p-Toluenesulfonic acid → HCID 11175796, compound

HRID 634053Notes

Reaction equation

HRID 634053 reaction equation
[Br:1][C:2]1[N:7]=[C:6]([C:8](=O)[CH3:9])[CH:5]=[CH:4][CH:3]=1.[CH:11]([C:14]1[CH:20]=[CH:19][CH:18]=[C:17]([CH:21]([CH3:23])[CH3:22])[C:15]=1[NH2:16])([CH3:13])[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:16][C:15]2[C:17]([CH:21]([CH3:22])[CH3:23])=[CH:18][CH:19]=[CH:20][C:14]=2[CH:11]([CH3:13])[CH3:12])[CH3:9])[CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 32484DiisopropylanilineHCID 5284359Calcium ChlorideHCID 112985782-Acetyl-6-bromopyridine

Product 1

HCID 11175796HCID 11175796, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In argon atmosphere, a mixture of 3.70 g (18.50 mmol) of 1-(6-bromopyridin-2-yl)ethanone, 3.27 g (18.50 mmol) of 2,6-diisopropylaniline, 50 mg of TsOH, and 150 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 30 ml of methanol. Yield 3.63 g (56%) of yellow crystalline solid. Anal. calc. for C19H23BrN2: C, 63.51; H, 6.45, N, 7.80. Found: C, 63.44; H, 6.40, N, 7.93. 1H NMR (CDCl3): δ 8.31 (dd, J=7.7 Hz, J=0.6 Hz, 1H, 3-H in pyridine), 7.66 (t, J=7.7 Hz, 1H, 4-H in pyridine), 7.57 (dd, J=7.7 Hz, J=0.6 Hz, 1H, 5-H in pyridine), 7.14-7.16 (m, 2H, 3, 5-H in 2, 6-iPr2C6H3), 7.08 (m, 1H, 4-H in 2, 6-iPr2C6H3), 2.68 (sep, J=6.7 Hz, 2H, CHMe2), 2.17 (s, 3H, MeC═N), 1.13 (d, J=6.7 Hz, 6H, CHMe2), 1.12 (d, J=6.7 Hz, 6H, CHMe2).

Workup

  1. temperaturewas refluxed for 2-3 h
  2. customevaporated to dryness
  3. customThe crude product was recrystallized from 30 ml of methanol

Sources & evidence

ORD record
ord-4d433dd9f1fd43d79455c08837e8cfb2
Source dataset
uspto-grants-2016_04
Patent number
US09321858B2

Reaction notes

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