Hydrochloric Acid → HCID 9801802, compound

HRID 1278797Notes

Reaction equation

HRID 1278797 reaction equation
I[C:2]1[C:11]2[S:12][C:13]([CH3:16])=[C:14]([CH3:15])[C:10]=2[C:9]([C:17]2[CH:22]=[CH:21][C:20]([O:23]S(C)(=O)=O)=[CH:19][CH:18]=2)=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[CH:7]2.[C:28]1([SH:34])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.[OH-].[Na+].Cl>CN(C)C=O.O>[CH3:16][C:13]1[S:12][C:11]2[C:2]([S:34][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)=[C:3]3[C:8](=[C:9]([C:17]4[CH:18]=[CH:19][C:20]([OH:23])=[CH:21][CH:22]=4)[C:10]=2[C:14]=1[CH3:15])[CH:7]=[CH:6][CH:5]=[CH:4]3

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7969ThiophenolHCID 14798Sodium HydroxideHCID 9914226HCID 9914226, compound

Product 1

HCID 9801802HCID 9801802, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
155 °C

Procedure

To a stirred suspension of methanesulfonic acid 4-(9-iodo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenyl ester (0.620 g, 1.22 mmol), and copper I oxide (0.192 g, 1.34 mmol) in anhydrous N,N-dimethylformamide (10 mL) was added thiophenol (0.270 mL, 2.68 mmol) and finely ground sodium hydroxide (0.107 g, 2.68 mmol) under a dry argon atmosphere. The vessel was sealed and heated at 155° C. for 9.5 hours. After stirring at ambient temperature for about 8 hours the reaction mixture was poured into water, acidified with hydrochloric acid and the organics were extracted into ether. The extracts were combined, filtered, washed with water and concentrated. The yellow solid residue was dissolved in dioxane (8 mL) and a 2.5 N soduim hydroxide solution (4.5 mL) was added. The vial was sealed and heated at 102° C. When the reaction was done (as indicated by thin layer chromatography) the mixture was cooled to room temperature, diluted with water, and acidified with hydrochloric acid. The organics were extracted with ether, combined with silica gel and the solvents were removed. The adsorbate was flash chromatographed (gradient 90/10-85/15 petroleum ether/ethyl acetate) and the solvents were chased with benzene and petroleum ether to give the tide compound as a white solid (0.426 g, 85%): NMR (DMSO-d6); δ 9.70 (s, 1H, OH), 8.40 (d, J=8 Hz, 1H), 7.56-7.51 (m, 2H), 7.44-7.40 (m, 1H), 7.25-7.12 (m, 5H), 7.02 (d, J=7 Hz, 2H), 6.93 (d, J=9 Hz, 2H), 3.67 (s, 3H), 1.62 (s, 3H); MS(EI): [M+] 412 (100%); Anal. calc. for C26H20OS2: C, 75.69, H, 4.89, N, 0.00. Found C, 74.98, H, 4.86, N, 0.13.

Workup

  1. customThe vessel was sealed
  2. extractionthe organics were extracted into ether
  3. filtrationfiltered
  4. washwashed with water
  5. concentrationconcentrated
  6. dissolutionThe yellow solid residue was dissolved in dioxane (8 mL)
  7. additiona 2.5 N soduim hydroxide solution (4.5 mL) was added
  8. customThe vial was sealed
  9. temperatureheated at 102° C
  10. temperaturewas cooled to room temperature
  11. additiondiluted with water
  12. extractionThe organics were extracted with ether
  13. customthe solvents were removed
  14. customchromatographed (gradient 90/10-85/15 petroleum ether/ethyl acetate)

Sources & evidence

ORD record
ord-dfdfbedf3bf84222a382d32bf950941f
Source dataset
uspto-grants-2002_09
Patent number
US06444670B2

Reaction notes

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