Hydrochloric Acid → 4-(6-Methoxy-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenol

HRID 1873144Notes

Reaction equation

HRID 1873144 reaction equation
[CH3:1][OH:2].[H-].[Na+].I[C:6]1[C:18]2[S:17][C:16]3[CH:19]=[CH:20][CH:21]=[CH:22][C:15]=3[C:14]=2[C:13]([C:23]2[CH:28]=[CH:27][C:26]([O:29]S(C)(=O)=O)=[CH:25][CH:24]=2)=[C:12]2[C:7]=1[CH:8]=[CH:9][CH:10]=[CH:11]2.Cl>CN(C)C=O.O.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:1][O:2][C:6]1[C:18]2[S:17][C:16]3[CH:19]=[CH:20][CH:21]=[CH:22][C:15]=3[C:14]=2[C:13]([C:23]2[CH:24]=[CH:25][C:26]([OH:29])=[CH:27][CH:28]=2)=[C:12]2[C:7]=1[CH:8]=[CH:9][CH:10]=[CH:11]2

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 887MethanolHCID 24758Sodium hydrideHCID 15481264Methanesulfonic acid 4-(6-Iodo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenyl ester

Product 1

HCID 154812714-(6-Methoxy-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenolYield 90%

Reagents, catalysts & solvents 3

HCID 178419050HCID 178419050, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To cold (ice bath) anhydrous methanol (13.2 mL) was added sodium hydride (80% by weight suspension in mineral oil, 1.70 g, 56.6 mmol) in three portions. After stirring in the cold for 0.5 hours and at ambient temperature for 50 minutes copper II chloride (0.251 g, 1.87 mmol) and solution of methanesulfonic acid 4-(6-iodo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenyl ester (3.00 g, 5.66 mmol) in dry N,N-dimethylformamide (24 mL) were added. The reaction mixture was heated at reflux for approximately 3 hours, cooled to room temperature, diluted with water (400 mL), acidified with 10% hydrochloric acid and extracted with diethyl ether. The extracts were combined, silica gel was added and the solvent removed. The adsorbate was flash chromatographed (40/60 petroleum ether/methylene chloride) to provide the title compound as a white solid (1.82 g, 90%): mp 218-223° C. (dec); NMR (CDCl3); δ 8.27 (ddd, J=8, 1, 1 Hz, 1H), 7.80 (ddd, J=8, 1, 1 Hz, 1H), 7.65 (ddd, J=8, 1, 1 Hz, 1H), 7.57 (ddd, J=8, 7, 1 Hz, 1H), 7.40 (ddd, J=8, 7, 1 Hz, 1H), 7.36 (ddd, J=8, 7, 1 Hz, 1H), 7.30-7.26 (m, 2H), 7.13-7.07 (m, 3H), 6.85 (ddd, J=8, 1, 1 Hz, 1H), 4.98 (s, 1H), 4.21 (S, 3H); MS (EI): [M+], 356 (100%); Anal. Calc. for C23H16O2S: C, 77.50, H, 4.52, N, 0.00; Found C, 76.79, H, 4.61, N, 0.11.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for approximately 3 hours
  3. extractionextracted with diethyl ether
  4. additionsilica gel was added
  5. customthe solvent removed
  6. customchromatographed (40/60 petroleum ether/methylene chloride)

Sources & evidence

ORD record
ord-2de88f2293b444c49a177ec97c59593a
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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