Benzyl Bromide → HCID 18687881, compound

HRID 1873208Notes

Reaction equation

HRID 1873208 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([C:8]2[C:17]3[C:18]4[CH:24]=[CH:23][CH:22]=[CH:21][C:19]=4[S:20][C:16]=3[C:15]([Br:25])=[C:14]3[C:9]=2[CH:10]=[CH:11][CH:12]=[CH:13]3)[CH:5]=[C:4]([OH:26])[C:3]=1[OH:27].C(=O)([O-])[O-].[K+].[K+].[CH2:34](Br)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1>CN(C=O)C>[Br:1][C:2]1[C:3]([O:27][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)=[C:4]([OH:26])[CH:5]=[C:6]([C:8]2[C:17]3[C:18]4[CH:24]=[CH:23][CH:22]=[CH:21][C:19]=4[S:20][C:16]=3[C:15]([Br:25])=[C:14]3[C:9]=2[CH:10]=[CH:11][CH:12]=[CH:13]3)[CH:7]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 18687808HCID 18687808, compound

Product 1

HCID 18687881HCID 18687881, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of 3-bromo-5-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-benzene-1,2-diol (0.390 g, 0.78 mmol) and potassium carbonate (0.108 g, 0.78 mmol) in DMF (4 mL) was stirred at 0 ° C. under a dry N2 atmosphere for 20 min. Benzyl bromide (0.093 mL, 0.78 mmol) was added dropwise to this mixture over a period of ten minutes. After the mixture was stirred at 0 ° C. for 6.5 h., the reaction mixture was quenched with aqueous hydrochloric acid to pH 1 and further diluted with water (60 mL) and aqueous mixture was extracted with methylene chloride (2×60 mL). The combined organic extracts were washed with water and dried with brine. Silica gel (5 mL) was added. Solvent was removed and the adsorbate was flash chromatographed (eluents: petroleum ether:methylene chloride 6:4 to petroleum ether:ethyl acetate 6:4) to provide a mixture (271 mg, 59%) of the title compound (87%) and 2-bromo-4-(6) -bromo-benzo[b]naphtho[2,3-d]thiophen- 11 -yl)-6-benzyloxy-phenol (13%). The mixture was used for next reaction without separation: NMR (CDCl3): δ8.35 (d, J=8 Hz, 1 H), 7.79 (d, J=8 Hz, 1 H), 7.72-7.33 (m, 9 H), 7.18 (d, J=2 Hz, 1 H), 7.17 (ddd, J=8, 7, 1 Hz, 1 H), 6.93 (d, J=2 Hz, 1H), 6.87 (d, J=8 Hz, 1 H), 5.71 (s, 1H), 5.32 (t, J=7 Hz,2 H).

Workup

  1. stirringAfter the mixture was stirred at 0 ° C. for 6.5 h.
  2. customthe reaction mixture was quenched with aqueous hydrochloric acid to pH 1
  3. additionfurther diluted with water (60 mL) and aqueous mixture
  4. extractionwas extracted with methylene chloride (2×60 mL)
  5. washThe combined organic extracts were washed with water
  6. dry with materialdried with brine
  7. additionSilica gel (5 mL) was added
  8. customSolvent was removed
  9. customchromatographed (eluents: petroleum ether:methylene chloride 6:4 to petroleum ether:ethyl acetate 6:4)

Sources & evidence

ORD record
ord-6a4ea6fa13374f6db61032bf3fd8c7f8
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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