반응 #10501

ord-1c01067372e44b6680ad32e1a7caf277

반응 방정식

C=CC(=O)O
acrylic acid
Nc1cc(Br)ccc1O
2-amino-4-bromo-phenol
CS(=O)(=O)O
methanesulfonic acid
O=P12OP3(=O)OP(=O)(O1)OP(=O)(O2)O3
phosphorus pentoxide
[Na+].[OH-]
NaOH
C=Cc1nc2cc(Br)ccc2o1
5-bromo-2-vinyl-benzooxazole
수율 45.1%

반응 조건

온도
78°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    workup.STIRRINGTo this well stirred suspension
  2. 2
    온도cooled to room temperature
  3. 3
    workup.ADDITIONThe mixture was then poured into a separatory funnel
  4. 4
    workup.STIRRINGshaken vigorously
  5. 5
    기타A small quantity of solid was removed by suction filtration
  6. 6
    workup.STIRRINGthe filtrate again shaken vigorously in a separatory funnel
  7. 7
    기타The organic phase was collected
  8. 8
    건조dried over Na2SO4
  9. 9
    농축concentrated in vacuo to a thick syrup
  10. 10
    기타that crystallized
  11. 11
    기타to give large yellow stars
  12. 12
    기타Purification by flash chromatography on silica gel (eluting with 1:1 hexane:dichloromethane)

실험 절차

A mixture of 12 g of methanesulfonic acid and 1.8 g of phosphorus pentoxide (P2O5) was stirred 12 hours. To this well stirred suspension was added 0.346 g (4.8 mmol) of acrylic acid and 0.808 g (4 mmol) of 2-amino-4-bromo-phenol. The reaction was heated at 78° C. for 5 hours, then cooled to room temperature. The reaction was then slowly poured into a well-stirred slurry of 15 mL of 50% aqueous NaOH in 200 g of ice and water. The mixture was then poured into a separatory funnel and shaken with 300 mL water, 200 mL of diethyl ether, and 75 mL of dichloromethane and shaken vigorously. A small quantity of solid was removed by suction filtration, and the filtrate again shaken vigorously in a separatory funnel. The organic phase was collected, dried over Na2SO4, and concentrated in vacuo to a thick syrup that crystallized to give large yellow stars. Purification by flash chromatography on silica gel (eluting with 1:1 hexane:dichloromethane) gave 0.404 g (45%) of 5-bromo-2-vinyl-benzooxazole as a white powder, mp 55–56° C. 1H NMR (300 MHz, CDCl3) δ 7.84 (d, J=1.8 Hz, 1H), 7.46 (dd, J=8.7, 1.8 Hz, 1 H), 7.40 (d, J=8.7 Hz, 1 H), 6.76 (dd, J=17, 10.5 Hz, 1 H), 6.50 (d, J=17 Hz, 1 H), 5.90 (d, J=10.5 Hz, 1 H); Mass spectrum: [M+H]+ at 224.0 & 226.0.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US07094790B2uspto-grants-2006_08