Ethanol → 5-Amino-4-(3-bromo-phenylsulfanyl)-thiophene-2-carbonitrile

HRID 132077Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]([S:8]([C:10]2[CH:11]=[C:12]([C:18]#[N:19])[S:13][C:14]=2[N+:15]([O-])=O)=O)[CH:5]=[CH:6][CH:7]=1.CCO>[Fe].C(O)(=O)C>[NH2:15][C:14]1[S:13][C:12]([C:18]#[N:19])=[CH:11][C:10]=1[S:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([Br:1])[CH:3]=1

Participants

Conditions

Temperature: 50 °C

Procedure

4-(3-Bromo-benzenesulfinyl)-5-nitro-thiophene-2-carbonitrile (Example 25: step e; 5.20 g, 15.33 mmol) was dissolved into EtOH (45 mL) and acetic acid (5 mL). The reaction was heated to 50° C. and then iron (4.28 g, 76.69 mmol) was added and the reaction was allowed to heat with stirring overnight. The reaction mixture was filtered through celite which was washed with MeOH and EtOAc to ensure that the product does not remain on the celite. The filtrate was concentrated and then dissolved into EtOAC and washed with brine. The organic layer was dried (MgSO4) and concentrated. The crude reaction mixture was purified by flash column (20% EtOAc in Hexanes) resulting in the desired product as a brown oil (1.5 g, 32%). 1H-NMR (CDCl3): δ 7.38 (1H, s), 7.31-7.29 (1H, m), 7.18 (1H, t, J=1.8, Hz), 7.14 (1H, t, J=7.9 Hz), 6.99-6.96 (1H, m), 5.06 (2H, br s).

Workup

temperatureto heat
filtrationThe reaction mixture was filtered through celite which
washwas washed with MeOH and EtOAc
concentrationThe filtrate was concentrated
dissolutiondissolved into EtOAC
washwashed with brine
dry with materialThe organic layer was dried (MgSO4)
concentrationconcentrated
customThe crude reaction mixture
customwas purified by flash column (20% EtOAc in Hexanes)

Sources & evidence

ORD record: ord-47091a318d0b4f17941ef7382e658b5f
Source dataset: uspto-grants-2008_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07385066B2

Reaction notes

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