Isoamyl Nitrite → HCID 68938345, compound

HRID 2218753Notes

Reaction equation

HRID 2218753 reaction equation
N[C:2]1[S:11][C:10]2[C:9](=[O:12])[C:8]3[CH:13]=[CH:14][CH:15]=[CH:16][C:7]=3[CH2:6][CH2:5][C:4]=2[N:3]=1.N(OCCC(C)C)=O>CN(C=O)C>[N:3]1[C:4]2[CH2:5][CH2:6][C:7]3[CH:16]=[CH:15][CH:14]=[CH:13][C:8]=3[C:9](=[O:12])[C:10]=2[S:11][CH:2]=1

Participants

4

Reactant 2

HCID 8053Isoamyl NitriteHCID 59770014HCID 59770014, compound

Product 1

HCID 68938345HCID 68938345, compoundYield 52.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

To a room temperature solution of 2-amino-9,10-dihydro-3-thia-1-aza-benzo[f]azulen-4-one (5.31 g, 23.1 mmol) in DMF (50 mL) is added isoamyl nitrite (5.95 g, 50.8 mmol) and the reaction stirred for 30 min. The reaction mixture is heated to 80° C. for 2 h, and then cooled to room temperature. The solvent is removed under reduced pressure and ice-cold H2O (100 mL) is added. The aqueous layer is extracted with EtOAc (2×150 mL) and the combined organic layers are dried (MgSO4), filtered and the solvent removed under reduced pressure. The dark red oil is subjected to flash chromatography (silica gel, 75:25 Hex/EtOAc) to afford the slightly impure product as an orange-red solid. The product is further purified by trituration using Hex/EtOAc (90:10) to afford the title compound (2.59 g, 52%) as an orange solid: Rf 0.33 (1:1 EtOAc/Hex); mp 83-86° C.; 1H NMR (300 MHz, CDCl3) 8.89 (s, 1H), 7.96 (dd, J=1.2, 7.7 Hz, 1H), 7.50 (dt, J=1.4, 7.4 Hz, 1H), 7.37 (m, 1H), 7.30 (d, J=7.5 Hz, 1H), 3.36 (m, 2H), 3.24 (m, 2H); ESI MS m/z 216 [C12H9NOS+H]+. Anal. Calcd for C12H9NOS: C, 66.95; H, 4.21; N, 6.51.

Workup

  1. temperaturecooled to room temperature
  2. customThe solvent is removed under reduced pressure and ice-cold H2O (100 mL)
  3. additionis added
  4. extractionThe aqueous layer is extracted with EtOAc (2×150 mL)
  5. dry with materialthe combined organic layers are dried (MgSO4)
  6. filtrationfiltered
  7. customthe solvent removed under reduced pressure
  8. customto afford the slightly impure product as an orange-red solid
  9. customThe product is further purified by trituration

Sources & evidence

ORD record
ord-28a5db4193ea4e90824cf0df9fbe5ed6
Source dataset
uspto-grants-2008_08
Patent number
US07411072B2

Reaction notes

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