Stannous chloride dihydrate → 2-tert-Butyl-4H-3-thia-4,9-diaza-benzo[f]azulen-10-ylamine hydrochloride

HRID 131375Notes

Reaction equation

HRID 131375 reaction equation
[C:1]([C:5]1[S:9][C:8]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[N+:17]([O-])=O)=[C:7]([C:20]#[N:21])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].O.O.[Sn](Cl)[Cl:25]>Cl.C(O)C>[ClH:25].[C:1]([C:5]1[S:9][C:8]2[NH:10][C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=3[N:17]=[C:20]([NH2:21])[C:7]=2[CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 210935385-tert-Butyl-2-(2-nitro-phenylamino)-thiophene-3-carbonitrile

Product 1

HCID 1357977472-tert-Butyl-4H-3-thia-4,9-diaza-benzo[f]azulen-10-ylamine hydrochlorideYield 90%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent

Procedure

Add 5-tert-butyl-2-(2-nitro-phenylamino)-thiophene-3-carbonitrile (21.2 g, 70 mmol) to a solution of tin(II)chloride dihydrate (46.1 g, 209 mmol) in conc. HCl (200 mL) and ethanol (600 mL). Reflux the mixture for 2 hours. Concentrate the solution to 200 mL and add to water (1 L). Filter and wash with water then hexanes to obtain the title compound as an orange powder (19.4 g): 1H NMR (DMSO-d6) δ 1.27 (s, 9H), 6.86 (d, 1H), 6.89 (s, 1H), 6.95 (d, 1H), 7.03 (t, 1H), 7.11 (t, 1H), 8.69 (s, 1H), 9.11 (s, 1H), 9.52 (s, 1H), 10.88 (s, 1H); MS (APCI) m/z (rel intensity) 272 (100).

Workup

  1. temperatureReflux the mixture for 2 hours
  2. concentrationConcentrate the solution to 200 mL
  3. additionadd to water (1 L)
  4. filtrationFilter
  5. washwash with water

Sources & evidence

ORD record
ord-e7944825a9da4c3ab6013f61ff6e1ea5
Source dataset
uspto-grants-2008_06
Patent number
US07384934B2

Reaction notes

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