Sulfuric Acid → Methyl 4-Chloro-2-(3-methoxy-3-oxo-1-propenyl)-benzoate

HRID 1282402Notes

Reaction equation

HRID 1282402 reaction equation
N([O-])=O.[Na+].N[C:6]1[CH:15]=[C:14]([Cl:16])[CH:13]=[CH:12][C:7]=1[C:8]([O:10][CH3:11])=[O:9].S(=O)(=O)(O)O.NS(O)(=O)=O.[C:27]([O:31][CH3:32])(=[O:30])[CH:28]=[CH2:29]>O.C/C(/[O-])=C/C(C)=O.C/C(/[O-])=C/C(C)=O.[Pd+2]>[Cl:16][C:14]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:6]([CH:29]=[CH:28][C:27]([O:31][CH3:32])=[O:30])[CH:15]=1

Participants

8

Reactant 5

HCID 1118Sulfuric AcidHCID 5987Sulfamic AcidHCID 7294Methyl AcrylateHCID 80001Methyl 4-chloroanthranilateHCID 23668193Sodium Nitrite

Product 1

HCID 69978143Methyl 4-Chloro-2-(3-methoxy-3-oxo-1-propenyl)-benzoate

Reagents, catalysts & solvents 2

HCID 5486778Palladium acetylacetonateCatalystHCID 962WaterSolvent2×

Conditions

Temperature
40 °C

Procedure

At 2° C., a solution of 79.5 g of sodium nitrite in 150 ml of water is added to a mixture of 185.5 g of methyl 2-amino-4-chlorobenzoate, 785 ml of water and 190.5 ml of concentrated sulfuric acid. Subsequently, the mixture is stirred for 30 minutes, and 5.3 g of amidosulfonic acid are then added. The resulting reaction mixture is added dropwise to 108.2 g of methyl acrylate. 766 mg of palladium acetylacetonate are then added to the reaction mixture, which is then heated to 40° C. After a further 3.5 hours at 40° C., the resulting precipitate is filtered off, giving, after drying, 248.3 g of methyl 4-chloro-2-(3-methoxy-3-oxo-1-propenyl)-benzoate of melting point 87-89° C.

Workup

  1. customThe resulting reaction mixture
  2. waitAfter a further 3.5 hours at 40° C.
  3. filtrationthe resulting precipitate is filtered off
  4. customgiving
  5. customafter drying

Sources & evidence

ORD record
ord-f0d2e0777bd340d48e756d85273b18f4
Source dataset
uspto-grants-2002_09
Patent number
US06455725B1

Reaction notes

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