Ethyl Acetate → 2-Bromo-4-chloro-1-[(2,2-diethoxyethyl)thio]benzene

HRID 2199694Notes

Reaction equation

C(=O)([O-])[O-].[K+].[K+].CO[CH:9](OC)[CH2:10]Br.[Br:14][C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[CH:17][C:16]=1[SH:22].[C:23]([O:26][CH2:27][CH3:28])(=[O:25])[CH3:24]>CN(C=O)C.O>[Br:14][C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[CH:17][C:16]=1[S:22][CH2:24][CH:23]([O:25][CH2:9][CH3:10])[O:26][CH2:27][CH3:28]

Participants

Conditions

Temperature: 70 °C

Procedure

Potassium carbonate (0.926 g, 9.34 mmol) then bromoacetaldehyde dimethyl acetal (1.35 g, 6.85 mmol) were added to a solution of 2-bromo-4-chlorobenzenethiol (1.397 g, 6.23 mmol) in anhydrous DMF (11 mL). The mixture was heated at 70° C. for 3 hours. After being allowed to cool to room temperature, the mixture was diluted with ethyl acetate and water. The resulting layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organics were washed with water then saturated NaCl (aq), dried over Na2SO4, filtered, then concentrated. The resulting light yellow oil was used directly for the following step. 1H NMR (500 MHz, CDCl3) δ 7.57 (d, J=2.0 Hz, 1H); 7.33 (d, J=8.5 Hz, 1H); 7.26 (dd, J=8.5, 2.0 Hz, 1H); 4.70 (t, J=5.5 Hz, 1H); 3.75-3.68 (m, 2H); 3.61-3.55 (m, 2H); 3.15 (d, J=5.5 Hz, 2H); 1.23 (t, 7.0 Hz, 6H).

Workup

temperatureto cool to room temperature
customThe resulting layers were separated
extractionthe aqueous phase was extracted with ethyl acetate
washThe combined organics were washed with water
dry with materialsaturated NaCl (aq), dried over Na2SO4
filtrationfiltered
concentrationconcentrated

Sources & evidence

ORD record: ord-243693533667479381d774eb63432a1f
Source dataset: uspto-grants-2016_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09359339B2

Reaction notes

Loading…