Aluminum(III) Chloride → Ethyl 2-(2-bromo-5-(4-iodo-3-nitrobenzoyl)thiophen-3-yl)acetate

HRID 1952489Notes

Reaction equation

HRID 1952489 reaction equation
[Br:1][C:2]1[S:3][CH:4]=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].[I:13][C:14]1[CH:22]=[CH:21][C:17]([C:18](Cl)=[O:19])=[CH:16][C:15]=1[N+:23]([O-:25])=[O:24].[Al+3].[Cl-].[Cl-].[Cl-]>C(Cl)Cl>[Br:1][C:2]1[S:3][C:4]([C:18](=[O:19])[C:17]2[CH:21]=[CH:22][C:14]([I:13])=[C:15]([N+:23]([O-:25])=[O:24])[CH:16]=2)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

5

Reactant 3

HCID 6451240Aluminum(III) ChlorideHCID 589329354-Iodo-3-nitrobenzoyl chlorideHCID 67496474Ethyl 2-(2-bromothiophen-3-yl)acetate

Product 1

HCID 67495826Ethyl 2-(2-bromo-5-(4-iodo-3-nitrobenzoyl)thiophen-3-yl)acetateYield 40%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of ethyl 2-(2-bromothiophen-3-yl)acetate (24.00 g, 96.32 mmol) and 4-iodo-3-nitrobenzoyl chloride (30.00 g, 96.32 mmol) in anhydrous CH2Cl2 (100 mL) was added AlCl3 (38.53 g, 288.96 mmol) over a period of 4 hours at room temperature. The resulting mixture was stirred for 2 days. The reaction mixture was slowly poured onto 200 g of ice and allowed to warm to room temperature. The aqueous phase was extracted with Et2O (4×30 mL), and the combined organic layer was dried over MgSO4, filtered, and then concentrated in vacuo. MPLC purification (Hex:EtOAc/4:1) of the residue gave 2 as a light yellow solid (20.00 g, 40%). 1H NMR (400 MHz, CDCl3) δ 8.26 (d, J=2.0 Hz, 1H), 8.21 (d, J=8.2 Hz, 1H), 7.69 (dd, J=2.0, 8.2 Hz, 1H), 7.48 (s, 1H), 4.19 (q, J=7.2 Hz, 2H), 3.66 (s, 2H), and 1.28 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 183.84, 169.61, 153.25, 142.83, 141.87, 138.32, 136.49, 135.94, 133.07, 125.69, 124.50, 91.79, 61.76, 35.20, and 14.42.

Workup

  1. extractionThe aqueous phase was extracted with Et2O (4×30 mL)
  2. dry with materialthe combined organic layer was dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customMPLC purification (Hex:EtOAc/4:1) of the residue

Sources & evidence

ORD record
ord-38b10cde7c0b4ec7a4fef6d41674b942
Source dataset
uspto-grants-2013_03
Patent number
US08404728B2

Reaction notes

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