3-Methoxybenzaldehyde → 2-Chloro-alpha-(3-methoxyphenyl)-3-pyridinemethanol

HRID 65535

Reaction equation

HRID 65535 reaction equation
C([Li])CCC.Br[C:7]1[C:8]([Cl:13])=[N:9][CH:10]=[CH:11][CH:12]=1.ClC1C([Li])=CC=CN=1.[CH:22](=[O:31])[C:23]1[CH:28]=[CH:27][CH:26]=[C:25]([O:29][CH3:30])[CH:24]=1>CCCCCC.CCOCC.O>[Cl:13][C:8]1[C:7]([CH:22]([C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([O:29][CH3:30])[CH:24]=2)[OH:31])=[CH:12][CH:11]=[CH:10][N:9]=1

Participants

8

Reactant 4

HCID 115693-MethoxybenzaldehydeHCID 6933243-Bromo-2-chloropyridineHCID 178418339ButyllithiumHCID 178506730HCID 178506730, compound

Product 1

HCID 201457332-Chloro-alpha-(3-methoxyphenyl)-3-pyridinemethanolYield 59.8%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Procedure

71.5 ml of a 2.1N solution of n-butyllithium in hexane are added to 19.2 g 3-bromo-2-chloropyridine (obtained according to J. D. Cook et. al. J. Chem. Soc., Section C, 1969 1973-8) in 300 ml anhydrous ether at -60° C. and under a static nitrogen atmosphere. To this freshly prepared solution of 2-chloro-3-pyridyllithium, a solution of m-anisaldehyde (13.6 g) in 100 ml anhydrous ether is added dropwise. The reaction mixture is stirred for 1 hr. at -60° C. and then is added to ice:water. The organic phase is separated and the aqueous phase is extracted with ether. The combined organic solutions are washed with water, dried (MgSO4) and solvent evaporated. The crude oil is chromatographed over SiO2 and eluted with chloroform, obtaining 14.9 g of title product as an oil which spontaneously crystallises. Recrystallisation from methanol: water affords pure product, m.p. 114°-5° C.; Cl 14.65 (14.20).

Workup

  1. additionat -60° C. and then is added to ice
  2. customThe organic phase is separated
  3. extractionthe aqueous phase is extracted with ether
  4. washThe combined organic solutions are washed with water
  5. dry with materialdried (MgSO4) and solvent
  6. customevaporated
  7. customThe crude oil is chromatographed over SiO2
  8. washeluted with chloroform

Sources & evidence

ORD record
ord-c596dab32d0148ffad05acd071cc1af8
Source dataset
uspto-grants-1986_09
Patent number
US04614833

Linked notes

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