Hydrochloric Acid → 4-Chloro-2-methoxycarbonyl-phenyl acetic acid methyl ester

HRID 869423Notes

Reaction equation

HRID 869423 reaction equation
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8](N)[CH:7]=[CH:6][C:5]=1[CH2:11][C:12]([O:14][CH3:15])=[O:13].N([O-])=O.[Na+].[ClH:21]>Cl[Cu]>[CH3:15][O:14][C:12](=[O:13])[CH2:11][C:5]1[CH:6]=[CH:7][C:8]([Cl:21])=[CH:9][C:4]=1[C:3]([O:2][CH3:1])=[O:16]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 123467642-Methoxycarbonylmethyl-5-amino-benzoic acid methyl esterHCID 23668193Sodium Nitrite

Product 1

HCID 128996554-Chloro-2-methoxycarbonyl-phenyl acetic acid methyl ester

Reagents, catalysts & solvents 1

HCID 62652Cuprous chlorideCatalyst

Procedure

5-amino-2-methoxycarbonylmethyl-benzoic acid methyl ester (5 g, 22.4 mmol) was dissolved in hydrochloric acid (50 mL). To the solution was added dropwise aq.NaNO2 (1.7 g, 24.6 mmol) at below 5° C. After addition completed, the color became maroon. Then CuCl (2.4 g, 24.6 mmol) solution was added to the reaction mixture. The reaction mixture was reacted at below 5° C. for 1 hour. The reaction mixture was extracted with dichloromethane. The organic layer was washed with water, dried over anhydrous Na2SO4, concentrated and purified by column chromatography on silica gel (petroleum ether/ethyl acetate=10/1) to give 2.3 g of 5-chloro-2-methoxycarbonylmethyl-benzoic acid methyl ester (18E).

Workup

  1. additionTo the solution was added dropwise aq
  2. customat below 5° C
  3. additionAfter addition
  4. customThe reaction mixture was reacted at below 5° C. for 1 hour
  5. extractionThe reaction mixture was extracted with dichloromethane
  6. washThe organic layer was washed with water
  7. dry with materialdried over anhydrous Na2SO4
  8. concentrationconcentrated
  9. custompurified by column chromatography on silica gel (petroleum ether/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-0158c757d10a489da2d1370808269264
Source dataset
uspto-grants-2015_03
Patent number
US08969373B2

Reaction notes

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