Acetic Anhydride → 2-Acetoxy-4-{4-[2-(4-Bromo-benzyl)-4,5-dimethyl-thiophene-3-carbonyl]-2-cyclopentyl-phenoxysulfonyl}-benzoic Acid

HRID 1067372Notes

Reaction equation

HRID 1067372 reaction equation
[Br:1][C:2]1[CH:42]=[CH:41][C:5]([CH2:6][C:7]2[S:8][C:9]([CH3:40])=[C:10]([CH3:39])[C:11]=2[C:12]([C:14]2[CH:33]=[CH:32][C:17]([O:18][S:19]([C:22]3[CH:30]=[CH:29][C:25]([C:26]([OH:28])=[O:27])=[C:24]([OH:31])[CH:23]=3)(=[O:21])=[O:20])=[C:16]([CH:34]3[CH2:38][CH2:37][CH2:36][CH2:35]3)[CH:15]=2)=[O:13])=[CH:4][CH:3]=1.[I-].[Mg+2].[I-].[C:46](OC(=O)C)(=[O:48])[CH3:47]>CCOCC>[C:46]([O:31][C:24]1[CH:23]=[C:22]([S:19]([O:18][C:17]2[CH:32]=[CH:33][C:14]([C:12]([C:11]3[C:10]([CH3:39])=[C:9]([CH3:40])[S:8][C:7]=3[CH2:6][C:5]3[CH:4]=[CH:3][C:2]([Br:1])=[CH:42][CH:41]=3)=[O:13])=[CH:15][C:16]=2[CH:34]2[CH2:35][CH2:36][CH2:37][CH2:38]2)(=[O:21])=[O:20])[CH:30]=[CH:29][C:25]=1[C:26]([OH:28])=[O:27])(=[O:48])[CH3:47]

Participants

5

Reactant 3

HCID 7918Acetic AnhydrideHCID 5462737Magnesium diiodideHCID 103052134-{4-[2-(4-Bromo-benzyl)-4,5-dimethyl-thiophene-3-carbonyl]-2-cyclopentyl-phenoxysulfonyl}-2-hydroxy-benzoic Acid

Product 1

HCID 234456562-Acetoxy-4-{4-[2-(4-Bromo-benzyl)-4,5-dimethyl-thiophene-3-carbonyl]-2-cyclopentyl-phenoxysulfonyl}-benzoic AcidYield 57%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

The tide compound was prepared according to the procedure in Example 22 using 4-{4-[2-(4-bromo-benzyl)-4,5-dimethyl-thiophene-3-carbonyl]-2-cyclopentyl-phenoxysulfonyl}-2-hydroxy-benzoic acid (0.211 g, 0.315 mmol), magnesium iodide (0.0876 g, 0.315 mmol) and acetic anhydride (2.5 mL) in ether. Purification on 2% H3PO4/MeOH treated silica gel, eluting with a 10 & 20% EtOAc/pet ether step gradient followed by crystallization from acetone/hexane gave 0.185 g (57%) of the tide compound as a white solid, mp 113-114° C. 1H NMR (DMSO-d6) δ1.27-1.34 (m, 2H), 1.51-1.58 (m, 2H), 1.63-1.78 (m, 4H), 1.80 (s, 3H), 2.25 (s, 3H), H), 2.95 (quintet, 1H), 3.86 (s, 2H), 6.97 (d, 2H), 7.24 (d, 1H), 7.38 (d, 2H) 7.52 (dd, 1H), 7.57 (d, 1H), 7.86 (d, 1H), 7.92 (dd, 1H), 8.16 (d, 1H) 13.8 (br s, 1H). mass spectrum (−ESI) m/z 709 (M−H). Anal. Calcd. for C34H31BrO8S2: C, 57.38; H, 4.39; N, 0.00. Found: C, 56.99; H, 4.38; N, 0.02.

Workup

  1. customThe tide compound was prepared
  2. customPurification on 2% H3PO4/MeOH
  3. additiontreated silica gel
  4. washeluting with a 10 & 20% EtOAc/pet ether step gradient
  5. customfollowed by crystallization from acetone/hexane

Sources & evidence

ORD record
ord-a14bd6d8513c47f18ebf5a7f32b84add
Source dataset
uspto-grants-2001_06
Patent number
US06248764B1

Reaction notes

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