Dimethylformamide → Methyl 6-amino-3-bromo-2-methoxybenzoate

HRID 1725986Notes

Reaction equation

HRID 1725986 reaction equation
[CH3:1][O:2][C:3]1[C:8]2[C:9](=[O:14])[O:10][C:11](=O)[NH:12][C:7]=2[CH:6]=[CH:5][CH:4]=1.CN(C=O)C.[Br:20]N1C(=O)CCC1=O>ClCCl>[NH2:12][C:7]1[C:8]([C:9]([O:10][CH3:11])=[O:14])=[C:3]([O:2][CH3:1])[C:4]([Br:20])=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 67184N-bromobutanimideHCID 107502955-Methoxy-2H-3,1-benzoxazine-2,4(1H)-dione

Product 1

HCID 68866280Methyl 6-amino-3-bromo-2-methoxybenzoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of Example 470A (9.8 g, 50.7 mmol), DMF (50 mL), and dichloromethane (150 mL) was cooled to 0° C., treated portionwise with N-bromosuccinimide (12.6 g, 76 mmol), stirred until all the starting material was consumed, and filtered. The filter cake was washed with dichloromethane combined filtrates were concentrated, treated with anhydrous methanol (450 mL), and heated to reflux for 54 hours. Purification by flash column chromatography on silica gel with 15% ethyl acetate/hexanes provided the desired product. MS (ESI(+)) m/e 260, 262 (M+H)+, 277, 279 (M+NH4)+, 282, 284 (M+Na)+; (ESI(−)) m/e 258, 260 (M−H)−; 1H NMR (300 MHz, DMSO-d6) δ 7.34 (d, 1H), 6.50 (d, 1H), 5.63 (s, 2H), 3.82 (s, 3H), 3.71 (s, 3H).

Workup

  1. customwas consumed
  2. filtrationfiltered
  3. washThe filter cake was washed with dichloromethane combined filtrates
  4. concentrationwere concentrated
  5. additiontreated with anhydrous methanol (450 mL)
  6. temperatureheated
  7. temperatureto reflux for 54 hours
  8. customPurification by flash column chromatography on silica gel with 15% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-8c67e89146b1419397671b5edb33516d
Source dataset
uspto-grants-2009_02
Patent number
US07491718B2

Reaction notes

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