반응 #7001

반응 방정식

NaNO2

5-methoxy-2-methyl aniline

HCl

HBF4

→

3-fluoro-4-methyl anisole

수율 31.0%

용매

H2O

반응 조건

후처리

1. 1
   workup.ADDITION40 mmol) was added cautiously
2. 2
   여과the resultant brown solid was filtered
3. 3
   세척washed with ice water (3×10 mL) and H2O (2×10 mL)
4. 4
   기타The solid was dried under high vacuum for 20 h
5. 5
   온도heated
6. 6
   온도(heat gun) until evolution of BF3 (white fumes)
7. 7
   기타The resulting brown oil was partitioned between EtOAc and H2O
8. 8
   건조The organic phase was dried (Na2SO4)
9. 9
   농축concentrated in vacuo
10. 10
    workup.DISTILLATIONdistilled by Kugelrohr

실험 절차

A mixture of 5-methoxy-2-methyl aniline (5.0 g; 36 mmol), HCl (7.6 mL of a 12 M solution; 91 mmol) and H2O (11 mL) was heated at 60° C. for 15 min until complete dissolution had occurred. The reaction was cooled to 0° C. and an aqueous solution of NaNO2 (2.5 g; 36 mmol) was added dropwise (internal temperature ≦7° C.). The reaction was stirred at 0° C. for 30 min and a 0° C. solution of HBF4 (5.3 mL of a 48% solution; 40 mmol) was added cautiously. The reaction was stirred at 0° C. for 20 min, and the resultant brown solid was filtered, washed with ice water (3×10 mL) and H2O (2×10 mL). The solid was dried under high vacuum for 20 h, then heated (heat gun) until evolution of BF3 (white fumes) had ceased. The resulting brown oil was partitioned between EtOAc and H2O. The organic phase was dried (Na2SO4), concentrated in vacuo and distilled by Kugelrohr to give 3-fluoro-4-methyl anisole (1.6 g; 31%) as a colorless oil.

출처