Hydrochloric Acid → 5-Benzyloxy-3,4'-difluorostilbene

HRID 78882Notes

Reaction equation

HRID 78882 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.[F:17][C:18]1[CH:25]=[CH:24][C:21]([CH:22]=[CH2:23])=[CH:20][CH:19]=1.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>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([F:16])[CH:12]=[C:13]([CH:23]=[CH:22][C:21]2[CH:24]=[CH:25][C:18]([F:17])=[CH:19][CH:20]=2)[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 678834-FluorostyreneHCID 112545161-(Benzyloxy)-3-bromo-5-fluorobenzene

Product 1

HCID 687418575-Benzyloxy-3,4'-difluorostilbeneYield 91%

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-fluorostyrene (1.53 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 (2.93 g, 91%) was obtained. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.49-7.34 (m, 7H), 7.08-6.81 (m, 6H), 6.60 (dt, 1H), 5.08 (s, 2H); 19F NMR (CDCl3, 282 MHz) δ −31666.54 (t), −32136.54 (t). HRMS (EI+) found 322.1169 M+, calcd 322.1169 for C21H16F2O.

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-e2dcfa49427c468ab0bc95107cd43e26
Source dataset
uspto-grants-2014_09
Patent number
US08841477B2

Reaction notes

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