Urea → Methyl 2-chloro-5-hydroxybenzoate

HRID 916715Notes

Reaction equation

HRID 916715 reaction equation
N[C:2]1[CH:3]=[CH:4][C:5]([Cl:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].N([O-])=[O:14].[Na+].N(O)=O.NC(N)=O>O.OS(O)(=O)=O.[O-]S([O-])(=O)=O.[Cu+2]>[CH3:10][O:9][C:7](=[O:8])[C:6]1[CH:11]=[C:2]([OH:14])[CH:3]=[CH:4][C:5]=1[Cl:12]

Participants

8

Reactant 4

HCID 1176UreaHCID 24529Nitrous AcidHCID 5200412Methyl 5-Amino-2-chlorobenzoateHCID 23668193Sodium Nitrite

Product 1

HCID 24820256Methyl 2-chloro-5-hydroxybenzoate

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
2.5 °C

Procedure

Compound (78) (9 g, 48.5 mmol) was subjected to diazotization using NaNO2 (4.5 g 48.5 mmol) in water (50 mL) and H2SO4 (10%, 100 mL). Excess nitrous acid was neutralized with urea. The reaction mixture was poured into a suspension of CuSO4. 5H2O (144 g, 577 mmol) and Cu2O (5.22 g, 41.4 mmol) in water (900 mL) at 0° C. The reaction mixture was stirred for 15 min. at 0-5° C. and was then extracted using diethyl ether (200 mL×3). The organic extract was washed, dried (anhy. Na2SO4), concentrated and purified using a silica gel column and 10% EtOAc in petroleum ether (60-80° C.) as eluant to obtain the title compound(80).

Workup

  1. customat 0° C
  2. extractionwas then extracted
  3. extractionThe organic extract
  4. washwas washed
  5. customdried (anhy
  6. concentrationNa2SO4), concentrated
  7. custompurified
  8. customa silica gel column and 10% EtOAc in petroleum ether (60-80° C.)
  9. customto obtain the title compound(80)

Sources & evidence

ORD record
ord-4c138d47d7aa4dcca595242a9ff7081e
Source dataset
uspto-grants-2007_09
Patent number
US07271193B2

Reaction notes

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