Potassium Hydroxide → 1-Amino-5,7-dibromo-1,4-dihydro-2,3-quinoxalinedione

HRID 53746Notes

Reaction equation

HRID 53746 reaction equation
FC1C(F)=C(F)C(F)=C2C=1[NH:4]C(=O)C(=O)N2.[Br:17][C:18]1[CH:27]=[C:26]([Br:28])[CH:25]=[C:24]2[C:19]=1[NH:20][C:21](=[O:30])[C:22](=[O:29])[NH:23]2.[OH-].[K+].NOS(O)(=O)=O>O>[NH2:4][N:23]1[C:24]2[C:19](=[C:18]([Br:17])[CH:27]=[C:26]([Br:28])[CH:25]=2)[NH:20][C:21](=[O:30])[C:22]1=[O:29]

Participants

6

Reactant 4

HCID 14797Potassium HydroxideHCID 76284hydroxylamine-O-sulfonic acid2×HCID 105917505,7-Dibromo-1,4-dihydro-2,3-quinoxalinedioneHCID 211899685,6,7,8-Tetrafluoro-1,4-dihydro-2,3-quinoxalinedione

Product 1

HCID 199586131-Amino-5,7-dibromo-1,4-dihydro-2,3-quinoxalinedioneYield 79%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

The procedure of Shin, S. C. and Lee. Y. Y., Taehan Hwahakhoe Chi 27 (5): 382-4 (1983) was adapted. 5,7-Dibromo-1,4-dihydroquinoxaline-2,3-dione (46 mg, 0.144 mmole) was dissolved into 3N KOH (2 mL) at 60° C. for 1 h, and NH2OSO3H (20 mg, 0.172 mmole, Aldrich) in distilled water (0.5 mL) was dropwise added into above solution with stirring at 60° C. Some precipitate came out after 15 mins, then a second 20 mg NH2OSO3H portion was added. The mixture was stirred at room temperature for 1 h. The white precipitate was collected by filtration, washed with cold distilled water (0.5 mL), affording crude 1-amino-5,7-dibromo-1,4-dihydro-2,3-quinoxalinedione (38 mg, 79%) after drying in the air at 60° C. for 2h (contains the isomeric 4-amino-5,7-dibromo-2,3-quinoxalinedione, by NMR, but it is not known which is produced in a greater amount). A 38 mg sample of crude 1-amino-5,7-dibromo-1,4-dihydro-2,3-quinoxalinedione was dissolved into distilled water (4 mL) at 60° C., the insoluble material was removed by filtration, and the filtrate was acidified with AcOH to pH=5 to give a white precipitate, which was collected by filtration and washed with cold distilled water (2×1 mL). The precipitate was dried at 60° C. for 2h affording 1-amino-5,7-dibromo-1,4-dihydro-2,3-quinoxalinedione (28 mg, 58.5%) as a white powder with some isomer. Mp: 273°-5° C. (dec. from 270° C.). IR (KBr, cm-1): 3435; 3289; 3190; 1719; 1672; 1625; 1584. NMR (1H, DMSO-d6): δ 5.831 ((s, 2H); 7.672 (d, J=15 Hz, 1H); 7.810 (d, J=15Hz, 1H); 11.275 (s, 1H). HRMS: calcd for C8H3N3O2Br2 (M+) m/z: 332.8746; Found: 332.8744.

Workup

  1. stirringThe mixture was stirred at room temperature for 1 h
  2. filtrationThe white precipitate was collected by filtration
  3. washwashed
  4. distillationwith cold distilled water (0.5 mL)

Sources & evidence

ORD record
ord-8b631b682d75484c8e20ac2e3ddbf358
Source dataset
uspto-grants-1997_04
Patent number
US05620979

Reaction notes

Loading…