Hydrochloric Acid → 4'-Acetoxy-5-benzyloxy-3-fluorostilbene

HRID 78884

Reaction equation

HRID 78884 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([F:16])[CH:12]=[C:13](Br)[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:17]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH:25]=[CH2:26])=[CH:23][CH:22]=1)(=[O:19])[CH3:18].CCN(CC)CC.Cl>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CCOC(C)=O>[C:17]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH:25]=[CH:26][C:13]2[CH:14]=[C:9]([O:8][CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH:10]=[C:11]([F:16])[CH:12]=2)=[CH:23][CH:22]=1)(=[O:19])[CH3:18]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 758214-Ethenylphenyl acetateHCID 112545161-(Benzyloxy)-3-bromo-5-fluorobenzene

Product 1

HCID 687420264'-Acetoxy-5-benzyloxy-3-fluorostilbeneYield 88%

Reagents, catalysts & solvents 4

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 5-benzyloxy-3-fluorophenyl bromide (2.81 g, 10 mmol), Pd(OAc)2 (0.067 g, 0.3 mmol), tri-o-tolylphosphine (0.18 g, 0.6 mmol), 4-acetoxystyrene (2.03 g, 12.5 mmol), and Et3N (1.26 g, 12.5 mmol) in 20 mL dry DMF was stirred at 100° C. for 24 hours under N2. The dark mixture was distributed between EtOAc and 1N HCl. The organic layer was separated and washed with water and brine, dried over Na2SO4, filtered, and evaporated. After flash column, the desired product (3.19 g, 88%) was obtained. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.51-7.34 (m, 7H), 7.11-6.82 (m, 6H), 6.60 (dt, 1H); 13C NMR (CDCl3, 75 MHz) δ 169.66, 165.64, 162.40, 160.47, 150.58, 140.07 (d), 136.59, 134.76, 129.41, 128.91, 128.41, 128.04 (d), 127.79 (d), 122.11, 109.36 (d), 105.86 (d), 101.91 (d), 70.57, 21.37; 19F NMR (CDCl3, 282 MHz) δ −31675.70 (t); HRMS (EI+) found 362.1302 M+, calcd 362.1318 for C23H19FO3.

Workup

  1. customThe organic layer was separated
  2. washwashed with water and brine
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. customevaporated

Sources & evidence

ORD record
ord-6671ef84d26e4bdab060dfa5e962ba4c
Source dataset
uspto-grants-2014_09
Patent number
US08841477B2

Linked notes

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