Hydrochloric Acid → (Z)-2-amino-6-(prop-1-enyl)benzonitrile

HRID 471601Notes

Reaction equation

Cl.[N+:2]([C:5]1[CH:12]=[CH:11][CH:10]=[C:9](/[CH:13]=[CH:14]\[CH3:15])[C:6]=1[C:7]#[N:8])([O-])=O.[OH-].[Na+]>CO.O1CCOCC1.[Fe]>[NH2:2][C:5]1[CH:12]=[CH:11][CH:10]=[C:9](/[CH:13]=[CH:14]\[CH3:15])[C:6]=1[C:7]#[N:8]

Participants

Conditions

Temperature: 0 °C

Procedure

Concentrated HCl (1.54 mL) was added to a suspension of (Z)-2-nitro-6-(prop-1-enyl)benzonitrile (Example 3c) (0.35 g, 1.86 mmol) in MeOH (30 mL) and 1,4-dioxane (15 mL) at room temperature, followed by portion wise addition of iron powder (0.73 g, 13.0 mmol). The obtained mixture was heated at refluxed for 2.5 h, cooled to 0° C. and the pH was adjusted to pH˜10 with aqueous 50% solution of NaOH. The mixture was extracted with EtOAc (3×50 mL), the combined extract was dried with MgSO4, filtered and concentrated. The residue was purified by chromatography on silica gel eluting with gradient 0% to 100% DCM in hexanes, to give 0.24 g (80%) of (Z)-2-amino-6-(prop-1-enyl)benzonitrile as a yellow oil. 1H NMR (400 MHz, DMSO-d6) δ 7.24-7.30 (m, 1H), 6.68 (d, J=8.4 Hz, 1H), 6.55 (d, J=7.2 Hz, 1H), 6.42-6.48 (m, 1H), 5.98 (broad s, 2H), 5.89-5.97 (m, 1H), 1.74-1.78 (m, 3H). MS 159 (MH+).

Workup

temperatureThe obtained mixture was heated
temperatureat refluxed for 2.5 h
extractionThe mixture was extracted with EtOAc (3×50 mL)
extractionthe combined extract
dry with materialwas dried with MgSO4
filtrationfiltered
concentrationconcentrated
customThe residue was purified by chromatography on silica gel eluting with gradient 0% to 100% DCM in hexanes

Sources & evidence

ORD record: ord-50aaece1d37d453eb360786b9cf43b4b
Source dataset: uspto-grants-2014_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08633186B2

Reaction notes

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