Water → HCID 76066664, compound

HRID 1873206Notes

Reaction equation

HRID 1873206 reaction equation
[CH3:1][O:2][C:3](=[O:39])[C@H:4]([O:12][C:13]1[C:18]([Br:19])=[CH:17][C:16]([C:20]2[C:29]3[C:30]4[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=4[S:32][C:28]=3[C:27]([OH:37])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)=[CH:15][C:14]=1[Br:38])[CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C(=O)([O-])[O-].[CH3:44][O:45][C:46](=[O:49])[CH2:47]Br.O>CN(C)C=O>[CH3:1][O:2][C:3](=[O:39])[CH:4]([O:12][C:13]1[C:18]([Br:19])=[CH:17][C:16]([C:20]2[C:29]3[C:30]4[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=4[S:32][C:28]=3[C:27]([O:37][CH2:47][C:46]([O:45][CH3:44])=[O:49])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)=[CH:15][C:14]=1[Br:38])[CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

6

Reactant 4

HCID 962WaterHCID 19660Carbonate IonHCID 60984Methyl bromoacetateHCID 53737468HCID 53737468, compound

Product 1

HCID 76066664HCID 76066664, compoundYield 74.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of (R)-2-[2,6-dibromo-4-(6-hydroxy-benzo[b]naphtho[2,3-d ]thiophen-11-yl)-phenoxy]-3-phenyl-propionic acid methyl ester (0.60 g, 0.906 mmol) in anhydrous N,N-dimethylformamide was added potassuim carbonate (0.376 g, 2.72 mmol, 3 eq) and methylbromoacetate (0.26 mL, 2.72 mmol, 3 eq) at room temperature under a dry nitrogen atmosphere. After stirring for 24 hours the reaction mixture was combined with water (60 mL) the organics were extracted with diethyl ether (2×100 mL). The extracts were combined and washed with water (2×100 mL) and brine (100 mL). Silica gel was added and the solvents removed. The adsorbate was twice flash chromatographed (eluent 88/12 petroleum ether/ethyl acetate and 85/15 ethyl ether/ethyl acetate) to provide the title compound as a white solid (0.493 g, 73%): NMR (CDCl3); δ8.38 (d, J=8 Hz, 1 H), 7.81 (d, J =Hz, 1 H), 7.64-7.59 (m, 3 H), 7.55 (d, J=8 Hz, 1 H), 7.48 (ddd, J=8, 7, 1 Hz, 1 H), 7.43-7.26 (m, 6 H), 7.16 (ddd, J=8,7,1 Hz, 1 H), 6.79 (d, J=8 Hz, 1 H), 5.25 (dd, J=8, 6 Hz, 1 H), 4.94 (s, 2 H), 3.92 (s, 3 H), 3.76 (s, 3 H), 3.57 (septet, J=7 Hz, 2 H); MS (EI): [M+], 2 bromine isotope pattern, 732 (1.8%), 734 (4%), 736 (0.8%); Anal. Calc. for C35H26Br2O6S:, 57.24, H, 3.57, N, 0.00. Found: C, 57.01, H, 3.42, N, -0.07.

Workup

  1. extractionorganics were extracted with diethyl ether (2×100 mL)
  2. washwashed with water (2×100 mL) and brine (100 mL)
  3. additionSilica gel was added
  4. customthe solvents removed
  5. customchromatographed (eluent 88/12 petroleum ether/ethyl acetate and 85/15 ethyl ether/ethyl acetate)

Sources & evidence

ORD record
ord-4453b1d9bd224d7c8abb8379ce512637
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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