N-Methylethylenediamine → 2-(3-Bromo-2-methylphenyl)-9-((2-(trimethylsilyl)ethoxy)methyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-1-one

HRID 1918829Notes

Reaction equation

HRID 1918829 reaction equation
[CH3:1][Si:2]([CH3:22])([CH3:21])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:9]2[CH2:16][CH2:17][NH:18][C:19](=[O:20])[C:8]1=2.[Br:23][C:24]1[CH:29]=[CH:28][CH:27]=[C:26](Br)[C:25]=1[CH3:31].C(=O)([O-])[O-].[Cs+].[Cs+].CNCCN>[Cu](I)I.O1CCOCC1>[Br:23][C:24]1[C:25]([CH3:31])=[C:26]([N:18]2[CH2:17][CH2:16][C:9]3[C:10]4[C:15](=[CH:14][CH:13]=[CH:12][CH:11]=4)[N:7]([CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:22])([CH3:21])[CH3:1])[C:8]=3[C:19]2=[O:20])[CH:27]=[CH:28][CH:29]=1

Participants

7

Reactant 4

HCID 8014N-MethylethylenediamineHCID 10796Cesium carbonateHCID 346812,6-DibromotolueneHCID 10358416HCID 10358416, compound

Product 1

HCID 580436472-(3-Bromo-2-methylphenyl)-9-((2-(trimethylsilyl)ethoxy)methyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-1-oneYield 41%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A 100-mL single-neck round-bottomed flask equipped with a magnetic stirrer and nitrogen inlet was charged with 117a (400 mg, 1.27 mmol), 2,6-dibromotoluene (633 mg, 2.53 mmol), cesium carbonate (828 mg, 2.54 mmol), N-methylethylenediamine (112 mg, 1.27 mmol) and 1,4-dioxane (20 mL). After bubbling nitrogen through the resulting suspension for 30 min, copper iodide (121 mg, 2.54 mmol) was added. A reflux condenser was attached to the flask, and the reaction mixture was heated at 100° C. for 16 h. After this time, the mixture was cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by flash column to afford 117b in 41% yield (251 mg) as a yellow oil: 1H NMR (500 MHz, CDCl3) d 7.71 (d, 1H, J=8.0 Hz), 7.68 (d, 1H, J=8.0 Hz), 7.63 (d, 1H, J=8.0 Hz), 7.47 (t, 1H, J=8.0 Hz), 7.32-7.28 (m, 2H), 7.21 (t, 1H, J=8.0 Hz), 6.13 (s, 2H), 4.15 (m, 1H), 3.93 (m, 1H), 3.69 (m, 2H), 3.29 (m, 2H), 2.45 (s, 3H), 0.95 (t, 2H, J=8.0 Hz), −0.07 (s, 9H).

Workup

  1. customA 100-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. concentrationThe filtrate was concentrated under reduced pressure
  7. customthe resulting residue was purified by flash column

Sources & evidence

ORD record
ord-e74d71a0508246b4a8d268f683b23b01
Source dataset
uspto-grants-2013_12
Patent number
US08618107B2

Reaction notes

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