2,4,6-Trimethylaniline → N-(4-(but-3-en-1-yl)phenyl)-2,4,6-trimethylaniline

HRID 882213Notes

Reaction equation

HRID 882213 reaction equation
CC(C)([O-])C.[K+].Br[C:8]1[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][CH:16]=[CH2:17])=[CH:10][CH:9]=1.[CH3:18][C:19]1[CH:25]=[C:24]([CH3:26])[CH:23]=[C:22]([CH3:27])[C:20]=1[NH2:21]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH2:14]([C:11]1[CH:12]=[CH:13][C:8]([NH:21][C:20]2[C:22]([CH3:27])=[CH:23][C:24]([CH3:26])=[CH:25][C:19]=2[CH3:18])=[CH:9][CH:10]=1)[CH2:15][CH:16]=[CH2:17]

Participants

7

Reactant 3

HCID 69132,4,6-TrimethylanilineHCID 106085454-(4-Bromophenyl)-1-buteneHCID 23665647Potassium tert-butoxide

Product 1

HCID 117970022N-(4-(but-3-en-1-yl)phenyl)-2,4,6-trimethylanilineYield 80.5%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of Pd2(dba)3 (517.6 mg, 5 mol % Pd), BINAP (1.06 g, 1.5 eq of Pd), and potassium tert-butoxide (3.05 g, 27.13 mmol) in 80 ml toluene was prepared in a round-bottom flask in a glove box. The 4-(4-bromophenyl)-1-butene (5.00 g, 22.6 mmol) and 2,4,6-trimethylaniline (3.80 ml, 27.13 mmol) were added by syringe, and the reaction mixture was stirred at 80° C. oil bath for 12 h. The mixture was quenched with a saturated NaHCO3(aq) solution and then concentrated under reduced pressure. The crude product was purified by column chromatography (t-butyl methyl ether/heptane (v/v)=3/97, Rf=0.3) to afford N-(4-(but-3-en-1-yl)phenyl)-2,4,6-trimethylaniline (4.83 g, 76.7%). 1H NMR (300 MHz, CDCl3): δ 6.95 (m, 4H), 6.44 (s, 1H), 6.42 (s, 1H), 5.87 (m, 1H), 5.01 (m, 2H+NH), 2.60 (t, 2H), 2.30 (s, 1H), 2.17 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 144.7, 138.8, 135.6, 135.2 (2C), 134.8, 131.5, 129.4 (2C), 129.2 (2C), 114.8, 113.6 (2C), 36.1, 34.8, 21.1, 18.5 (2C). MS (EI): m/z: calc. for C19H23N: 265.18. found 265.18.

Workup

  1. customwas prepared in a round-bottom flask in a glove box
  2. customThe mixture was quenched with a saturated NaHCO3(aq) solution
  3. concentrationconcentrated under reduced pressure
  4. customThe crude product was purified by column chromatography (t-butyl methyl ether/heptane (v/v)=3/97, Rf=0.3)

Sources & evidence

ORD record
ord-80d8fa38e2e644afab72d792459dd64c
Source dataset
uspto-grants-2015_03
Patent number
US08993793B1

Reaction notes

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