(Dimethyl sulfide)trihydroboron → 4-[3-Nitro-5-(trifluoromethyl)benzyl]morpholine

HRID 1917902Notes

Reaction equation

HRID 1917902 reaction equation
[O:1]1[CH2:6][CH2:5][N:4]([C:7]([C:9]2[CH:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[C:11]([N+:19]([O-:21])=[O:20])[CH:10]=2)=O)[CH2:3][CH2:2]1.CSC.B>C1COCC1>[N+:19]([C:11]1[CH:10]=[C:9]([CH:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=1)[CH2:7][N:4]1[CH2:3][CH2:2][O:1][CH2:6][CH2:5]1)([O-:21])=[O:20]

Participants

4

Reactant 2

HCID 12423031(Dimethyl sulfide)trihydroboronHCID 219549894-(3-Nitro-5-trifluoromethyl-benzoyl)-morpholine

Product 1

HCID 219550054-[3-Nitro-5-(trifluoromethyl)benzyl]morpholineYield 27%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

In a round bottomed flask morpholino(3-nitro-5-(trifluoromethyl)phenyl)methanone (1.60 g, 5.25 mmol) was dissolved in 8 mL of anhydrous THF and cooled to 0 C. To this solution, a 2 M solution of Borane-dimethyl sulfide (10.5 mL, 21 mmol) in THF was added dropwise. The reaction was stirred overnight while warming to room temperature. The solution was then concentrated to an oil. This was partitioned between dichloromethane and water, then basified with 1 M sodium hydroxide solution, and extracted twice. The extracts were combined, washed with water and brine. They were then dried over magnesium sulfate, filtered and concentrated and purified by silica gel chromatography (using a 0-50% ethyl acetate/hexane gradient) to afford 4-(3-nitro-5-trifluoromethyl-benzyl)-morpholine (409 mg, 27% yield). 1H NMR (DMSO-d6) δ 8.46 (s, 1H), 8.4 (s, 1H), 8.15 (s, 1H), 3.7 (s, 2H), 3.6 (m, 4H), 2.4 (s, 4H).

Workup

  1. temperaturecooled to 0 C
  2. concentrationThe solution was then concentrated to an oil
  3. customThis was partitioned between dichloromethane and water
  4. extractionextracted twice
  5. washwashed with water and brine
  6. dry with materialThey were then dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by silica gel chromatography (

Sources & evidence

ORD record
ord-77904a3615904387929dd709390927e4
Source dataset
uspto-grants-2013_12
Patent number
US08618289B2

Reaction notes

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