Dimethylamine, hydrochloride → HCID 86729462, compound

HRID 712391Notes

Reaction equation

HRID 712391 reaction equation
Cl.[CH3:2][NH:3][CH3:4].C[Al](C)C.[CH2:9]([N:12]([CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH2:13][C:14](OC)=[O:15])[CH:10]=[CH2:11]>C1(C)C=CC=CC=1.C1COCC1>[CH2:9]([N:12]([CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH2:13][C:14]([N:3]([CH3:4])[CH3:2])=[O:15])[CH:10]=[CH2:11]

Participants

6

Reactant 3

HCID 10473Dimethylamine, hydrochlorideHCID 10798914Methyl 2-(allyl(benzyl)amino)acetateHCID 16682925Trimethylaluminum

Product 1

HCID 86729462HCID 86729462, compoundYield 83.7%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
20 °C

Procedure

To a solution of dimethylamine hydrochloride (2.08 g, 25.5 mmol, 8.0 eq) in anhydrous toluene (10 mL) at 5° C. under N2 was added trimethyl aluminum (1.0M in toluene, 25.5 mL, 25.5 mmol, 8.0 eq) dropwise over 1 h. The reaction mixture was heated to 20° C. and stirred for another 2 h. To a mixture of methyl 2-(allyl(benzyl)amino)acetate (0.70 g, 3.19 mmol, 1.0 eq) in anhydrous toluene (50 mL) and THF (15 mL) at 5° C. was added the above reaction mixture and the reaction mixture was heated at 70° C. for 48 h. Then the mixture was cooled to 0° C. and quenched with a small amount of water. The organic phase was separated from the mixture, and the water phase was extracted with EtOAc (10 mL×3). The combined organic phases were washed with brine, dried over anhydrous Na2SO4 and filtrated. The filtrate was concentrated in vacuo and the residue was chromatographed with a silica gel column (50:1 (v/v) CH2Cl2/CH3OH) to afford the title compound as colorless oil (0.62 g, 77%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 233.3 (M+1); 1H NMR (400 MHz, CDCl3) δ: 2.86 (3H, s), 2.94 (3H, s), 3.16 (2H, d, J=6.8 Hz), 3.24 (2H, s), 5.16 (2H, m), 5.86 (1H, m), 7.18-7.27 (5H, m) ppm.

Workup

  1. additionwas added the above reaction mixture
  2. temperaturethe reaction mixture was heated at 70° C. for 48 h
  3. temperatureThen the mixture was cooled to 0° C.
  4. customquenched with a small amount of water
  5. customThe organic phase was separated from the mixture
  6. extractionthe water phase was extracted with EtOAc (10 mL×3)
  7. washThe combined organic phases were washed with brine
  8. dry with materialdried over anhydrous Na2SO4
  9. filtrationfiltrated
  10. concentrationThe filtrate was concentrated in vacuo
  11. customthe residue was chromatographed with a silica gel column (50:1 (v/v) CH2Cl2/CH3OH)

Sources & evidence

ORD record
ord-438c7dcd9ff8472ab38b002f70fc991d
Source dataset
uspto-grants-2015_11
Patent number
US09181277B2

Reaction notes

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