Hydrochloric Acid → 3-(Pyridin-2-yl)benzaldehyde

HRID 48044Notes

Reaction equation

HRID 48044 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[Li]CCCC.Br[C:14]1[CH:15]=[C:16]([CH:19]=[CH:20][CH:21]=1)[CH:17]=[O:18].Cl>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1COCC1>[N:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[C:14]1[CH:15]=[C:16]([CH:19]=[CH:20][CH:21]=1)[CH:17]=[O:18]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 79732-BromopyridineHCID 765833-BromobenzaldehydeHCID 178418339Butyllithium

Product 1

HCID 37100393-(Pyridin-2-yl)benzaldehydeYield 38.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Ex-587A) To a THF solution (8 mL) of 2-bromopyridine (1.30 g, 8.23 mmol) at −78° C. was added 1.6 M n-BuLi in hexanes (5.3 mL, 8.48 mmol). The resulting dark red solution was stirred at −78° C. for 10 min, and a solution of 0.5 M ZnCI2 in THF (18 mL, 9.0 mmol) was added giving a light brown slurry. After warming to room temperature, 3-bromobenzaldehyde (0.816 mL, 7.0 mmol) and Pd(PPh3)4 (0.242 g, 0.21 mmol) were added, and the mixture was stirred for 18 h at room temperature under argon. The reaction mixture was poured into 1 N HCl (30 mL) and washed with diethyl ether. The aqueous layer was neutralized with NaHCO3 and extracted with diethyl ether. The solvent was removed in vacuo to give the crude product as an oil. Purification by flash chromatography on silica gel eluting with 20% ethyl acetate in hexane gave 0.49 g (38%) of the desired 3-(2-pyridinyl)benzaldehyde product as a colorless oil. GCMS: m/z=183 [M+].

Workup

  1. customgiving a light brown slurry
  2. temperatureAfter warming to room temperature
  3. stirringthe mixture was stirred for 18 h at room temperature under argon
  4. washwashed with diethyl ether
  5. extractionextracted with diethyl ether
  6. customThe solvent was removed in vacuo
  7. customto give the crude product as an oil
  8. customPurification by flash chromatography on silica gel eluting with 20% ethyl acetate in hexane

Sources & evidence

ORD record
ord-51551e47c08d40f780073ed798d6e6a3
Source dataset
uspto-grants-2004_03
Patent number
US06699898B2

Reaction notes

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