Iodine → HCID 9914226, compound

HRID 1278796Notes

Reaction equation

HRID 1278796 reaction equation
[CH3:1][C:2]1[S:6][C:5]2[CH:7]=[C:8]3[C:13](=[C:14]([C:15]4[CH:20]=[CH:19][C:18]([O:21][S:22]([CH3:25])(=[O:24])=[O:23])=[CH:17][CH:16]=4)[C:4]=2[C:3]=1[CH3:26])[CH:12]=[CH:11][CH:10]=[CH:9]3.S(=O)(=O)(O)O.II.[I:34](O)(=O)=O.S(=O)(O)[O-].[Na+]>O1CCCC1.C(O)(=O)C>[I:34][C:7]1[C:5]2[S:6][C:2]([CH3:1])=[C:3]([CH3:26])[C:4]=2[C:14]([C:15]2[CH:20]=[CH:19][C:18]([O:21][S:22]([CH3:25])(=[O:24])=[O:23])=[CH:17][CH:16]=2)=[C:13]2[C:8]=1[CH:9]=[CH:10][CH:11]=[CH:12]2

Participants

8

Reactant 5

HCID 807IodineHCID 1118Sulfuric AcidHCID 24345Iodic acidHCID 9800141HCID 9800141, compoundHCID 23665763Sodium Bisulfite

Product 1

HCID 9914226HCID 9914226, compoundYield 69.9%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methanesulfonic acid 4-(2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenyl ester (3.00 g, 7.84 mmol), in tetrahydrofuran (31.5 mL), 80% aqueous acetic acid (16 mL) and concentrated sulfuric acid (0.87 mL) was added iodine (1.59 g, 6.27 mmol, 0.8 eq) and iodic acid (0.414 g, 2.35 mmol, 0.9 eq) at room temperature. The mixture was stirred at room temperature for 12 days. The reaction mixture was poured into a dilute aqueous solution of sodium bisulfite (200 mL) and the organics were extracted with ether (2×200 mL). The extracts were combined and silica gel was added. The solvents were removed and the adsorbate was flash chromatographed (90/10 petroleum ether/ethyl acetate) without achieving purification. The recovered material was purified by high pressure liquid chromatography which gave recovered starting material (30.5%) and gave the title compound as a white solid (0.835 g, 30%): mp 212-213° C.; NMR (DMSO-d6); δ 8.09 (d, J=8 Hz, 1H), 7.64-7.58 (m, 1H), 7.54-7.42 (m, 5H), 7.43 (d, J=8 Hz, 1H), 3.47 (s, 3H, SO3CH3), 2.42 (s, 3H), 1.50 (s, 3H); MS(EI): [M+] 508 (100%); Anal. calc. for C21H17IO3S2, C, 49.61, H, 3.37, N, 0.00. Found: C, 49.44, H, 3.52, N, 0.03.

Workup

  1. extractionthe organics were extracted with ether (2×200 mL)
  2. additionsilica gel was added
  3. customThe solvents were removed
  4. customchromatographed (90/10 petroleum ether/ethyl acetate)
  5. custompurification
  6. customThe recovered material was purified by high pressure liquid chromatography which
  7. customgave
  8. customrecovered

Sources & evidence

ORD record
ord-de29ed204fb3471a958066e16200c874
Source dataset
uspto-grants-2002_09
Patent number
US06444670B2

Reaction notes

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