Ammonium Chloride → Methyl E-4-[3-(3,5-difluoro-4-triisopropylsilanyloxybenzyl)-5-(2-hydroxyphenyl)pent-4-enyl]-benzoate

HRID 1921887Notes

Reaction equation

HRID 1921887 reaction equation
C([Li])CCC.[Br-].[OH:7][C:8]1[CH:33]=[CH:32][CH:31]=[CH:30][C:9]=1[CH2:10][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[F:34][C:35]1[CH:36]=[C:37]([CH:54]=[C:55]([F:68])[C:56]=1[O:57][Si:58]([CH:65]([CH3:67])[CH3:66])([CH:62]([CH3:64])[CH3:63])[CH:59]([CH3:61])[CH3:60])[CH2:38][CH:39]([CH:52]=O)[CH2:40][CH2:41][C:42]1[CH:51]=[CH:50][C:45]([C:46]([O:48][CH3:49])=[O:47])=[CH:44][CH:43]=1.[Cl-].[NH4+]>CCCCCC.C1COCC1>[F:34][C:35]1[CH:36]=[C:37]([CH:54]=[C:55]([F:68])[C:56]=1[O:57][Si:58]([CH:59]([CH3:61])[CH3:60])([CH:65]([CH3:67])[CH3:66])[CH:62]([CH3:63])[CH3:64])[CH2:38][CH:39](/[CH:52]=[CH:10]/[C:9]1[CH:30]=[CH:31][CH:32]=[CH:33][C:8]=1[OH:7])[CH2:40][CH2:41][C:42]1[CH:51]=[CH:50][C:45]([C:46]([O:48][CH3:49])=[O:47])=[CH:44][CH:43]=1

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 2724142(2-Hydroxybenzyl)triphenylphosphonium bromideHCID 57971950Methyl 4-[3-(3,5-difluoro-4-triisopropylsilanyloxybenzyl)-4-oxobutyl]benzoateHCID 178418339Butyllithium

Product 1

HCID 57971924Methyl E-4-[3-(3,5-difluoro-4-triisopropylsilanyloxybenzyl)-5-(2-hydroxyphenyl)pent-4-enyl]-benzoate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

7.49 ml (11.98 mmol) of a 1.6 M solution of n-butyllithium in hexane are slowly added to a solution of 2.38 g (5.14 mmol) of (2-hydroxybenzyl)triphenylphosphonium bromide in 50 ml of THF at 0° C. Then, at this temperature, 2.16 g (4.28 mmol) of methyl 4-[3-(3,5-difluoro-4-triisopropylsilanyloxybenzyl)-4-oxobutyl]benzoate are slowly metered in. The reaction solution is stirred at 0° C. for 2 hours and then mixed with 100 ml of saturated ammonium chloride solution and extracted with diethyl ether. The combined organic phases are washed with saturated sodium chloride solution and dried over sodium sulfate. After filtration, the solvent is concentrated to dryness. The resulting crude product is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 10:1). 2.37 g (90% of theory) of a colorless solid are obtained.

Workup

  1. extractionextracted with diethyl ether
  2. washThe combined organic phases are washed with saturated sodium chloride solution
  3. dry with materialdried over sodium sulfate
  4. filtrationAfter filtration
  5. concentrationthe solvent is concentrated to dryness
  6. customThe resulting crude product is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 10:1)
  7. custom2.37 g (90% of theory) of a colorless solid are obtained

Sources & evidence

ORD record
ord-2747e676aab84468842ee476c50906c2
Source dataset
uspto-grants-2012_05
Patent number
US08173704B2

Reaction notes

Loading…