Lawesson's reagent → 7-bromo-4,5-dihydrospiro[benzo[b][1,4]diazepine-3,1'-cyclopropane]-2(1H)-thione

HRID 1485430Notes

Reaction equation

HRID 1485430 reaction equation
[Br:1][C:2]1[CH:15]=[CH:14][C:5]2[NH:6][C:7](=O)[C:8]3([CH2:11][NH:12][C:4]=2[CH:3]=1)[CH2:10][CH2:9]3.COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:25])=CC=1>O1CCCC1>[Br:1][C:2]1[CH:15]=[CH:14][C:5]2[NH:6][C:7](=[S:25])[C:8]3([CH2:11][NH:12][C:4]=2[CH:3]=1)[CH2:10][CH2:9]3

Participants

4

Reactant 2

HCID 87949Lawesson's reagentHCID 709789007-bromo-4,5-dihydrospiro[benzo[b][1,4]diazepine-3,1'-cyclopropan]-2(1H)-one

Product 1

HCID 867185037-bromo-4,5-dihydrospiro[benzo[b][1,4]diazepine-3,1'-cyclopropane]-2(1H)-thioneYield 44.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 7-bromo-4,5-dihydrospiro[benzo[b][1,4]diazepine-3,1′-cyclopropan]-2(1H)-one (267 mg, 1.0 mmol) and Lawesson's reagent (606 mg, 1.5 mmol) in tetrahydrofuran (15 mL) was heated to 80° C., and maintained at the same temperature for 1 hours. The mixture was concentrated. To the residue was added water (50 mL), extracted with ethyl acetate (50 mL). The organic phase was washed with water (50 mL*2), dried by sodium sulfate, filtered and concentrated to give a residue. The residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=6:1) to afford 7-bromo-4,5-dihydrospiro[benzo[b][1,4]diazepine-3,1′-cyclopropane]-2(1H)-thione (125 mg, 44%).

Workup

  1. temperaturemaintained at the same temperature for 1 hours
  2. concentrationThe mixture was concentrated
  3. additionTo the residue was added water (50 mL)
  4. extractionextracted with ethyl acetate (50 mL)
  5. washThe organic phase was washed with water (50 mL*2)
  6. dry with materialdried by sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give a residue
  10. customThe residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=6:1)

Sources & evidence

ORD record
ord-d62d78ea428c41fe80dacecc2a5d6beb
Source dataset
uspto-grants-2016_08
Patent number
US09422292B2

Reaction notes

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