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

HRID 2236345Notes

Reaction equation

HRID 2236345 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-98875ee0694845e39c0be7c0bfc81326
Source dataset
uspto-grants-2010_05
Patent number
US07714161B2

Reaction notes

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