Urea → Methyl 2-chloro-5-hydroxybenzoate

HRID 1363410Notes

Reaction equation

HRID 1363410 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8](N)[CH:7]=[CH:6][C:5]=1[Cl:11].N([O-])=[O:14].[Na+].N(O)=O.NC(N)=O>O.OS(O)(=O)=O>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([OH:14])[CH:7]=[CH:6][C:5]=1[Cl:11]

Participants

7

Reactant 4

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

Product 1

HCID 24820256Methyl 2-chloro-5-hydroxybenzoate

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
2.5 °C

Procedure

Compound of example 156 (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 (3×200 mL). The organic extract was washed, dried (anhydrous 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.

Workup

  1. extractionwas then extracted
  2. extractionThe organic extract
  3. washwas washed
  4. dry with materialdried (anhydrous Na2SO4)
  5. concentrationconcentrated
  6. custompurified
  7. customa silica gel column and 10% EtOAc in petroleum ether (60-80° C.)

Sources & evidence

ORD record
ord-c538b334077741188d1e3a199963026a
Source dataset
uspto-grants-2011_02
Patent number
US07884127B2

Reaction notes

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