Triethylborane → 3-Chloro-5-ethylbenzaldehyde

HRID 587783Notes

Reaction equation

HRID 587783 reaction equation
P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(B([CH2:14][CH3:15])CC)C.Br[C:17]1[CH:18]=[C:19]([CH:22]=[C:23]([Cl:25])[CH:24]=1)[CH:20]=[O:21]>C1COCC1.CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:25][C:23]1[CH:22]=[C:19]([CH:18]=[C:17]([CH2:14][CH3:15])[CH:24]=1)[CH:20]=[O:21]

Participants

7

Reactant 3

HCID 7357TriethylboraneHCID 62657Potassium Phosphate, TribasicHCID 177509523-Bromo-5-chlorobenzaldehyde

Product 1

HCID 840830783-Chloro-5-ethylbenzaldehydeYield 42.9%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

PdCl2(dppf)(37 mg, 0.046 mmol), potassium phosphate (1.93 g, 9.11 mmol) and triethylborane (1M in hexane, 0.45 g, 4.56 mmol) were added to a solution of 3-bromo-5-chloro-benzaldehyde (1.0 g, 4.56 mmol) in THF (20 mL) at ambient temperature and the mixture was refluxed for 12 h. The reaction mixture was brought to ambient temperature, diluted with EtOAc and washed with water. The organic layer was dried (Na2SO4), filtered, concentrated and the residue was purified by column chromatography on silica (100-200 mesh) eluting with 2% EtOAc in petroleum ether to afford the title compound (330 mg, 41%) as a pale yellow liquid: 1H NMR (400 MHz, DMSO-d6) δ 9.97 (s, 1H), 7.75 (d, J=1.6 Hz 1H), 7.73 (s, 1H), 7.65 (s, 1H), 2.74-2.68 (m, 2H), 1.23 (t, J=7.6 Hz, 3H); ESIMS m/z 168.0 ([M]+); IR (thin film) 3071, 1699, 692 cm−1.

Workup

  1. temperaturethe mixture was refluxed for 12 h
  2. customwas brought to ambient temperature
  3. washwashed with water
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customthe residue was purified by column chromatography on silica (100-200 mesh)
  8. washeluting with 2% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-cc58cae17ae949b88dd8aa6a8cb27bac
Source dataset
uspto-grants-2016_01
Patent number
US09226501B2

Reaction notes

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