Formaldehyde → HCID 68742758, compound

HRID 1958753Notes

Reaction equation

[C:1]([C:9]1[CH:10]=[C:11]([CH:13]=[CH:14][CH:15]=1)[NH2:12])#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[CH3:16][O-].[Na+].C=O.[BH4-].[Na+]>CO>[CH3:16][NH:12][C:11]1[CH:13]=[CH:14][CH:15]=[C:9]([C:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])[CH:10]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 3-(oct-1-ynyl)aniline (1.34 g, 6.67 mmol) in MeOH (35 mL) was added NaOMe (25% wt. in MeOH, 7.7 mL), followed by paraformaldehyde (1.0 g, 33.3 mmol). The resulting mixture was refluxed 2 h under argon. After cooling to 0° C., NaBH4 (1.27 g, 33.4 mmol) was added and the mixture was refluxed for 90 min. The reaction mixture was then cooled to rt, quenched with ice and extracted with dichloromethane (50 mL+30 mL). The combined extracts were washed with H2O and brine and dried (Na2SO4). Flash chromatography (eluent: EtOAc/Hex=1:10 to 1:6) gave N-methyl-3-(oct-1-ynyl)aniline as a light yellow oil (920 mg, 64%). 1H NMR (400 MHz, CDCl3) δ 7.10 (t, 1H, J=7.8 Hz), 6.77 (d, 1H, J=7.2 Hz), 6.66 (s, 1H), 6.55 (d, 1H, J=8.4 Hz), 3.80 (s, br, 1H, NH), 2.84 (s, 3H), 2.40 (t, 3H, J=7.0 Hz), 1.61 (quint, 2H, J=7.4 Hz), 1.46 (quint, 2H, J=6.8 Hz), 1.38-1.25 (m, 4H), 0.92 (t, 3H, J=6.6 Hz).

Workup

temperatureThe resulting mixture was refluxed 2 h under argon
temperaturethe mixture was refluxed for 90 min
temperatureThe reaction mixture was then cooled to rt
customquenched with ice
extractionextracted with dichloromethane (50 mL+30 mL)
washThe combined extracts were washed with H2O and brine
dry with materialdried (Na2SO4)

Sources & evidence

ORD record: ord-331e27088e4a4e6f9b7e569cf0c4d4a6
Source dataset: uspto-grants-2013_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08410150B2

Reaction notes

Loading…