Propargyl bromide → HCID 15380030, compound

HRID 1735022Notes

Reaction equation

HRID 1735022 reaction equation
[CH2:1]1[N:12]2[C:13]3[C:3](=[CH:4][CH:5]=[CH:6][C:7]=3[C:8](=[O:18])[NH:9][C:10]3[CH:17]=[CH:16][CH:15]=[CH:14][C:11]=32)[CH2:2]1.[H-].[Na+].[CH2:21](Br)[C:22]#[CH:23].[OH-].[Na+]>CN(C)C=O>[CH2:23]([N:9]1[C:8](=[O:18])[C:7]2[CH:6]=[CH:5][CH:4]=[C:3]3[CH2:2][CH2:1][N:12]([C:13]=23)[C:11]2[CH:14]=[CH:15][CH:16]=[CH:17][C:10]1=2)[C:22]#[CH:21]

Participants

6

Reactant 4

HCID 7842Propargyl bromideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 15380028Dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepin-6-one

Product 1

HCID 15380030HCID 15380030, compoundYield 19.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture prepared from 1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]-benzodiazepin-6-one (8.3 gm, 35 mmole) and sodium hydride (1.65 gm, 50% in oil, 1.0 eq) in dimethylformamide (DMF, 80 ml) was stirred at room temperature for 1.5 hours under N2. It was cooled to ~0° C. To this solution was charged propargyl bromide (16.5 gm, 80% in toluene, 3 eq) and the mixture was stirred for another 1.5 hours at 0° C. At the end of the reaction, the solution was poured into 10% NaOH (250 ml), and extracted with dichloromethane (DCM 1 l). The DCM solution was washed with NaOH (250 ml), water (2×300 ml) and brine (2×300 ml), then dried over MgSO4 and concentrated to an oil. Purification was accomplished by flash chromatography (SiO2 column, 200 gm, eluted with 1:1 hexane:DCM, 4 l). The material thus purified weighed 7.1 gm, (74%) as an oil. It turned to solid upon trituration with ether. A 3 gram portion of this material was recrystallized from ether (150 ml) to afford 1.9 gm of yellow crystals, m.p. 104°-105° C.

Workup

  1. temperatureIt was cooled to ~0° C
  2. stirringthe mixture was stirred for another 1.5 hours at 0° C
  3. customAt the end of the reaction
  4. extractionextracted with dichloromethane (DCM 1 l)
  5. washThe DCM solution was washed with NaOH (250 ml), water (2×300 ml) and brine (2×300 ml)
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated to an oil
  8. customPurification
  9. washwas accomplished by flash chromatography (SiO2 column, 200 gm, eluted with 1:1 hexane:DCM, 4 l)
  10. customThe material thus purified
  11. customA 3 gram portion of this material was recrystallized from ether (150 ml)

Sources & evidence

ORD record
ord-34f793892826478abcc8e2cac1d3d3d9
Source dataset
uspto-grants-1996_07
Patent number
US05536717

Reaction notes

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