Malonic Acid → Bis(2,4,6-trichlorophenyl) propanedioate

HRID 1958233Notes

Reaction equation

HRID 1958233 reaction equation
[C:1]([OH:7])(=[O:6])[CH2:2][C:3]([OH:5])=[O:4].[Cl:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[C:11]([Cl:16])[C:10]=1O.P(Cl)(Cl)(Cl)=O>>[Cl:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[C:11]([Cl:16])[C:10]=1[O:4][C:3](=[O:5])[CH2:2][C:1]([O:7][C:10]1[C:9]([Cl:8])=[CH:14][C:13]([Cl:15])=[CH:12][C:11]=1[Cl:16])=[O:6]

Participants

4

Reactant 3

HCID 867Malonic AcidHCID 69142,4,6-TrichlorophenolHCID 24813Phosphorus oxychloride

Product 1

HCID 2783450Bis(2,4,6-trichlorophenyl) propanedioateYield 100.6%

Conditions

Temperature
70 °C

Procedure

A mixture of malonic acid (20 g, 192 mmol), 2,4,6-trichlorophenol (72 g, 365 mmol), and phosphorus oxychloride (38 mL, 403.2 mmol) was stirred at reflux for 12 hours. The reaction mixture was cooled to 70° C. and poured into ice water. The solid was collected by filtration, washed with water, and air dried to give malonic acid bis-(2,4,6-trichloro-phenyl) ester (85 g, 95%). A solution of malonic acid bis-(2,4,6-trichloro-phenyl) ester (85 g, 183.6 mmol) and ethyl 3-aminocrotonate (26.1 g, 202 mmol) in bromobenzene (100 mL) was stirred at reflux for 50 min. The reaction mixture was cooled to 50° C. and diluted with EtOAc (260 mL). The solid was collected by filtration, washed with water, and air dried to give 4,6-dihydroxy-2-methyl nicotinic acid ethyl ester (31 g, 86%).

Workup

  1. temperatureat reflux for 12 hours
  2. filtrationThe solid was collected by filtration
  3. washwashed with water, and air
  4. customdried

Sources & evidence

ORD record
ord-bb1c5607d59240c8a0db4f8aabc3d1e9
Source dataset
uspto-grants-2013_04
Patent number
US08410109B2

Reaction notes

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