Hydrochloric Acid → HCID 21954972, compound

HRID 2095102Notes

Reaction equation

HRID 2095102 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH3:8])[CH:7]=1.BrN1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[NH:38]1[CH2:43][CH2:42][O:41][CH2:40][CH2:39]1.Cl>C(Cl)(Cl)(Cl)Cl.C1COCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:7]=1)[CH2:8][N:38]1[CH2:43][CH2:42][O:41][CH2:40][CH2:39]1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 7187Benzoyl PeroxideHCID 8083MorpholineHCID 67184N-bromobutanimideHCID 949565-Fluoro-2-nitrotoluene

Product 1

HCID 21954972HCID 21954972, compoundYield 18.7%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 8028TetrahydrofuranSolvent

Procedure

5-Fluoro-2-nitrotoluene (1.55 g, 10 mmol), N-bromosuccinimide (1.82 g, 10 mmol), and benzoyl peroxide (0.1 g, 0.4 mmol) were dissolved in CCl4 (50 mL), heated at reflux, and irradiated with light (100 W bulb) for 4 hours. The reaction mixture was filtered and concentrated. The residue was dissolved in THF (50 mL). Morpholine (1.9 g, 22 mmol) was added to the THF solution. The mixture was stirred at ambient temperature for 1 hour and then filtered. The solvent of the filtrate was evaporated. The bright orange residue obtained was then mixed with 5% HCl solution (30 mL) and extracted with ethyl acetate (2×25 mL). The aqueous layer was basified with NaOH solution to pH 8 and then extracted with methylene chloride. Both ethyl acetate solution and methylene chloride solution were dried over anhydrous Na2SO4 separately. Evaporation of ethyl acetate solution afforded an orange oil which was recrystallized from hexane:ether solution to yield 450 mg of a yellow solid, 4-(3-methyl-4-nitrophenyl)morpholine (18%), the by-product. Evaporation of methylene chloride solution afforded 660 mg of the desired compound, 4-(5-fluoro-2-nitrobenzyl)morpholine (27.5%).

Workup

  1. temperatureheated
  2. temperatureat reflux
  3. customirradiated with light (100 W bulb) for 4 hours
  4. filtrationThe reaction mixture was filtered
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in THF (50 mL)
  7. filtrationfiltered
  8. customThe solvent of the filtrate was evaporated
  9. customThe bright orange residue obtained
  10. extractionextracted with ethyl acetate (2×25 mL)
  11. extractionextracted with methylene chloride
  12. dry with materialBoth ethyl acetate solution and methylene chloride solution were dried over anhydrous Na2SO4 separately
  13. customEvaporation of ethyl acetate solution
  14. customafforded an orange oil which
  15. customwas recrystallized from hexane

Sources & evidence

ORD record
ord-b826fdccd57543838db57af42887e639
Source dataset
uspto-grants-2013_05
Patent number
US08445694B2

Reaction notes

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