Hydrochloric Acid → HCID 68535779, compound

HRID 341350Notes

Reaction equation

HRID 341350 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4](O)[CH:5]=[CH:6][CH:7]=1.Br[CH2:10][CH2:11][CH2:12][C:13]([O:15]CC)=[O:14].[OH-:18].[K+].Cl.[CH3:21]S(C)=O>C(O)C.O>[CH3:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:6][CH:7]=1)[CH2:21][O:18][CH2:10][CH2:11][CH2:12][C:13]([OH:15])=[O:14]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 342M-CresolHCID 679Dimethyl SulfoxideHCID 14797Potassium Hydroxide2×HCID 76300Ethyl 4-bromobutyrate

Product 1

HCID 68535779HCID 68535779, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent4×

Procedure

A suspension of 3-methylphenol (200 g, 1.85 mol), ethyl 4-bromobutanoate (433 g, 2.11 mol), potassium hydroxide (155.7 g, 2.78 mol), 500 mL of water in 2500 mL of Dimethylsulfoxide (DMSO) in a 5-L flask was stirred at room temperature overnight. An additional 500 g water was added, and the reaction mixture was heated at 75° C. for 2 hours. Potassium hydroxide (155.7 g, 2.78 mol) was added. The reaction was stirred for an additional 30 min. The thick slurry was transferred in a 22-L flask. Addition of water (6 L) to the slurry with stirring caused the dissolution of the slurry. Concentrated HCl (300 mL) was slowly added. During the reaction, the temperature of the reaction mixture was maintained at about 36° C. with external cooling with ice. After the addition, the mixture was further cooled overnight to 10° C. The resulting solid was collected by filtration, washed with 100 mL of water, and dried with in-house vacuum for 2 days. Further drying high vacuum overnight afforded 311.88 g of the crude material. Recryallization in a mixture of ethanol (400 mL) and water (150 mL) yielded 290.94 g (81%) of the desired product as a solid. Mp: 53-54° C. HPLC Rt 5.13 min.; 1H NMR (DMSO d6, 300 MHz) δ: 1.88 (m, 2H), 2.22 (s, 3H), 2.33 (t, 2H), 3.89 (t, 2H), 6.62-6.72 (m, 3H), 7.10 (m, 1H), 12.20 (s, 1H). Anal. Calcd for C11H14O3: C, 67.82; H, 7.28. Found: C, 67.90; H, 7.36.

Workup

  1. temperaturethe reaction mixture was heated at 75° C. for 2 hours
  2. stirringThe reaction was stirred for an additional 30 min
  3. customThe thick slurry was transferred in a 22-L flask
  4. stirringwith stirring
  5. dissolutionthe dissolution of the slurry
  6. customDuring the reaction
  7. temperaturethe temperature of the reaction mixture was maintained at about 36° C.
  8. temperaturewith external cooling with ice
  9. additionAfter the addition
  10. filtrationThe resulting solid was collected by filtration
  11. washwashed with 100 mL of water
  12. customdried with in-house vacuum for 2 days
  13. customFurther drying high vacuum overnight
  14. customafforded 311.88 g of the crude material

Sources & evidence

ORD record
ord-2ecd7e8ee1944ac6b775f2e9c34e1cc7
Source dataset
uspto-grants-2014_11
Patent number
US08895777B2

Reaction notes

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