Carbon Dioxide → (R)-2-chloro-1-(2,4-dichlorophenyl)ethan-1-ol

HRID 1533118Notes

Reaction equation

HRID 1533118 reaction equation
C(=O)=O.C(Cl)(Cl)(Cl)Cl.[Cl:9][CH2:10][C:11]([C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=1[Cl:20])=[O:12].N(CCO)CCO>C1COCC1>[Cl:9][CH2:10][C@@H:11]([C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=1[Cl:20])[OH:12]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 5943Carbon TetrachlorideHCID 8113DiethanolamineHCID 202502,2',4'-Trichloroacetophenone

Product 1

HCID 7003711(R)-2-chloro-1-(2,4-dichlorophenyl)ethan-1-olYield 112%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-25 °C

Procedure

To a solution containing 16 g (49.90 mmol) of (−)-DIP-Cl in 30 mL of anhydrous THF, at −25° C. (dry ice, CCl4), under nitrogen, was added 10 g (44.74 mmol) of 2,2′,4′-trichloroacetophenone. The stoppered solution was stirred at −25° C. for about 7 hours, and then at room temperature overnight. THF was removed in vacuo, and (+)-α-pinene was removed under high vacuum at room temperature overnight. The resulting viscous colorless oil was dissolved in 200 mL of anhydrous ether, and cooled to 0° C. Diethanolamine (10.50 g, 0.10 mol) was added to the filtrate, and stirring was continued for 3 hours at room temperature. The white solid obtained was removed by filtration and washed with anhydrous ether. The colorless solution was evaporated to dryness to yield a viscous colorless oil. This oil was flash chromatographed on silica gel, first with hexanes to remove (+)-α-pinene. The product was eluted from the column with 93% hexanes/7% acetone to yield 11.30 g of a white solid. This solid was crystallized from hexanes at 0° C. Yield: 5.75 g (57%); TLC: 95% hexanes/5% acetone, Rf=0.10.

Workup

  1. customat room temperature
  2. customovernight
  3. customTHF was removed in vacuo, and (+)-α-pinene
  4. customwas removed under high vacuum at room temperature overnight
  5. dissolutionThe resulting viscous colorless oil was dissolved in 200 mL of anhydrous ether
  6. temperaturecooled to 0° C
  7. stirringstirring
  8. waitwas continued for 3 hours at room temperature
  9. customThe white solid obtained
  10. customwas removed by filtration
  11. washwashed with anhydrous ether
  12. customThe colorless solution was evaporated to dryness
  13. customto yield a viscous colorless oil
  14. customchromatographed on silica gel, first with hexanes
  15. customto remove (+)-α-pinene
  16. washThe product was eluted from the column with 93% hexanes/7% acetone

Sources & evidence

ORD record
ord-804d7f31972d4a0ea396b8bbf83b5c3e
Source dataset
uspto-grants-2001_03
Patent number
US06207695B1

Reaction notes

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