indium(III)bromide → HCID 67495813, compound

HRID 1952508Notes

Reaction equation

HRID 1952508 reaction equation
[Br:1][C:2]1[S:3][C:4]([C:13](=[O:29])[C:14]2[CH:19]=[CH:18][C:17]([C:20]#[C:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[C:16]([NH2:28])[CH:15]=2)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].[Br-].[Br-].[Br-].[In+3]>C1(C)C=CC=CC=1>[Br:1][C:2]1[S:3][C:4]([C:13]([C:14]2[CH:15]=[C:16]3[C:17]([CH:20]=[C:21]([C:22]4[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=4)[NH:28]3)=[CH:18][CH:19]=2)=[O:29])=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

4

Reactant 2

HCID 167051indium(III)bromideHCID 86664846HCID 86664846, compound

Product 1

HCID 67495813HCID 67495813, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 3 (1.37 g, 2.75 mmol) in EtOAc (50 mL) was added stannous chloride dihydrate (2.5 g, 11.08 mmol). The resulting mixture was refluxed for 1 hour under N2. The reaction mixture was poured into a saturated NaHCO3 solution (50 mL) and extracted with EtOAc (150 mL). The organic layer was washed with aqueous NaHCO3 solution (3×30 mL), dried over MgSO4, filtered, and then concentrated in vacuo. MPLC purification (Hex/EtOAc 4:1) of the residue gave the desired intermediate ethyl (2-bromo-5-(3-amino-4-(phenylethynyl)benzoyl)-thiophen-3-yl)acetate as a yellow foam (1.28 g, 100%). To a 100 mL flask containing freshly distilled toluene (20 mL) were added ethyl (2-bromo-5-(3-amino-4-(phenylethynyl)benzoyl)thiophen-3-yl)acetate (1.28 g, 2.70 mmol) and indium tribromide (500 mg, 1.41 mmol) under N2. The resulting mixture was refluxed for 12 hours. The solvent was removed in vacuo. MPLC purification (Hex:EtOAc/4:1) of the residue gave 4 as a yellow amorphous solid (454 mg, 56%). 1H NMR (400 MHz, CDCl3) δ 8.88 (s, 1H), 8.02 (s, 1H), 7.74 (d, J=7.6 Hz, 2H), 7.70-7.64 (m, 2H), 7.56 (s, 1H), 7.49 (t, J=7.6 Hz, 2H), 7.40 (t, J=7.6 Hz, 1H), 6.90 (s, 1H), 4.19 (q, J=7.2 Hz, 2H), 3.66 (s, 2H), and 1.27 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 187.62, 170.13, 144.16, 142.47, 136.69, 135.86, 135.05, 133.38, 131.84, 130.69, 129.31, 128.77, 128.70, 125.92, 121.81, 120.27, 113.73, 100.08, 61.67, 35.43, and 14.44.

Workup

  1. temperatureThe resulting mixture was refluxed for 12 hours
  2. customThe solvent was removed in vacuo
  3. customMPLC purification (Hex:EtOAc/4:1) of the residue

Sources & evidence

ORD record
ord-4cea83d6f582401593f26040f5977f43
Source dataset
uspto-grants-2013_03
Patent number
US08404728B2

Reaction notes

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