Dimethylformamide → 4-[6-(2-Dimethylamino-ethylsulfanyl)-benzo[b]naphtho[2,3-d]thiophen-11-yl]-phenol

HRID 1873145Notes

Reaction equation

HRID 1873145 reaction equation
I[C:2]1[C:14]2[S:13][C:12]3[CH:15]=[CH:16][CH:17]=[CH:18][C:11]=3[C:10]=2[C:9]([C:19]2[CH:24]=[CH:23][C:22]([O:25]S(C)(=O)=O)=[CH:21][CH:20]=2)=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[CH:7]2.Cl.CN([CH:34]([SH:36])C)C.[OH-].[Na+].[CH3:39][N:40]([CH3:43])[CH:41]=O>>[CH3:39][N:40]([CH3:43])[CH2:41][CH2:34][S:36][C:2]1[C:14]2[S:13][C:12]3[CH:15]=[CH:16][CH:17]=[CH:18][C:11]=3[C:10]=2[C:9]([C:19]2[CH:20]=[CH:21][C:22]([OH:25])=[CH:23][CH:24]=2)=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[CH:7]2

Participants

5

Reactant 4

HCID 6228DimethylformamideHCID 14798Sodium HydroxideHCID 15481264Methanesulfonic acid 4-(6-Iodo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenyl esterHCID 22036395N,N-dimethylaminoethanethiol hydrochloride

Product 1

HCID 186877714-[6-(2-Dimethylamino-ethylsulfanyl)-benzo[b]naphtho[2,3-d]thiophen-11-yl]-phenolYield 87%

Conditions

Temperature
155 °C

Procedure

To a suspension of methanesulfonic acid 4-(6-iodo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenyl ester (1.00 g, 1.89 mmol), dimethylaminoethanethiol hydrochloride (0.614 g, 4.34 mmol, 2.3 eq) and copper I oxide (0.316 g, 8.69 mmol, 1.17 eq) in anhydrous N,N-dimethylformamide (24 mL) was added finely ground sodium hydroxide (0.348 g, 8.69 mmol, 4.6 eq) at room temperature in a pressure vessel. The vessel was flushed with argon, sealed and heated with stirring at 155° C. (oil bath) for 6 hours and at ambient temperature for 12 hours. The reaction mixture was poured into water (100 mL) and extracted with ether. The solid which remained as a suspension in the aqueous phase was filtered. The filtrate was extracted once more with ether. The extracts were combined and silica gel was added. The solvents were removed and the adsorbate was flash chromatographed (gradient 94/6-95/5) methylene chloride:isopropanol to give the title compound as a solid (0.707 g, 87%): NMR (DMSO-d6); δ 9.83 (s, 1H, OH), 8.65 (d, J=8 Hz, 1H), 7.98 (d, J=8 Hz, 1H), 7.71 (ddd, J=8, 7, 1 Hz, 1H), 7.61 (d, J=8 Hz, 1H), 7.50 (ddd, J=8, 7, 1 Hz, 1H), 7.43 (ddd, J=8, 7, 1 Hz, 1H), 7.21-7.05 (m, 3H), 7.08-7.04 (m, 2H), 6.73 (d, J=8 Hz, 1H), 3.35-3.27 (m,), 3.10 (t, J=6 Hz, 2H), 2.21-2.08 (broad singlet, 6H); MS(EI): [M+] 429.

Workup

  1. customThe vessel was flushed with argon
  2. customsealed
  3. temperatureheated
  4. waitat ambient temperature for 12 hours
  5. additionThe reaction mixture was poured into water (100 mL)
  6. extractionextracted with ether
  7. filtrationwas filtered
  8. extractionThe filtrate was extracted once more with ether
  9. additionsilica gel was added
  10. customThe solvents were removed
  11. customchromatographed (gradient 94/6-95/5) methylene chloride

Sources & evidence

ORD record
ord-9e9e5091fa314c07a3632e934423c860
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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