted with POCl3 into 2-chloro-7,8-benzoquinoxaline, m. 128-9°. N-(6-nitro-o-tolyl)glycine in EtOH hydrogenated over Raney Ni at 60° and 60 atm. yielded 1,2,3,4-tetrahydro-5-methyl-2-oxoquinoxaline, m. 177-80°, readily oxidized to 2-hydroxy-5-methylquinoxaline, m. 282-3°. 2-Chloro-7,8-benzoquinoxaline and piperidine refluxed 1.5 h. gave 2-piperidino-7,8-benzoquinoxaline, m. 101.5-2.5°. 2-Piperidino-5,6-benzoquinoxaline, m. 124-5°, was similarly prepared Cl slowly passed 1 h. into 5,6-benzoquinoxaline in glacial HOAc, and the solution filtered and diluted with H2O yielded, on purification, dichloro-5,6-benzoquinoxaline, m. 187-8°. Methylation of 2,3-dihydroxy-6-nitroquinoxaline with Me2SO4 gave 3-hydroxy-1-methyl-6(or 7)-nitro-2(1H)-quinoxalinone, m. 344°. 6(or 7)-Cyano-3-hydroxy-1-methyl-2(1H)-quinoxalinone, m. 353-4°, is similarly prepared
Journal of the Chemical Society published new progress about Oxidation. 23088-24-6 belongs to class quinoxaline, and the molecular formula is C9H5N3, Recommanded Product: 6-Quinoxalinecarbonitrile.
Referemce:
Quinoxaline – Wikipedia,
Quinoxaline | C8H6N2 | ChemSpider