Triethylamine → Ethyl 2-(2-bromo-5-(3-nitro-4-(phenylethynyl)benzoyl)thiophen-3-yl)acetate

HRID 1952506Notes

Reaction equation

HRID 1952506 reaction equation
[Br:1][C:2]1[S:3][C:4]([C:13](=[O:24])[C:14]2[CH:19]=[CH:18][C:17](I)=[C:16]([N+:21]([O-:23])=[O:22])[CH:15]=2)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].[C:25]1([C:31]#[CH:32])[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.C([O-])([O-])=O.[K+].[K+].CCN(CC)CC>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[Br:1][C:2]1[S:3][C:4]([C:13](=[O:24])[C:14]2[CH:19]=[CH:18][C:17]([C:32]#[C:31][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)=[C:16]([N+:21]([O-:23])=[O:22])[CH:15]=2)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 11430Potassium CarbonateHCID 67495826Ethyl 2-(2-bromo-5-(4-iodo-3-nitrobenzoyl)thiophen-3-yl)acetate

Product 1

HCID 67495694Ethyl 2-(2-bromo-5-(3-nitro-4-(phenylethynyl)benzoyl)thiophen-3-yl)acetateYield 72%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of 2 (2.00 g, 3.82 mmol), phenylacetylene (0.47 mL, 4.28 mmol), Pd(PPh3)2Cl2 (137 mg, 0.19 mmol), K2CO3 (542 mg, 3.92 mmol), and Et3N (0.55 mL, 3.95 mmol) in DMF (5 mL) was stirred for 24 h at room temperature. Water (10 mL) was added to the mixture and then extracted with Et2O (3×30 mL). The combined organic layer was washed with brine (3×15 mL), dried over MgSO4, and then concentrated in vacuo. MPLC purification (Hex:EtOAc/5:1) of the residue gave 3 as a yellow amorphous solid (1.37 g, 72%). 1H NMR (400 MHz, CDCl3) δ 8.52 (s, 1H), 8.04 (d, J=8.0 Hz, 1H), 7.84 (d, J=8.0 Hz, 1H), 7.63-7.61 (m, 2H), 7.52 (s, 1H), 7.43-7.37 (m, 3H), 4.19 (q, J=7.2 Hz, 2H), 3.67 (s, 2H), and 1.28 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 183.93, 169.64, 149.51, 142.13, 136.97, 136.36, 135.90, 135.24, 132.92, 132.52, 130.11, 128.82, 125.57, 124.25, 122.73, 122.06, 101.10, 84.72, 61.75, 35.26, and 14.42.

Workup

  1. extractionextracted with Et2O (3×30 mL)
  2. washThe combined organic layer was washed with brine (3×15 mL)
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customMPLC purification (Hex:EtOAc/5:1) of the residue

Sources & evidence

ORD record
ord-b4c185eb191b4bafb95d9e68a818d141
Source dataset
uspto-grants-2013_03
Patent number
US08404728B2

Reaction notes

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