Water → ethyl 10-[(3RS,4RS)-3-ethyl-7-hydroxy-3-(4-hydroxyphenyl)thiochroman-4-yl]-2-(7,7,8,8,8-pentafluorooctyl)decanoate

HRID 1267757Notes

Reaction equation

HRID 1267757 reaction equation
B(Br)(Br)Br.[CH2:5]([C:7]1([C:46]2[CH:51]=[CH:50][C:49]([O:52]C)=[CH:48][CH:47]=2)[CH:16]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH:25]([CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][C:37]([F:43])([F:42])[C:38]([F:41])([F:40])[F:39])[C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:15]2[C:10](=[CH:11][C:12]([O:44]C)=[CH:13][CH:14]=2)[S:9][CH2:8]1)[CH3:6].O>ClCCl>[CH2:5]([C:7]1([C:46]2[CH:51]=[CH:50][C:49]([OH:52])=[CH:48][CH:47]=2)[CH:16]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH:25]([CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][C:37]([F:43])([F:42])[C:38]([F:40])([F:39])[F:41])[C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:15]2[C:10](=[CH:11][C:12]([OH:44])=[CH:13][CH:14]=2)[S:9][CH2:8]1)[CH3:6]

Participants

5

Reactant 3

HCID 962WaterHCID 25134Boron tribromideHCID 18546256ethyl 10-[(3RS,4RS)-3-ethyl-7-methoxy-3-(4-methoxyphenyl)thiochroman-4-yl]-2-(7,7,8,8,8-pentafluorooctyl)decanoate

Product 1

HCID 18546284ethyl 10-[(3RS,4RS)-3-ethyl-7-hydroxy-3-(4-hydroxyphenyl)thiochroman-4-yl]-2-(7,7,8,8,8-pentafluorooctyl)decanoateYield 55%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
10 °C

Procedure

A solution of boron tribromide in dichloromethane (1.0 M, 8.82 ml, 8.82 mmol) was added dropwise to a solution of ethyl 10-[(3RS,4RS)-3-ethyl-7-methoxy-3-(4-methoxyphenyl)thiochroman-4-yl]-2-(7,7,8,8,8-pentafluorooctyl)decanoate (1.05 g, 1.47 mmol) in dichloromethane (15 ml) at −78° C. under argon atmosphere. The reaction mixture was warmed with stirring up to 10° C. over 3 hours. Water was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the resulting residue was dissolved in ethanol (5 ml) and mixed with concentrated sulfuric acid (1 drop), followed by heating under reflux for 12 hours. Water was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel flash column chromatography (eluent: hexane/ethyl acetate=2/1) to give ethyl 10-[(3RS,4RS)-3-ethyl-7-hydroxy-3-(4-hydroxyphenyl)thiochroman-4-yl]-2-(7,7,8,8,8-pentafluorooctyl)decanoate (550 mg, Yield 55%).

Workup

  1. temperatureThe reaction mixture was warmed
  2. extractionwas then extracted with ethyl acetate
  3. washThe organic layer was washed with water and saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationAfter distilling off the solvent
  6. dissolutionthe resulting residue was dissolved in ethanol (5 ml)
  7. additionmixed with concentrated sulfuric acid (1 drop)
  8. temperatureby heating
  9. temperatureunder reflux for 12 hours
  10. additionWater was added to the reaction mixture, which
  11. extractionwas then extracted with ethyl acetate
  12. washThe organic layer was washed with saturated aqueous sodium chloride
  13. dry with materialdried over anhydrous magnesium sulfate
  14. distillationAfter distilling off the solvent
  15. customthe residue was purified by silica gel flash column chromatography (eluent: hexane/ethyl acetate=2/1)

Sources & evidence

ORD record
ord-05f1788a4a7947d78c072d4d9d58ce1a
Source dataset
uspto-grants-2003_04
Patent number
US06552068B1

Reaction notes

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