Aluminium lithium hydride → 2-Methyl-N2-phenyl-N1-(2,4,6-trimethylphenyl)-1,2-propanediamine

HRID 333016Notes

Reaction equation

HRID 333016 reaction equation
Br[C:2]([CH3:16])([CH3:15])[C:3]([NH:5][C:6]1[C:11]([CH3:12])=[CH:10][C:9]([CH3:13])=[CH:8][C:7]=1[CH3:14])=O.[H-].[Al+3].[Li+].[H-].[H-].[H-]>C(COC)OC>[C:7]1([CH3:14])[CH:8]=[C:9]([CH3:13])[CH:10]=[C:11]([CH3:12])[C:6]=1[NH:5][CH2:3][C:2]([CH3:16])([NH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH3:15]

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 66899878HCID 66899878, compound

Product 1

HCID 1231805712-Methyl-N2-phenyl-N1-(2,4,6-trimethylphenyl)-1,2-propanediamine

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution of the amide (100 mg, 0.337 mmol) in dry dimethoxyethane (2 ml) was added lithium aluminum hydride (80 mg, 2.1 mmol), and the mixture was refluxed for 1 day. After cooling to room temperature, the reaction was quenched by adding H2O (0.08 ml), 15% aqueous NaOH (0.08 ml), and H2O (0.24 ml) successively. The white precipitation was filtered off and the filtrate was purified by column chromatography on silica (eluent: Hexane/Ethyl acetate=10/1) to give N1-mesityl-2-methyl-N2-phenylpropane-1,2-diamine as a pale yellow solid (54 mg, 0.192 mmol, Y=57%). The diamine (1.45 g, 5.14 mmol) was converted to the corresponding dihydrochloride salt (1.83 g, 5.14 mmol, 100%) by treating with HCl solution (4 M in dioxane). A mixture of this salt (500 mg, 1.4 mmol) and triethyl orthoformate (4.7 ml) was stirred at 130° C. for 5 min then cooled. After cooling to room temperature, the white precipitation was collected by filtration washing with large amount of diethyl ether and then with acetone to give the desired imidazolidinium chloride salt (367 mg, 1.12 mmol, Y=80%). 1H NMR (300 MHz, CDCl3): δ 9.76 (s, 1H), 7.65-7.62 (m, 2H), 7.49-7.47 (m, 3H), 6.92 (s, 2H), 4.13 (s, 2H), 2.39 (s, 6H), 2.27 (s, 3H), 1.69 (s, 6H). 13C NMR (75 MHz, CDCl3): δ 158.4, 140.2, 134.9, 132.3, 130.2, 130.0, 129.9, 129.8, 127.4, 68.6, 63.7, 26.7, 20.9, 18.1. IR: 3401 (m), 2975 (w), 1624 (s), 1592 (m), 1301 (w), 1263 (m), 1219 (m), 856 (w), 776 (w) cm−1. HRMS Calc'd for C20H25N2: 293.2018. Meas: 293.2021.

Workup

  1. temperaturethe mixture was refluxed for 1 day
  2. customthe reaction was quenched
  3. additionby adding H2O (0.08 ml), 15% aqueous NaOH (0.08 ml), and H2O (0.24 ml) successively
  4. customThe white precipitation
  5. filtrationwas filtered off
  6. customthe filtrate was purified by column chromatography on silica (eluent: Hexane/Ethyl acetate=10/1)

Sources & evidence

ORD record
ord-d0fe840834a34363a05fbcb279f22a1d
Source dataset
uspto-grants-2014_11
Patent number
US08877936B2

Reaction notes

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