Water → HCID 53363953, compound

HRID 449811Notes

Reaction equation

HRID 449811 reaction equation
[H-].[Na+].[NH2:3][C:4]1[CH:5]=[CH:6][C:7]([N:12]2[CH2:17][CH2:16][O:15][CH2:14][CH2:13]2)=[C:8]([CH:11]=1)[CH2:9][OH:10].[CH2:18](Cl)[CH:19]=[CH2:20].O>O1CCCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[CH2:20]([O:10][CH2:9][C:8]1[CH:11]=[C:4]([NH2:3])[CH:5]=[CH:6][C:7]=1[N:12]1[CH2:13][CH2:14][O:15][CH2:16][CH2:17]1)[CH:19]=[CH2:18]

Participants

8

Reactant 4

HCID 962WaterHCID 7850Allyl chlorideHCID 24758Sodium hydrideHCID 23136616(5-Amino-2-morpholinophenyl)methanol

Product 1

HCID 53363953HCID 53363953, compoundYield 50.3%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of NaH in cold tetrahydrofuran (80 mg/20 mL), 5-amino-2-morpholinobenzyl alcohol (400 mg, 2 mmol) was added. The mixture was stirred for 15 minutes then allyl chloride (150 mg, 2 mmol) and tetrabutylammonium iodide (37 mg, 5 mol %) were added. The resulting mixture was stirred at room temperature for 2 hours then at 60° C. overnight. After cooling to room temperature, water was added (200 μL) and the mixture stirred for 10 minutes then diluted with ethyl acetate. The organic phase was washed sequentially with 10% aqueous ammonium chloride and brine, dried over anhydrous Na2SO4, filtered and concentrated to give a yellow solid. The crude product was purified with 50% ethyl acetate in petroleum spirit to obtain 3-((allyloxy)methyl)-4-morpholinobenzenamine as a light orange oil (250 mg, 50% yield). 1H NMR (300 MHz, CDCl3) δ 6.95 (d, J=8.3 Hz, 1H), 6.82 (d, J=2.7 Hz, 1H), 6.61 (dd, J=8.2, 2.7 Hz, 1H), 6.10-5.90 (m, 1H), 5.34-5.28 (m, 1H), 5.23 (dd, J=10.5, 1.9 Hz, 1H), 4.57 (s, 2H), 4.07-4.05 (m, 2H), 3.80 (t, J=4.8 Hz, 4H), 3.55 (br s, 2H), 2.83 (t, J=4.6 Hz, 4H). LC-ESI-MS (method B) rt 5.91 min.; m/z 249.3 [M+H]+.

Workup

  1. additionwas added
  2. stirringThe resulting mixture was stirred at room temperature for 2 hours
  3. customat 60° C.
  4. customovernight
  5. stirringthe mixture stirred for 10 minutes
  6. washThe organic phase was washed sequentially with 10% aqueous ammonium chloride and brine
  7. dry with materialdried over anhydrous Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give a yellow solid
  11. customThe crude product was purified with 50% ethyl acetate in petroleum spirit

Sources & evidence

ORD record
ord-73b1d02e6fea46e3b16f98edc0b7ec23
Source dataset
uspto-grants-2013_07
Patent number
US08486941B2

Reaction notes

Loading…