Dimethylformamide → 7-Chloro-2-methyl-10-methylsulfanyl-4H-3-thia-4,9-diaza-benzo[f]azulene

HRID 131386Notes

Reaction equation

HRID 131386 reaction equation
[Cl:1][C:2]1[CH:17]=[CH:16][C:5]2[NH:6][C:7]3[S:8][C:9]([CH3:15])=[CH:10][C:11]=3[C:12](=[S:14])[NH:13][C:4]=2[CH:3]=1.[CH3:18]N(C=O)C.C(=O)([O-])[O-].[K+].[K+].IC>CC(OC)(C)C>[Cl:1][C:2]1[CH:17]=[CH:16][C:5]2[NH:6][C:7]3[S:8][C:9]([CH3:15])=[CH:10][C:11]=3[C:12]([S:14][CH3:18])=[N:13][C:4]=2[CH:3]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 597321217-Chloro-2-methyl-4,9-dihydro-3-thia-4,9-diaza-benzo[f]azulene-10-thione

Product 1

HCID 1360903747-Chloro-2-methyl-10-methylsulfanyl-4H-3-thia-4,9-diaza-benzo[f]azuleneYield 96.7%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

Stir 7-chloro-2-methyl-4,9-dihydro-3-thia-4,9-diaza-benzo[f]azulene-10-thione (59.1 g, 0.210 mol) and DMF (236.4 mL) under nitrogen for 15 minutes at ambient temperature. Add powdered potassium carbonate (61.1 g, 0.442 mol); stir 15 minutes at ambient temperature. Add iodomethane (26.2 mL, 0.421 mol) and stir 2.5 hours at ambient temperature. Add MTBE (591 mL) and stir 15 minutes at ambient temperature. Filter and rinse solids with MTBE (59.1 mL). Wash the organic filtrate with water (3×591 mL), then dry over sodium sulfate, filter and concentrate under reduced pressure to give 60.0 g (96.7%) of crude product. 1H NMR (500 MHz, DMSO-d6) δ 2.22 (s, 3H), 2.39 (s, 3H), 6.47 (d, 1H), 6.57 (d, 1H), 6.86 (d, 1H), 6.97(dd, 1H), 8.09 (bs, 1H). 13C NMR (100 MHz, DMSO-d6) δ 13.24, 14.70, 120.58, 120.62, 121.67, 125.64, 127.51, 127.52, 127.77, 141.65, 142.16, 153.99, 165.48.

Workup

  1. filtrationFilter
  2. washrinse solids with MTBE (59.1 mL)
  3. washWash the organic filtrate with water (3×591 mL)
  4. dry with materialdry over sodium sulfate
  5. filtrationfilter
  6. concentrationconcentrate under reduced pressure

Sources & evidence

ORD record
ord-164f807d1e4a49b1a9f3100890ce353b
Source dataset
uspto-grants-2008_06
Patent number
US07384934B2

Reaction notes

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