Lawesson's reagent → 6-Fluoro-2-methyl-4,9-dihydro-3-thia-4,9-diazabenzo[f]azulene-10-thione

HRID 131345Notes

Reaction equation

HRID 131345 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:14][C:13](=O)[C:12]3[CH:11]=[C:10]([CH3:16])[S:9][C:8]=3[NH:7][C:6]=2[CH:17]=1.COC1C=CC(P2(=S)SP(=S)(C3C=CC(OC)=CC=3)[S:27]2)=CC=1>ClCCCl>[F:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:14][C:13](=[S:27])[C:12]3[CH:11]=[C:10]([CH3:16])[S:9][C:8]=3[NH:7][C:6]=2[CH:17]=1

Participants

4

Reactant 2

HCID 87949Lawesson's reagentHCID 58626001HCID 58626001, compound

Product 1

HCID 588606526-Fluoro-2-methyl-4,9-dihydro-3-thia-4,9-diazabenzo[f]azulene-10-thione

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
81.5 °C

Procedure

Add 6-fluoro-2-methyl-4,9-dihydro-3-thia-4,9-diaza-benzo[f]azulen-10-one (65.2 g, 0.263 mol) and 2,4-Bis-(4-methoxy-phenyl)-[1,3,2,4]dithiadiphosphetane 2,4-disulfide (Lawesson's Reagent, 63.7 g, 0.157 mol) to 1,2-dichloroethane (DCE, 3500 mL) with stirring. Heat to gentle reflux (80-83° C.) for 30 minutes, and then allow cooling to ambient temperature. Filter the product and rinse with DCE. Dry at 50-60° C. to give 61.9 (89%) the title compound: 1H NMR (400 MHz, DMSO-d6) δ 10.98 (bs, 1H), 8.87 (bs, 1H), 7.00 (m, 1H), 6.88 (s, 1H), 6.78(m, 1H), 6.56 (m, 1H), 2.22 (s, 3H). HRMS (ES) exact mass M+H calcd for C12H9FN2S2 265.0269; found 265.0276.

Workup

  1. temperatureHeat
  2. temperatureallow cooling to ambient temperature
  3. filtrationFilter the product
  4. washrinse with DCE
  5. customDry at 50-60° C.

Sources & evidence

ORD record
ord-6283afc170c549a6988cbdf5beb63d6f
Source dataset
uspto-grants-2008_06
Patent number
US07384934B2

Reaction notes

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