Sodium Bromide → 2,6-Dichloro-3-fluorobenzaldehyde

HRID 2046911Notes

Reaction equation

[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[CH2:10][OH:11].[Br-].[Na+].CC1(C)N([O])C(C)(C)CCC1.Cl[O-].[Na+].C(=O)(O)[O-].[Na+]>ClCCl>[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[CH:10]=[O:11]

Participants

Conditions

Temperature: -7 °C

Procedure

To a solution of (2,6-Dichloro-3-fluorophenyl)methanol (100 g, 0.51 mol) in dichloromethane (450 mL) was added a solution of sodium bromide (54 g, 0.53 mol, in 90 mL water). The rapidly stirred biphasic mixture was cooled to −7° C. and TEMPO (1.54 g, 0.0100 mol) was added. A solution of 0.81M sodium hypochlorite (823 mL, 0.66 mol) saturated with sodium bicarbonate (75 g) was added dropwise over a period of 1 h while maintaining the temperature below −2° C. After the addition the reaction mixture was stirred for 30 min. The two layers separated and the DCM layer was washed with aq. solution of sodium thiosulfate. The DCM layer was dried (Na2SO4) and concentrated on rotary evaporator without using vacuum (aldehyde is volatile) to give the title compound as a solid, mp. 63-65° C. 1H NMR (CDCl3, 300 MHz): δ=7.23 (dd, 1H, J=7.8, 9.0 Hz), 7.35 (dd, 1H, J=4.5, 9.3 Hz), 10.2 (s, 1H).

Workup

temperaturewhile maintaining the temperature below −2° C
additionAfter the addition the reaction mixture
customThe two layers separated
washthe DCM layer was washed with aq. solution of sodium thiosulfate
dry with materialThe DCM layer was dried (Na2SO4)
concentrationconcentrated on rotary evaporator

Sources & evidence

ORD record: ord-c726c3fe37a0491eb1616882804c3306
Source dataset: uspto-grants-2013_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08592448B2

Reaction notes

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