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

HRID 1952499Notes

Reaction equation

HRID 1952499 reaction equation
[Br:1][C:2]1[S:3][C:4]([C:12](=[O:23])[C:13]2[CH:18]=[CH:17][C:16](I)=[C:15]([N+:20]([O-:22])=[O:21])[CH:14]=2)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH3:11])=[O:9].[C:24]1([C:30]#[CH:31])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=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:12](=[O:23])[C:13]2[CH:18]=[CH:17][C:16]([C:31]#[C:30][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)=[C:15]([N+:20]([O-:22])=[O:21])[CH:14]=2)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH3:11])=[O:9]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 11430Potassium CarbonateHCID 67496104Methyl 2-(2-bromo-5-(4-iodo-3-nitrobenzoyl)thiophen-3-yl)acetate

Product 1

HCID 67496466Methyl 2-(2-bromo-5-(3-nitro-4-(phenylethynyl)benzoyl)thiophen-3-yl)acetate

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of 2 (150 mg, 0.29 mmol), phenylacetylene (32 μL, 0.29 mmol), Pd(PPh3)2Cl2 (21 mg, 0.03 mmol), K2CO3 (42 mg, 0.29 mmol), and Et3N (40 μL, 0.29 mmol) in DMF (3 mL) was stirred for 24 hours at room temperature. Water (5 mL) was added to the mixture and then extracted with EtOAc (3×10 mL). The combined organic layer was washed with brine, dried over MgSO4, and concentrated in vacuo. MPLC purification (Hex:EtOAc/5:1) of the residue gave 3 as a solid foam (101 mg, 71%). 1H NMR (400 MHz, CDCl3) δ 8.54 (d, J=1.6 Hz, 1H), 8.06 (dd, J=1.6, 8.0 Hz, 1H), 7.86 (d, J=8.4 Hz, 1H), 7.64 (m, 2H), 7.52 (s, 1H), 7.42 (m, 3H), 3.75 (s, 3H), and 3.70 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 183.9, 170.1, 149.5, 142.2, 137.0, 136.3, 135.7, 135.3, 132.9, 132.5, 130.1, 128.8, 125.6, 124.3, 122.8, 122.1, 101.1, 84.7, 52.7, and 35.0.

Workup

  1. extractionextracted with EtOAc (3×10 mL)
  2. washThe combined organic layer was washed with brine
  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-18c15c1c195647bdb765a4f243b6e239
Source dataset
uspto-grants-2013_03
Patent number
US08404728B2

Reaction notes

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