Chlorine → 3,5-Dichloro-2-fluoro-6-hydroxybenzaldehyde

HRID 855138Notes

Reaction equation

[Cl:1][C:2]1[C:3]([F:11])=[C:4]([C:7]([OH:10])=[CH:8][CH:9]=1)[CH:5]=[O:6].[Cl:12]Cl>C(O)(=O)C.O>[Cl:1][C:2]1[C:3]([F:11])=[C:4]([C:7]([OH:10])=[C:8]([Cl:12])[CH:9]=1)[CH:5]=[O:6]

Participants

Conditions

Temperature: 60 °C

Procedure

To 20 g (114.6 mmole) of 3-chloro-2-fluoro-6-hydroxybenzaldehyde in 250 mL of glacial acetic acid was added 27.8 g of Cl2 gas over a period of 30 min. The mixture was stirred and heated to 60° C. for 2 hrs and allowed to stir at rt overnight. The reaction mixture was diluted with 1L of water and extracted four times with diethyl ether. Combined extracts were washed with water and sat. brine and concd in vacuo to afford a slurry. Addition of 250 mL of water afforded a solid which was collected by filtration and allowed to air dry for 8 hrs to afford 20.42 g (85%) of a yellow solid: mp 58-62° C.; 1H NMR (CDCl3/400 MHz) 7.65 (d, 1H, J=7.5 Hz), 10.26 (s, 1H), 11.88 (s, 1H); 13C NMR (CDCl3/100 MHz) 111.2 (d, J=12.0 Hz), 118.2 (d, J=4.6 Hz), 127.8, 137.6 (C—H, d, J=2.1 Hz), 156.8 (d, J=3.0 Hz), 158.3 (d, J=260.8 Hz), 191.4 (CHO, d, J=8.8 Hz); 19F NMR (CDCl3/400 MHz) −124.7 (d, 1F, J=7.7 Hz); MS (EI) 208 (M+, 100); 207 (91); HRMS (EI) m/z calcd for (C7H3O2Cl2F) 207.9494, found 207.9470.

Workup

stirringto stir at rt overnight
extractionextracted four times with diethyl ether
washCombined extracts were washed with water and sat. brine and concd in vacuo
customto afford a slurry
customafforded a solid which
filtrationwas collected by filtration
customto air dry for 8 hrs

Sources & evidence

ORD record: ord-5762d4d4ead44ce5bbdc67c0e450db23
Source dataset: uspto-grants-2007_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07259266B2

Reaction notes

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