تفاعل #342117

ord-3d0f3b3a5d104fabbe96ee66cebd9ef1

معادلة التفاعل

C1COCCN1
Morpholine
Cc1cc(F)ccc1[N+](=O)[O-]
5-Fluoro-2-nitrotoluene
O=C1CCC(=O)N1Br
N-bromosuccinimide
O=C(OOC(=O)c1ccccc1)c1ccccc1
benzoyl peroxide
Cl
HCl
O=[N+]([O-])c1ccc(F)cc1CN1CCOCC1
yellow solid
المردود 18.7%
O=[N+]([O-])c1ccc(F)cc1CN1CCOCC1
4-(5-Fluoro-2-nitrobenzyl)morpholine
المردود 18.7%

المذيبات

ظروف التفاعل

الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    درجة الحرارةheated
  2. 2
    درجة الحرارةat reflux
  3. 3
    أخرىirradiated with light (100 W bulb) for 4 hours
  4. 4
    ترشيحThe reaction mixture was filtered
  5. 5
    تركيزconcentrated
  6. 6
    workup.DISSOLUTIONThe residue was dissolved in THF (50 mL)
  7. 7
    ترشيحfiltered
  8. 8
    أخرىThe solvent of the filtrate was evaporated
  9. 9
    أخرىThe bright orange residue obtained
  10. 10
    استخلاصextracted with ethyl acetate (2×25 mL)
  11. 11
    استخلاصextracted with methylene chloride
  12. 12
    تجفيفBoth ethyl acetate solution and methylene chloride solution were dried over anhydrous Na2SO4 separately
  13. 13
    أخرىEvaporation of ethyl acetate solution
  14. 14
    أخرىafforded an orange oil which
  15. 15
    أخرىwas recrystallized from hexane

الإجراء التجريبي

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%).

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US07875728B2uspto-grants-2011_01