Ammonium Chloride → 4-[9-(t-Butyldimethylsilyloxy)-1-nonynyl]-4-hydroxy-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman

HRID 1792299Notes

Reaction equation

HRID 1792299 reaction equation
[Si:1]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]#[CH:17])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([Li])CCC.[CH3:23][O:24][C:25]1[CH:34]=[C:33]2[C:28]([C:29](=[O:44])[C:30]([C:36]3[CH:41]=[CH:40][C:39]([O:42][CH3:43])=[CH:38][CH:37]=3)([CH3:35])[CH2:31][S:32]2)=[CH:27][CH:26]=1.[Cl-].[NH4+]>O1CCCC1>[Si:1]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]#[C:17][C:29]1([OH:44])[C:28]2[C:33](=[CH:34][C:25]([O:24][CH3:23])=[CH:26][CH:27]=2)[S:32][CH2:31][C:30]1([C:36]1[CH:37]=[CH:38][C:39]([O:42][CH3:43])=[CH:40][CH:41]=1)[CH3:35])([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 109799547-Methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-oneHCID 140273559-(t-Butyldimethylsilyloxy)-1-nonyneHCID 178418339Butyllithium

Product 1

HCID 220331564-[9-(t-Butyldimethylsilyloxy)-1-nonynyl]-4-hydroxy-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochromanYield 99.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-20 °C

Procedure

To a solution of 9-(t-butyldimethylsilyloxy)-1-nonyne (12 g, 47.15 mmol) in dry tetrahydrofuran (150 ml) was added dropwise n-butyl lithium (25.5ml, 42.43 mmol, 1.66 mole/l in tetrahydrofuran) at −78° C., which was then stirred at −20° C. for 1 hour. Then, to this reaction mixture was added 7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-one (3 g, 9.54 mmol) dissolved in tetrahydrofuran at the same temperature for 30 minutes, and the resulting mixture was stirred at −10° C. for 24 hours. After the reaction was completed, saturated ammonium chloride solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography (n-hexane:ethyl acetate=9:1) to stoichiometrically give the title compound (5.40 g) as a colorless oil.

Workup

  1. stirringthe resulting mixture was stirred at −10° C. for 24 hours
  2. extractionthe mixture was extracted with ethyl acetate
  3. dry with materialThe extract was dried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-387e02a14d2d4adaad47adce56c50edc
Source dataset
uspto-grants-2006_07
Patent number
US07074819B2

Reaction notes

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