Ethyl chloroformate → HCID 15021948, compound

HRID 345365Notes

Reaction equation

HRID 345365 reaction equation
C([Li])CCC.[CH2:6]([C:8]12[CH2:15][O:14][C:11]([C:16]3[CH:21]=[CH:20][C:19]([C:22]#[CH:23])=[CH:18][CH:17]=3)([O:12][CH2:13]1)[O:10][CH2:9]2)[CH3:7].Cl[C:25]([O:27][CH2:28][CH3:29])=[O:26]>O1CCCC1>[CH2:6]([C:8]12[CH2:9][O:10][C:11]([C:16]3[CH:17]=[CH:18][C:19]([C:22]#[C:23][C:25]([O:27][CH2:28][CH3:29])=[O:26])=[CH:20][CH:21]=3)([O:14][CH2:15]1)[O:12][CH2:13]2)[CH3:7]

Participants

5

Reactant 3

HCID 10928Ethyl chloroformateHCID 30656912,6,7-Trioxabicyclo(2.2.2)octane, 4-ethyl-1-(4-ethynylphenyl)-HCID 178418339Butyllithium

Product 1

HCID 15021948HCID 15021948, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

n-Butyl lithium solution (0.67 ml, 1.6M in hexane) was added to a stirred solution of 4-ethyl-1-(4-ethynylphenyl)-2,6,7-trioxabicyclo[2,2,2]octane (200 mg) in tetrahydrofuran (5 ml) at 0° C. under nitrogen. The solution was maintained at 0° C. for 10 minutes when ethyl chloroformate (0.1 ml) was added neat. The solution was allowed to warm to room temperature over 1.5 hours. The reaction was quenched with water (1 ml) and the solvent was removed under vacuum. The residue was taken up in ether and washed with water and brine. The ethereal solution was dried over anhydrous magnesium sulphate and then evaporated in vacuo. The residue was extracted with boiling hexane and afforded ethyl 3-[4-(4-ethyl-2,6,7-trioxabicyclo[2,2,2]oct-1-yl)phenyl]prop-2-ynoate (67 mg) as an off-white crystalline solid on cooling.

Workup

  1. additionwas added neat
  2. customThe reaction was quenched with water (1 ml)
  3. customthe solvent was removed under vacuum
  4. washwashed with water and brine
  5. dry with materialThe ethereal solution was dried over anhydrous magnesium sulphate
  6. customevaporated in vacuo
  7. extractionThe residue was extracted with boiling hexane

Sources & evidence

ORD record
ord-f69b1562e2e4450099c7b8b6fbfe282c
Source dataset
uspto-grants-1991_10
Patent number
US05057508

Reaction notes

Loading…