Ethyl chloroformate → HCID 59921282, compound

HRID 1019230Notes

Reaction equation

HRID 1019230 reaction equation
[Li]C(C)(C)C.Br[C:7]1[CH:12]=[C:11]([CH:13]=[CH:14][O:15][CH3:16])[CH:10]=[CH:9][C:8]=1[CH:17]([CH3:19])[CH3:18].Cl[C:21]([O:23][CH2:24][CH3:25])=[O:22]>C1COCC1>[CH:17]([C:8]1[CH:9]=[CH:10][C:11]([CH:13]=[CH:14][O:15][CH3:16])=[CH:12][C:7]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22])([CH3:19])[CH3:18]

Participants

5

Reactant 3

HCID 10928Ethyl chloroformateHCID 59921297HCID 59921297, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 59921282HCID 59921282, compoundYield 220.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

tert-BuLi solution (1.7 M in pentane, 800 mL; 1.59 M in pentane, 2L; 4.5 mol total) was added via cannula over 135 minutes under nitrogen into a solution of 1-Bromo-6-isopropyl-3-(2-methoxyvinyl)benzene (C) (500 g, 1.96 mol) in anhydrous THF (3 L) at −50 to −75° C. The mixture was stirred for 1 hour after addition was complete. The solution was then transferred via cannula into a chilled (kept below −50° C.) solution of ethyl chloroformate (562 mL, 5.88 moles) in anhydrous THF (2 L), and the resultant solution was stirred for 68 minutes. The reaction was quenched by addition of 1 L of saturated aqueous NH4Cl with stirring, followed by the addition of 2 L of water. The organic phase was separated, washed with a 10% NaCl solution. The solution was concentrated under vacuum to approximately. Evaporation furnished the crude product as a light yellow or greenish yellow liquid. A total of 3 batches were produced according to the above procedures, and 1.7 kg of crude product was obtained. The crude liquid product was distilled under high vacuum (0.9 mm Hg) and distillates in the range of 158 to 165° C. were collected to obtain 1075 g (yield 73%) of product. The following values were obtained by nuclear magnetic resonance spectroscopy:

Workup

  1. additionafter addition
  2. customThe reaction was quenched by addition of 1 L of saturated aqueous NH4Cl
  3. stirringwith stirring
  4. additionfollowed by the addition of 2 L of water
  5. customThe organic phase was separated
  6. washwashed with a 10% NaCl solution
  7. concentrationThe solution was concentrated under vacuum to approximately
  8. customEvaporation
  9. customfurnished the crude product as a light yellow or greenish yellow liquid
  10. customA total of 3 batches were produced
  11. custom1.7 kg of crude product was obtained
  12. distillationThe crude liquid product was distilled under high vacuum (0.9 mm Hg)
  13. customdistillates in the range of 158 to 165° C.
  14. customwere collected

Sources & evidence

ORD record
ord-f0b806f54bd64c99b2f5222430e0aa47
Source dataset
uspto-grants-2002_11
Patent number
US06486202B1

Reaction notes

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