Ethyl Acetate → HCID 86668040, compound

HRID 538328Notes

Reaction equation

HRID 538328 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][N:3]=1.[Li+].CC([N-]C(C)C)C.[CH2:17]([O:19][C:20](Cl)=[O:21])[CH3:18].[NH4+].[Cl-].[C:25]([O:28][CH2:29][CH3:30])(=[O:27])C>C1COCC1>[CH2:17]([O:19][C:20](=[O:21])[CH:8]([C:6]1[CH:5]=[CH:4][N:3]=[C:2]([Br:1])[CH:7]=1)[C:25]([O:28][CH2:29][CH3:30])=[O:27])[CH3:18]

Participants

7

Reactant 5

HCID 8857Ethyl AcetateHCID 10928Ethyl chloroformateHCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 27340872-Bromo-4-methylpyridine

Product 1

HCID 86668040HCID 86668040, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

2-Bromo-4-methyl pyridine (70.0 g, 407 mmol) was added drop wise to a cooled (−78° C.) solution of LDA (2.0 M in toluene/THF/ethyl benzene, 610.4 ml, 1.22 mol) in dry THF (600 ml) for 30 min. ethylchloroformate (132.3 g, 1.22 mol) was added to the resultant reaction mixture with addition funnel at −78° C. and stirring continued for 90 min. Reaction mixture was treated with saturated NH4Cl solution and worked up with ethyl acetate by washing with water, brine followed by drying over anhy. Na2SO4. Organic layer was concentrated under reduced pressure to obtain crude product which was purified by column chromatography with 10% ethyl acetate in Hexane to furnish title compound as a brown color oily liquid. Yield: 115.0 g (89%). TLC (10% ethyl acetate in hexane) Rf=0.15; LCMS: RtH8=1.475 [M+1]+=315.8 and 317.8; HPLC RtH9=7.30 min (86.7%); 1H NMR (400 MHz, CDCl3) b 8.38 (d, 1H), 7.56 (t, 1H), 7.34 (dd, 1H), 4.55 (s, 1H), 4.29-4.18 (m, 4H), 1.28 (t, 6H).

Workup

  1. additionwas added to the resultant
  2. customreaction mixture
  3. additionwith addition funnel at −78° C.
  4. customReaction mixture
  5. washby washing with water, brine
  6. customby drying over anhy
  7. concentrationOrganic layer was concentrated under reduced pressure
  8. customto obtain crude product which
  9. customwas purified by column chromatography with 10% ethyl acetate in Hexane

Sources & evidence

ORD record
ord-f91ca58f0e4f41f5983dde8220895431
Source dataset
uspto-grants-2014_10
Patent number
US08865712B2

Reaction notes

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