Water → N,N-Dimethyl-2-(7-nitro-2H-benzo[b][1,4]oxazin-4(3H)-yl)ethanamine

HRID 424474Notes

Reaction equation

HRID 424474 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[NH:12][CH2:11][CH2:10][O:9][C:8]=2[CH:13]=1)([O-:3])=[O:2].[H-].[Na+].Cl.Cl[CH2:18][CH2:19][N:20]([CH3:22])[CH3:21].O>CN(C=O)C>[CH3:21][N:20]([CH3:22])[CH2:19][CH2:18][N:12]1[CH2:11][CH2:10][O:9][C:8]2[CH:13]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=[CH:6][C:7]1=2

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 11636816N,N-Dimethylaminoethyl chloride hydrochlorideHCID 184161517-Nitro-3,4-dihydro-2H-1,4-benzoxazine

Product 1

HCID 66704389N,N-Dimethyl-2-(7-nitro-2H-benzo[b][1,4]oxazin-4(3H)-yl)ethanamineYield 63%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 7-nitro-3,4-dihydro-2H-benzo[b][1,4]oxazine (240 mg, 1.33 mmol) in DMF (10 mL) was treated with NaH (170 mg, 4.26 mmol, 60% wt in mineral oil) at 0° C., resulting in an orange mixture. The mixture was then treated with 2-chloro-N,N-dimethylethanamine hydrochloride (384 mg, 2.66 mmol), resulting in a dark red mixture. The reaction was stirred at room temperature for 1 hour. At this time, the reaction was then heated to 90° C. and stirred for another 45 minutes. The reaction was cooled to room temperature, water (15 mL) was added, and the reaction was extracted into EtOAc (2×12 mL). The combined organic layers were washed with brine (3×5 mL), dried (Na2SO4), filtered, and concentrated. The residue was subjected to flash chromatography on silica gel: CH2Cl2 followed by 5:95 (2M NH3 in MeOH):CH2Cl2 to give a yellow/orange solid (210 mg, 63%). 1H-NMR (DMSO-d6) δ 7.75 (dd, J=2.7, 9.0 Hz, 1H), 7.48 (d, J=2.7 Hz, 1H), 6.82 (d, J=9.0 Hz, 1H), 4.18 (t, J=4.5 Hz, 2H), 3.57-3.53 (m, 4H), 2.54-2.45 (m, 2H), 2.23 (s, 6H).

Workup

  1. customresulting in an orange mixture
  2. customresulting in a dark red mixture
  3. temperatureAt this time, the reaction was then heated to 90° C.
  4. stirringstirred for another 45 minutes
  5. temperatureThe reaction was cooled to room temperature
  6. extractionthe reaction was extracted into EtOAc (2×12 mL)
  7. washThe combined organic layers were washed with brine (3×5 mL)
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-02e5b64775f24a698f24e053384d3904
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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