p-Toluenesulfonic acid → N-[1-(6-Bromopyridin-2-yl)ethylidene]-2,6-diethylaniline

HRID 634050Notes

Reaction equation

HRID 634050 reaction equation
[Br:1][C:2]1[N:7]=[C:6]([C:8](=O)[CH3:9])[CH:5]=[CH:4][CH:3]=1.[CH2:11]([C:13]1[CH:19]=[CH:18][CH:17]=[C:16]([CH2:20][CH3:21])[C:14]=1[NH2:15])[CH3:12].CC1C=CC(S(O)(=O)=O)=CC=1.[Cl-].[Cl-].[Ca+2]>C1(C)C=CC=CC=1>[Br:1][C:2]1[N:7]=[C:6]([C:8](=[N:15][C:14]2[C:16]([CH2:20][CH3:21])=[CH:17][CH:18]=[CH:19][C:13]=2[CH2:11][CH3:12])[CH3:9])[CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 113692,6-DiethylanilineHCID 5284359Calcium ChlorideHCID 112985782-Acetyl-6-bromopyridine

Product 1

HCID 117652848N-[1-(6-Bromopyridin-2-yl)ethylidene]-2,6-diethylaniline

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In argon atmosphere, a mixture of 6.00 g (30.0 mmol) of 1-(6-bromopyridin-2-yl)ethanone, 4.69 g (31.5 mmol) of 2,6-diethylaniline, 50 mg of TsOH, and 300 ml of toluene was refluxed for 2-3 h using a Soxhlet apparatus with an extraction thimble filled with anhydrous CaCl2. The reaction mixture was cooled to ambient temperature, passed through a short layer of silica gel 60 (40-63 um), and then evaporated to dryness. The crude product was recrystallized from 50 ml of methanol. Yield 6.20 g (63%) of a yellow crystalline solid. Anal. calc. for C17H19BrN2: C, 61.64; H, 5.78, N, 8.46. Found: C, 61.83; H, 5.88, N, 8.39. 1H NMR (CDCl3): δ 8.32 (dd, J=7.8 Hz, J=0.7 Hz, 1H, 3-H in pyridine), 7.65 (t, J=7.8 Hz, 1H, 4-H in pyridine), 7.57 (dd, J=7.8 Hz, J=0.7 Hz, 1H, 5-H in pyridine), 7.09-7.11 (m, 2H, 3, 5-H in 2, 6-Et2C6H3), 7.02 (m, 1H, 4-H in 2, 6-Et2C6H3), 2.33 (m, 4H, CH2Me), 2.16 (s, 3H, CH3C═N), 1.11 (t, J=7.6 Hz, 6H, CH2Me).

Workup

  1. temperaturewas refluxed for 2-3 h
  2. customevaporated to dryness
  3. customThe crude product was recrystallized from 50 ml of methanol

Sources & evidence

ORD record
ord-f2a5dd0dcbe943d9ac24ca6ea67432d8
Source dataset
uspto-grants-2016_04
Patent number
US09321858B2

Reaction notes

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