Triethylamine → HCID 53940889, compound

HRID 651418Notes

Reaction equation

HRID 651418 reaction equation
[F:1][C:2]([F:14])([F:13])[C:3]1[CH:4]=[C:5](CC(O)=O)[CH:6]=[CH:7][CH:8]=1.S(Cl)(Cl)=O.[K].[C:20]([O:26][CH2:27][CH3:28])(=[O:25])[CH2:21][C:22]([O-:24])=O.[CH2:29](N(CC)CC)C.[Cl-].[Mg+2].[Cl-]>C(#N)C.CN(C)C=O.ClCCl>[C:20]([O:26][C:27]1[CH:28]=[CH:7][CH:8]=[C:3]([C:2]([F:1])([F:13])[F:14])[C:4]=1[CH2:5][CH3:6])(=[O:25])[CH2:21][C:22]([CH3:29])=[O:24]

Participants

10

Reactant 6

HCID 8471TriethylamineHCID 24386Thionyl ChlorideHCID 676953-(Trifluoromethyl)benzeneacetic acidHCID 3595298Propanedioic acid, monoethyl esterHCID 5360315Magnesium ChlorideHCID 5462222Potassium

Product 1

HCID 53940889HCID 53940889, compoundYield 23,398.4%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

(3-Trifluoromethylphenyl)acetic acid (25.1 g, 0.12 mol) is added to a solution of dichloromethane (200 ml) and dimethylformamide (1 ml). Thionyl chloride (18.2 g, 0.15 mol) is then added dropwise and the resulting solution is stirred overnight. The solution is then concentrated under reduced pressure to give the crude acid chloride in nearly quantitative yield. The potassium salt of ethyl malonate (41.3 g, 0.24 mmol) is dissolved in acetonitrile (400 ml) and is cooled to 0° C. Triethylamine (23.23 g, 0.23 mol) and magnesium chloride(28.8 g, 0.30 mol) are then added and the slurry is warmed to 25° C. and is stirred for 2 hours. The slurry then is cooled to 0° C. and the acid chloride is added over 1 hour. The mixture is allowed to warm to room temperature and is stirred overnight. The solvent is removed under reduced pressure and the resulting solid is suspended in toluene (200 ml) and is cooled to 0° C. Ice cold 4N hydrochloric acid is then slowly added. The organic phase is separated and washed with 4N hydrochloric acid, water and finally saturated brine. The organic phase is dried and concentrated. The crude product is then purified by distillation to give ethyl-(3-trifluoromethylphenyl) acetoacetate (15.4 g).

Workup

  1. concentrationThe solution is then concentrated under reduced pressure
  2. customto give the crude acid chloride in nearly quantitative yield
  3. temperaturethe slurry is warmed to 25° C.
  4. stirringis stirred for 2 hours
  5. temperatureThe slurry then is cooled to 0° C.
  6. temperatureto warm to room temperature
  7. stirringis stirred overnight
  8. customThe solvent is removed under reduced pressure
  9. temperatureis cooled to 0° C
  10. additionIce cold 4N hydrochloric acid is then slowly added
  11. customThe organic phase is separated
  12. washwashed with 4N hydrochloric acid, water and finally saturated brine
  13. customThe organic phase is dried
  14. concentrationconcentrated
  15. distillationThe crude product is then purified by distillation

Sources & evidence

ORD record
ord-d2f9ddd35b99440498aab88d320a5de1
Source dataset
uspto-grants-2001_08
Patent number
US06281219B1

Reaction notes

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