Ethylparaben → Ethyl 4-(4,4-dimethyl-6-thiochromanoyloxy)benzoate

HRID 2050981Notes

Reaction equation

HRID 2050981 reaction equation
[CH3:1][C:2]1([CH3:15])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([C:12]([OH:14])=[O:13])[CH:10]=2)[S:5][CH2:4][CH2:3]1.C(N(CC)CC)C.O[C:24]1[CH:34]=[CH:33][C:27]([C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:26][CH:25]=1>C(Cl)(Cl)Cl>[CH3:1][C:2]1([CH3:15])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([C:12]([O:14][C:24]3[CH:34]=[CH:33][C:27]([C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:26][CH:25]=3)=[O:13])[CH:10]=2)[S:5][CH2:4][CH2:3]1

Participants

5

Reactant 3

HCID 8434EthylparabenHCID 8471TriethylamineHCID 198342284,4-Dimethyl-3,4-dihydro-2H-1-benzothiopyran-6-carboxylic acid

Product 1

HCID 19834227Ethyl 4-(4,4-dimethyl-6-thiochromanoyloxy)benzoate

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A solution of 280 mg (1.26 mmol) of 4,4-dimethyl-6-carboxythiochroman and 252 mg (2.52 mmol) of triethylamine in 15 ml of chloroform was stirred at room temperature for 0.5 hours and then treated with 481 mg (1.26 mmol) of bias(2-oxo-3-oxazolidinyl)phosphinic chloride. The reaction mixture was stirred for 0.5 h, treated with 209 mg (1.26 mmol) of ethyl 4-hydroxybenzoate and then stirred at room temperature for a further 12 hours. The reaction mixture was washed successively with dilute HCl and saturated sodium bicarbonate solutions. The organic layer was concentrated in-vacuo and the resultant crude product purified by flash chromatography (silica; 10% ethyl acetate in hexane) followed by reversed-phase high pressure liquid chromatography (Whatman Partisil M20 10/50 ODS-2; 10% water in acetonitrile) to give the title compound as a colorless oil. PMR (CDCl3): δ1.38 (6H, s), 1.42 (3H, t, J~7.0 Hz), 1.98 (2H, m), 3.07 (2H, m), 4.39 (2H, q, J~7.0 Hz), 7.20 (1H, d, J~9.0 Hz), 7.28 (2H, d, J~8.1 Hz), 7.82 (1H, dd, J~9.0, 1.8 Hz), 8.12 (2H, d, J~8.1 Hz), 8.17 (1H, d, J~1.8 Hz).

Workup

  1. stirringstirred at room temperature for a further 12 hours
  2. washThe reaction mixture was washed successively with dilute HCl and saturated sodium bicarbonate solutions
  3. concentrationThe organic layer was concentrated in-vacuo
  4. customthe resultant crude product purified by flash chromatography (silica; 10% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-7eb71e1c9640480d8da446c5e8ee93c1
Source dataset
uspto-grants-1991_05
Patent number
US05015658

Reaction notes

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