Morpholine → 4-(Morpholinomethyl)-3-nitrobenzonitrile

HRID 659164Notes

Reaction equation

HRID 659164 reaction equation
Br[CH2:2][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][C:4]=1[N+:11]([O-:13])=[O:12].[NH:14]1[CH2:19][CH2:18][O:17][CH2:16][CH2:15]1.C(N(CC)CC)C>C(Cl)Cl>[O:17]1[CH2:18][CH2:19][N:14]([CH2:2][C:3]2[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][C:4]=2[N+:11]([O-:13])=[O:12])[CH2:15][CH2:16]1

Participants

5

Reactant 3

HCID 8083MorpholineHCID 8471TriethylamineHCID 219055094-(Bromomethyl)-3-nitrobenzonitrile

Product 1

HCID 666325634-(Morpholinomethyl)-3-nitrobenzonitrileYield 80%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 4-(bromomethyl)-3-nitrobenzonitrile (7.12 g, 29.55 mmol) and morpholine (3.09 g, 35.45 mmol) in CH2Cl2 (98 mL) was added triethylamine (8.97 g, 88.64 mmol) dropwise at 0° C. The mixture was stirred at room temperature for 1.5 h and evaporated to dryness under reduced pressure. The residue was diluted with water (40 mL) and extracted with CH2Cl2 (3×100 mL). The CH2Cl2 solution was washed with water (50 mL), dried over anhydrous Na2SO4, filtered and evaporated to dryness under reduced pressure. The residue was purified by MPLC on silica gel using a mixture of EtOAc and hexane as eluent to give 4-(morpholinomethyl)-3-nitrobenzonitrile (5.84 g, 80%) as a yellow solid. 1H NMR (400 MHz, CDCl3): δ 8.12 (s, 1H), 7.83 (br s, 2H), 3.84 (s, 2H), 3.67 (t, 4H, J=4.6 Hz), 2.45 (t, 4H, J=4.6 Hz).

Workup

  1. customevaporated to dryness under reduced pressure
  2. additionThe residue was diluted with water (40 mL)
  3. extractionextracted with CH2Cl2 (3×100 mL)
  4. washThe CH2Cl2 solution was washed with water (50 mL)
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationfiltered
  7. customevaporated to dryness under reduced pressure
  8. customThe residue was purified by MPLC on silica gel using
  9. additiona mixture of EtOAc and hexane as eluent

Sources & evidence

ORD record
ord-978f2cef2d2440d7a16e207f7aaf582d
Source dataset
uspto-grants-2011_12
Patent number
US08080568B1

Reaction notes

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