Potassium Carbonate → 4-[(2-Chloro-4-formylphenyl)sulfanyl]-2-methylphenoxy-acetic acid ethyl ester

HRID 985050Notes

Reaction equation

HRID 985050 reaction equation
C([O-])([O-])=O.[K+].[K+].[CH2:7]([O:9][C:10](=[O:21])[CH2:11][O:12][C:13]1[CH:18]=[CH:17][C:16]([SH:19])=[CH:15][C:14]=1[CH3:20])[CH3:8].[Cl:22][C:23]1[CH:24]=[C:25]([CH:28]=[CH:29][C:30]=1Cl)[CH:26]=[O:27]>CN(C=O)C>[CH2:7]([O:9][C:10](=[O:21])[CH2:11][O:12][C:13]1[CH:18]=[CH:17][C:16]([S:19][C:30]2[CH:29]=[CH:28][C:25]([CH:26]=[O:27])=[CH:24][C:23]=2[Cl:22])=[CH:15][C:14]=1[CH3:20])[CH3:8]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 227103,4-DichlorobenzaldehydeHCID 16641178Ethyl (4-mercapto-2-methylphenoxy)acetate

Product 1

HCID 207681164-[(2-Chloro-4-formylphenyl)sulfanyl]-2-methylphenoxy-acetic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

An oven-dried 500 mL round-bottomed flask was charged with finely powdered K2CO3 (31.8 g, 230 mmol) and anhydrous DMF (104 mL). Next, a solution of compound 10.3 (26.1 g, 115 mmol) and 3,4-dichlorobenzaldehyde (21.0 g, 120 mmol) in anhydrous DMF (52 mL) was added dropwise at 90° C., and the reaction was vigorously stirred at same temperature for 1 h. The reaction mixture was poured into 468 mL of ice-water and extracted with 3×200 mL of AcOEt. The combined organics were sequentially washed with 2×200 mL of water and 100 mL of brine, dried over Na2SO4, and concentrated to a yellow oil, which was then purified by flash chromatography (SiO2 gel 60 N, eluted with 10% AcOEt/hexane—20% AcOEt/hexane). The fractions containing only desired product were combined and concentrated to a slightly yellow oil (34.9 g). 1H NMR (300 MHz) (CDCl3) δ 9.85 (1H, s); 7.81 (1H, d, J=1.5 Hz); 7.50 (1H, dd, J=1.8, 8.1 Hz); 7.37-7.35 (2H, m); 6.80-6.74 (2H, m); 4.71 (2H, s); 4.30 (2H, q, J=7.2 Hz); 2.32 (3H, s); 1.32 (3H, t, J=7.2 Hz).

Workup

  1. extractionextracted with 3×200 mL of AcOEt
  2. washThe combined organics were sequentially washed with 2×200 mL of water and 100 mL of brine
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated to a yellow oil, which
  5. customwas then purified by flash chromatography (SiO2 gel 60 N, eluted with 10% AcOEt/hexane—20% AcOEt/hexane)
  6. additionThe fractions containing only desired product
  7. concentrationconcentrated to a slightly yellow oil (34.9 g)

Sources & evidence

ORD record
ord-87e4e313c2204ff8946ac5e12350593c
Source dataset
uspto-grants-2005_03
Patent number
US06869975B2

Reaction notes

Loading…