1,2-Ethanediamine, N1,N1,N2-trimethyl- → HCID 86649360, compound

HRID 2401445Notes

Reaction equation

HRID 2401445 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH2:8])[N:3]=1.[CH3:9][N:10]([CH3:15])[CH2:11][CH2:12][NH:13][CH3:14].C(N(C(C)C)C(C)C)C>C(O)CC>[ClH:1].[ClH:1].[CH3:9][N:10]([CH3:15])[CH2:11][CH2:12][N:13]([CH3:14])[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH2:8])[N:3]=1

Participants

5

Reactant 3

HCID 673381,2-Ethanediamine, N1,N1,N2-trimethyl-HCID 81531DiisopropylethylamineHCID 2233322-Amino-4-chloropyrimidine

Product 1

HCID 86649360HCID 86649360, compoundYield 33.9%

Reagents, catalysts & solvents 1

HCID 10311-PropanolSolvent

Conditions

Temperature
200 °C

Procedure

A mixture of 4-chloropyrimidin-2-amine (CAS#3993-78-0, 0.100 g, 0.00077 mole), N1,N1,N2-trimethylethane-1,2-diamine (CAS#142-25-6, 0.082 g, 0.00077 mole), and N-ethyl-N-isopropylpropan-2-amine (0.94 mL, 0.00540 mole) in n-propanol (2 mL) was heated at 200° C. under microwave irradiation for 15 minutes. Volatiles were removed under reduced pressure and the residue was partitioned between ethyl acetate and saturated aqueous sodium carbonate. The organic layer was dried (MgSO4) and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by chromatography with silica gel, eluting with 97:3:0.5 to 95:5:1 DCM/MeOH/Et3N. Fractions containing product were combined and concentrated under reduced pressure. The residue was dissolved in ethyl acetate. This solution was dried (MgSO4) and filtered. The filtrate was concentrated under reduced pressure and the residue was dissolved in a minimum of methanol. This solution was acidified with a 4.0 M solution of HCl in dioxane. Ether was added to induce crystallization. Crystals were collected by filtration to provide N4-(2-(dimethylamino)ethyl)-N4-methylpyrimidine-2,4-diamine dihydrochloride (0.035 g, 15.8% yield). 1H NMR (300 MHz, CD3OD) δ ppm 3.00 (s, 6H), 3.25 (s, 3H), 3.46 (t, J=6 Hz, 2H), 4.14 (t, J=6 Hz, 2H), 6.40 (d, J=7 Hz, 1H), 7.75 (d, J=7 Hz, 1H). MS (DCl—NH3) m/z=196 (M+H)+.

Workup

  1. customVolatiles were removed under reduced pressure
  2. customthe residue was partitioned between ethyl acetate and saturated aqueous sodium carbonate
  3. dry with materialThe organic layer was dried (MgSO4)
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. customthe residue was purified by chromatography with silica gel
  7. washeluting with 97:3:0.5 to 95:5:1 DCM/MeOH/Et3N
  8. additionFractions containing product
  9. concentrationconcentrated under reduced pressure
  10. dissolutionThe residue was dissolved in ethyl acetate
  11. dry with materialThis solution was dried (MgSO4)
  12. filtrationfiltered
  13. concentrationThe filtrate was concentrated under reduced pressure
  14. dissolutionthe residue was dissolved in a minimum of methanol
  15. additionEther was added
  16. customcrystallization
  17. filtrationCrystals were collected by filtration

Sources & evidence

ORD record
ord-28998ebbe1b24bad957fc7f3ce3e8459
Source dataset
uspto-grants-2014_08
Patent number
US08796297B2

Reaction notes

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