Ethyl formate → HCID 21941886, compound

HRID 2216284Notes

Reaction equation

HRID 2216284 reaction equation
Br[C:2]1[C:3]([NH:9][CH2:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[N:4][C:5]([Cl:8])=[N:6][CH:7]=1.C([Li])CCC.[CH2:20]([O:22]C=O)C>C1COCC1>[Cl:8][C:5]1[N:4]=[C:3]([NH:9][CH2:10][C:11]([CH3:14])([CH3:13])[CH3:12])[C:2]([CH:20]=[O:22])=[CH:7][N:6]=1

Participants

5

Reactant 3

HCID 8025Ethyl formateHCID 21941888HCID 21941888, compoundHCID 178418339Butyllithium

Product 1

HCID 21941886HCID 21941886, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (5-bromo-2-chloro-pyrimidin-4-yl)-(2,2-dimethyl-propyl)-amine (30 g, 108 mmol) in THF (500 ml) is added n-butyllithium (1.6 mol/l in n-hexane, 148 ml, 237 mmol) dropwise at −78° C. and the mixture is stirred for 10 min. Ethylformate (19 ml, 230 mol) is added dropwise to the mixture at −78° C., and the reaction mixture is allowed to warm to ambient temperature. After being stirred for 1 hour, the reaction mixture is quenched with saturated NH4Cl at −78° C. and then extracted with AcOEt. The combined extracts are washed with water, brine, dried over MgSO4 and concentrated under reduced pressure. The residue is purified by silica gel column chromatography (eluent:n-hexane:AcOEt=4:1) give 2-chloro-4-(2,2-dimethyl-propylamino)-pyrimidine-5-carbaldehyde. Rf=0.56 (n-hexane:AcOEt=1:1). 1H NMR (400 MHz, DMSO-d6) δ 1.00 (s, 9H), 3.41 (d, 2H), 8.40 (s, 1H), 8.88 (brs, 1H), 9.84 (s, 1H).

Workup

  1. stirringAfter being stirred for 1 hour
  2. customthe reaction mixture is quenched with saturated NH4Cl at −78° C.
  3. extractionextracted with AcOEt
  4. washThe combined extracts are washed with water, brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe residue is purified by silica gel column chromatography (eluent:n-hexane:AcOEt=4:1)

Sources & evidence

ORD record
ord-178109071b6c4588a8d76eedd176931b
Source dataset
uspto-grants-2006_09
Patent number
US07112589B2

Reaction notes

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