1,3-Dibromo-5,5-dimethylhydantoin → HCID 86668439, compound

HRID 1424652Notes

Reaction equation

HRID 1424652 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[CH:3]=1.[Br:14]N1C(C)(C)C(=O)N(Br)C1=O.OS([O-])=O.[Na+].CCOC(C)=O>ClCCCl>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[C:3]=1[Br:14]

Participants

6

Reactant 4

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 8857Ethyl AcetateHCID 23665763Sodium BisulfiteHCID 86668302Methyl 4-amino-6-chloro-5-fluoropicolinate

Product 1

HCID 86668439HCID 86668439, compoundYield 61%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
83 °C

Procedure

Methyl 4-amino-6-chloro-5-fluoropicolinate (1.0 g, 4.9 mmol) was combined with 1,3-dibromo-5,5-dimethylhydantoin (1.7 g, 5.9 mmol) in 1,2-dichloroethane (15 mL) and heated at reflux (83° C.) for 4 h. The cooled mixture was stirred with 10% NaHSO3 solution and EtOAc (30 mL). The organic phase was separated, washed with water (2×20 mL), brine (10 mL), dried (Na2SO4) and concentrated. The residue was purified by silica gel chromatography (5-50% EtOAc-hexane) to give an orange solid (840 mg, 61%): mp 138-139° C.; EIMS m/z 282, 284; 1H NMR (400 MHz, CDCl3) δ 5.09 (s, 2H, NH2), 3.97 (s, 3H, Me); 19F NMR (376 MHz, CDCl3) δ −135.55 (s).

Workup

  1. temperatureheated
  2. customThe organic phase was separated
  3. washwashed with water (2×20 mL), brine (10 mL)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel chromatography (5-50% EtOAc-hexane)

Sources & evidence

ORD record
ord-c015a575258e47be8d78e6f5cf6f5967
Source dataset
uspto-grants-2015_01
Patent number
US08927731B2

Reaction notes

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