Hydrochloric Acid → HCID 18687787, compound

HRID 1873203Notes

Reaction equation

HRID 1873203 reaction equation
[OH-:1].[Na+].[Br:3][C:4]1[CH:9]=[C:8]([C:10]2[C:19]3[C:20]4[CH:26]=[CH:25][CH:24]=[CH:23][C:21]=4[S:22][C:18]=3[C:17]([Br:27])=[C:16]3[C:11]=2[CH:12]=[CH:13][CH:14]=[CH:15]3)[CH:7]=[C:6]([Br:28])[C:5]=1[OH:29].[OH2:30].O.O.O.Cl[C:35](Cl)(Cl)[C:36]([CH3:39])(O)[CH3:37].Cl>O>[Br:28][C:6]1[CH:7]=[C:8]([C:10]2[C:19]3[C:20]4[CH:26]=[CH:25][CH:24]=[CH:23][C:21]=4[S:22][C:18]=3[C:17]([Br:27])=[C:16]3[C:11]=2[CH:12]=[CH:13][CH:14]=[CH:15]3)[CH:9]=[C:4]([Br:3])[C:5]=1[O:29][C:36]([CH3:39])([CH3:37])[C:35]([OH:30])=[O:1]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 108406542,6-Dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenolHCID 18430714HCID 18430714, compound

Product 1

HCID 18687787HCID 18687787, compoundYield 67.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Solid sodium hydroxide (0.682 g, 17.05 mmol) was added in three equal portions to a 0° C., stirred suspension of 2,6-dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d ]thiophen-11-yl)-phenol (0.800 g, 1.421 mmol), 1,1,1 -trichloro-2-methyl-2-propanol tetrahydrate (1.06 g, 4.263 mmol) in acteone (7.5 mL) over 3 h period. The resulting suspension was warmed to room temperature and stirred for 15 h. The reaction mixture was added to water, acidified with 10% aqueous HCl and extracted with ether. To the ether phase was added acid washed (2% phosphoric acid in methanol) silica gel and the solvent was removed. The adsorbate was flash chromatographed (2% phosphoric acid in methanol treated silica gel; eluent: gradient: 9:1 to 8:2 petroleum ether:ethyl acetate) to provide the title compound as an white solid (0.620g, 67%): mp 197-199° C.: NMR (DMSO-d6); δ13.00 (broad s, 1 H), 8.29 (d, J=8 Hz, 1 H), 8.09 (d, J=8 Hz, 1 H), 7.85 (s, 2 H), 7.81 (ddd, J=7, 6, 1 Hz, 1 H), 7.67-7.60 (m, 2 H), 7.52 (ddd, J=8, 7, 1 Hz, 1 H), 7.23 (ddd, J=8, 7, 1 Hz, 1 H), 6.60 (d, J=8 Hz, 1 H), 1.70 (s, 6 H); MS (-ESI): [M-H], 3 bromine isotope pattern, 645 (20%), 647 (60%) 649 (1000%) 651 (30%); Anal. Calc. for C26H17Br3O3S: C, 48.10, H, 2.64, N, 0.00. Found: C, 47.78, H, 2.76 , N, 0.31.

Workup

  1. stirringstirred for 15 h
  2. extractionextracted with ether
  3. additionTo the ether phase was added acid
  4. washwashed (2% phosphoric acid in methanol) silica gel
  5. customthe solvent was removed
  6. customchromatographed
  7. addition(2% phosphoric acid in methanol treated silica gel; eluent: gradient: 9:1 to 8:2 petroleum ether:ethyl acetate)

Sources & evidence

ORD record
ord-fa03c64e9a484975af4da1e26a07009c
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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