Triethylborane → 3-Chloro-5-ethylbenzaldehyde

HRID 1503801Notes

Reaction equation

HRID 1503801 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-db80a8333a1c4a57a4fae3b0bb34a8bb
Source dataset
uspto-grants-2015_12
Patent number
US09212164B2

Reaction notes

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