Potassium Hydroxide → N-[1-(6-Bromopyridin-2-yl)-1-methylethyl]-2,6-diethylaniline

HRID 634051Notes

Reaction equation

[Br:1][C:2]1[N:7]=[C:6]([C:8](=[N:10][C:11]2[C:16]([CH2:17][CH3:18])=[CH:15][CH:14]=[CH:13][C:12]=2[CH2:19][CH3:20])[CH3:9])[CH:5]=[CH:4][CH:3]=1.[CH3:21][Al](C)C.[OH-].[K+]>C1(C)C=CC=CC=1>[Br:1][C:2]1[N:7]=[C:6]([C:8]([NH:10][C:11]2[C:16]([CH2:17][CH3:18])=[CH:15][CH:14]=[CH:13][C:12]=2[CH2:19][CH3:20])([CH3:21])[CH3:9])[CH:5]=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 0 °C

Procedure

In argon atmosphere, to a mixture of 6.20 g (18.7 mmol) of N-[1-(6-bromopyridin-2-yl)ethylidene]-2,6-diethylaniline in 110 ml of dry toluene cooled to 0° C., a solution of 2.70 g (37.4 mmol) of AlMe3 in 40 ml of dry toluene was added dropwise for 10 min. The reaction mixture was slowly warmed to room temperature, stirred for 25 min at 40° C., and then cooled to 0° C. Further on, 150 ml of 5% KOH was added dropwise by vigorous stirring for 1 h at this temperature. The aqueous layer was separated, the organic layer was washed with 100 ml of water, 100 ml of brine, dried over Na2SO4, and then evaporated to dryness. Yield 6.40 g (98%) of yellow oil. Anal. Calc. for C18H23BrN2: C, 62.25; H, 6.68, N, 8.07. Found: C, 62.40; H, 6.82, N, 8.04. 1H NMR (CDCl3): δ 7.61 (dd, J=7.5 Hz, J=0.6 Hz, 1H, 5-H in pyridine), 7.51 (t, J=7.5 Hz, 1H, 4-H in pyridine), 7.34 (dd, J=7.5 Hz, J=0.6 Hz, 1H, 3-H in pyridine), 6.97-7.03 (m, 3H, 3, 4, 5-H in 2, 6-Et2C6H3), 3.97 (br.s, 1H, NH), 2.45 (q, J=7.5 Hz, 4H, CH2Me), 1.46 (s, 6H, Me2C), 1.11 (t, J=7.5 Hz, 6H, CH2Me).

Workup

temperatureThe reaction mixture was slowly warmed to room temperature
temperaturecooled to 0° C
stirringby vigorous stirring for 1 h at this temperature
customThe aqueous layer was separated
washthe organic layer was washed with 100 ml of water, 100 ml of brine
dry with materialdried over Na2SO4
customevaporated to dryness

Sources & evidence

ORD record: ord-7cc08fdb809e43feb40cb65fd848dc0f
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09321858B2

Reaction notes

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