N,N'-Dimethylethylenediamine → HCID 59375026, compound

HRID 872169Notes

Reaction equation

HRID 872169 reaction equation
[C:1]([C:5]1[CH:13]=[C:12]2[C:8]([CH2:9][NH:10][C:11]2=[O:14])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[Br:15][C:16]1[CH:21]=[CH:20][CH:19]=[C:18](Br)[C:17]=1[CH3:23].C(=O)([O-])[O-].[Cs+].[Cs+].CNCCNC>[Cu](I)I.O1CCOCC1>[Br:15][C:16]1[C:17]([CH3:23])=[C:18]([N:10]2[CH2:9][C:8]3[C:12](=[CH:13][C:5]([C:1]([CH3:4])([CH3:2])[CH3:3])=[CH:6][CH:7]=3)[C:11]2=[O:14])[CH:19]=[CH:20][CH:21]=1

Participants

7

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 10796Cesium carbonateHCID 346812,6-DibromotolueneHCID 58124096HCID 58124096, compound

Product 1

HCID 59375026HCID 59375026, compoundYield 66%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
105 °C

Procedure

A 250-mL single-neck round-bottomed flask equipped with a magnetic stirrer and nitrogen inlet was charged with 107c (775 mg, 4.10 mmol), 2,6-dibromotoluene (2.05 g, 8.19 mmol), cesium carbonate (2.67 g, 8.19 mmol), N,N′-dimethylethylenediamine (361 mg, 4.10 mmol) and 1,4-dioxane (15 mL). After bubbling nitrogen through the resulting suspension for 30 min, copper iodide (390 mg, 2.05 mmol) was added. A reflux condenser was attached to the flask, and the reaction mixture was heated at 105° C. for 16 h. After this time, the mixture was cooled to room temperature and filtered. The filtrate was diluted with ethyl acetate (100 mL) and water (50 mL), and the layers were separated. The aqueous layer was extracted with ethyl acetate (50 mL), and the combined organic layers were washed with brine (50 mL) and dried over sodium sulfate. The drying agent was removed by filtration. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by flash column chromatography (silica, 80:20 hexanes/ethyl acetate) to afford 107d in 66% yield (972 mg) as an amorphous off-white solid: mp 120-122° C.; 1H NMR (500 MHz, CDCl3) δ 7.99 (d, J=1.5 Hz, 1H), 7.68 (dd, J=8.0, 1.5 Hz, 1H), 7.60 (dd, J=8.0, 1.5 Hz, 1H), 7.46 (dd, J=8.0, 0.5 Hz, 1H), 7.22 (dd, J=8.0, 1.0 Hz, 1H), 7.14 (t, J=8.0 Hz, 1H), 4.67 (s, 2H), 2.31 (s, 3H), 1.40 (s, 9H); MS (ESI+) m/z 358.1 (M+H).

Workup

  1. customA 250-mL single-neck round-bottomed flask equipped with a magnetic stirrer and nitrogen inlet
  2. customAfter bubbling nitrogen through the resulting suspension for 30 min
  3. customA reflux condenser was attached to the flask
  4. temperatureAfter this time, the mixture was cooled to room temperature
  5. filtrationfiltered
  6. additionThe filtrate was diluted with ethyl acetate (100 mL) and water (50 mL)
  7. customthe layers were separated
  8. extractionThe aqueous layer was extracted with ethyl acetate (50 mL)
  9. washthe combined organic layers were washed with brine (50 mL)
  10. dry with materialdried over sodium sulfate
  11. customThe drying agent was removed by filtration
  12. concentrationThe filtrate was concentrated under reduced pressure
  13. customthe resulting residue was purified by flash column chromatography (silica, 80:20 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-185b0e9086194b61803b34eaed822ab6
Source dataset
uspto-grants-2015_03
Patent number
US08975260B2

Reaction notes

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