Hydrochloric Acid → 4-[(2-Chloro-4-hydroxymethylphenyl)sulfanyl]-2-methylphenoxy-acetic acid ethyl ester

HRID 1991160Notes

Reaction equation

HRID 1991160 reaction equation
[CH2:1]([O:3][C:4](=[O:24])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([S:13][C:14]2[CH:19]=[CH:18][C:17]([CH:20]=[O:21])=[CH:16][C:15]=2[Cl:22])=[CH:9][C:8]=1[CH3:23])[CH3:2].CCO.[BH4-].[Na+].Cl>C1COCC1>[CH2:1]([O:3][C:4](=[O:24])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([S:13][C:14]2[CH:19]=[CH:18][C:17]([CH2:20][OH:21])=[CH:16][C:15]=2[Cl:22])=[CH:9][C:8]=1[CH3:23])[CH3:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 702EthanolHCID 4311764Sodium borohydrideHCID 207681164-[(2-Chloro-4-formylphenyl)sulfanyl]-2-methylphenoxy-acetic acid ethyl ester

Product 1

HCID 207681184-[(2-Chloro-4-hydroxymethylphenyl)sulfanyl]-2-methylphenoxy-acetic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

An oven-dried 500 mL round-bottomed flask was charged with compound 10.4 (34.9 g, 95.7 mmol), EtOH (175 mL) and THF (17.5 mL). Next, sodium borohydride (1.10 g, 29.1 mmol) was added in 3 portions at 0° C., and the reaction was vigorously stirred at 0° C. for 1 h. The reaction mixture was poured into 463 mL of 0.25 N HCl at 0° C. and the product was extracted with 3×200 mL of AcOEt. The combined organics were washed sequentially 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 20% AcOEt/hexane-30% AcOEt/hexane). The fractions containing only desired product were combined and concentrated to a slightly yellow oil (33.5 g). 1H NMR (400 MHz) (CDCl3) δ 7.37 (1H, d, J=1.5 Hz); 7.31-7.28 (2H, m); 7.05 (1H, dd, J=1.8, 8.2 Hz); 6.77 (1H, d, J=8.2 Hz); 6.72 (1H, d, J=8.3 Hz); 4.67 (2H, s); 4.61 (2H, d, J=5.9 Hz); 4.28 (2H, q, J=7.2 Hz); 2.29 (3H, s); 1.66 (1H, t, J=5.9 Hz); 1.31 (3H, t, J=7.2 Hz).

Workup

  1. extractionthe product was extracted with 3×200 mL of AcOEt
  2. washThe combined organics were washed sequentially 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 20% AcOEt/hexane-30% AcOEt/hexane)
  6. additionThe fractions containing only desired product
  7. concentrationconcentrated to a slightly yellow oil (33.5 g)

Sources & evidence

ORD record
ord-f9460f056ab445ef9feffd47c615d767
Source dataset
uspto-grants-2010_01
Patent number
US07645779B2

Reaction notes

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