8-(t-Butyldimethylsilyloxy)-1-octyne → 4-[8-(t-Butyldimethylsilyloxy)-1-octynyl]-4-hydroxy-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman

HRID 1792348Notes

Reaction equation

HRID 1792348 reaction equation
[Si:1]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]#[CH:16])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([Li])CCC.[CH3:22][O:23][C:24]1[CH:33]=[C:32]2[C:27]([C:28](=[O:43])[C:29]([C:35]3[CH:40]=[CH:39][C:38]([O:41][CH3:42])=[CH:37][CH:36]=3)([CH3:34])[CH2:30][S:31]2)=[CH:26][CH:25]=1>O1CCCC1>[Si:1]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]#[C:16][C:28]1([OH:43])[C:27]2[C:32](=[CH:33][C:24]([O:23][CH3:22])=[CH:25][CH:26]=2)[S:31][CH2:30][C:29]1([C:35]1[CH:36]=[CH:37][C:38]([O:41][CH3:42])=[CH:39][CH:40]=1)[CH3:34])([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 104217908-(t-Butyldimethylsilyloxy)-1-octyneHCID 109799547-Methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-oneHCID 178418339Butyllithium

Product 1

HCID 220330184-[8-(t-Butyldimethylsilyloxy)-1-octynyl]-4-hydroxy-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochromanYield 870.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-10 °C

Procedure

8-(t-Butyldimethylsilyloxy)-1-octyne (12 g, 49.9 mmol) was dissolved in dry tetrahydrofuran (150 ml) under argon atmosphere and then cooled to −78C. 2.5M n-Butyllithium (18 ml, 44.9 mmol) was added dropwise thereto, and the mixture was warmed to −10° C. and stirred for 1 hour and then cooled to −78° C. 7-Methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-one (860 mg,2.9 mmol) was added portionwise and then warmed to room temperature and stirred for 1.5 hour. The mixture was quenched by water. The reaction solvent was evaporated off, then the residue was dissolved in ethyl acetate, which was washed with water. The organic solvent was dried over anhydrous magnesium sulfate and removed by evaporation under vacuum. This product was purified by column chromatography on silica gel, eluting with 10% ethyl acetate in n-hexane. After removal of the solvent, 14 g of the title compound was obtained as colorless oil. (yield: 99.3%)

Workup

  1. temperaturecooled to −78C
  2. temperaturecooled to −78° C
  3. temperaturewarmed to room temperature
  4. stirringstirred for 1.5 hour
  5. customThe mixture was quenched by water
  6. customThe reaction solvent was evaporated off
  7. dissolutionthe residue was dissolved in ethyl acetate
  8. washwhich was washed with water
  9. dry with materialThe organic solvent was dried over anhydrous magnesium sulfate
  10. customremoved by evaporation under vacuum
  11. customThis product was purified by column chromatography on silica gel
  12. washeluting with 10% ethyl acetate in n-hexane
  13. customAfter removal of the solvent

Sources & evidence

ORD record
ord-0687bd6360714687a6b4063ebd39624c
Source dataset
uspto-grants-2006_07
Patent number
US07074819B2

Reaction notes

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