반응 #2201632

반응 방정식

HCl

ethyl bromoacetate

6,7-dichloro-2H-1,4-benzoxazin-3(4H)-one

trifluoroacetic acid

→

ethyl (6,7-dichloro-3-oxo-2,3-dihydro-4H-1,4-benzoxazin-4-yl)acetate

수율 84.0%

용매

CH3CN H2O

DMF

반응 조건

후처리

1. 1
   기타A 1 L round-bottom flask was purged with argon
2. 2
   workup.ADDITIONcharged with sodium hydride (6.94 g of a 60% dispersion of NaH in mineral oil, 0.174 mol) and 60 mL of anhydrous DMF
3. 3
   온도The reaction mixture was maintained at 0° C. for one hour
4. 4
   온도This reaction mixture was maintained at 0° C. for thirty minutes
5. 5
   온도to warm to room temperature
6. 6
   온도was maintained at room temperature for thirty minutes
7. 7
   기타had formed (Rt=7.5 min)
8. 8
   기타the product precipitated immediately as a yellow solid
9. 9
   workup.STIRRINGThe suspension was stirred for 10 minutes
10. 10
    여과the solid was filtered off
11. 11
    기타to give a yellow filter cake
12. 12
    세척The solid was rinsed with ice-cold ethanol (3×200 mL) and hexanes (3×200 mL)
13. 13
    기타dried under high vacuum

실험 절차

A 1 L round-bottom flask was purged with argon and charged with sodium hydride (6.94 g of a 60% dispersion of NaH in mineral oil, 0.174 mol) and 60 mL of anhydrous DMF. This suspension was magnetically stirred and cooled to 0° C. in an ice-bath and then treated slowly with a suspension of 6,7-dichloro-2H-1,4-benzoxazin-3(4H)-one (22.2 g. 0.102 mol) in 140 mL of anhydrous DMF. The reaction mixture was maintained at 0° C. for one hour and then treated slowly with ethyl bromoacetate (29.4 mL, 0.265 mol) over a period of 5-10 minutes. This reaction mixture was maintained at 0° C. for thirty minutes, allowed to warm to room temperature, and then was maintained at room temperature for thirty minutes. HPLC (Eclipse XDB-C18, 4.6×250 mm, 5 micron, 1-99% CH3CN/H2O with 0.1% trifluoroacetic acid) showed that all of the starting material (Rt=6.2 min) was gone and that a new compound had formed (Rt=7.5 min). The reaction mixture was poured into 5.5 L of 5% aqueous HCl and the product precipitated immediately as a yellow solid. The suspension was stirred for 10 minutes and the solid was filtered off to give a yellow filter cake. The solid was rinsed with ice-cold ethanol (3×200 mL) and hexanes (3×200 mL) and then dried under high vacuum to give ethyl (6,7-dichloro-3-oxo-2,3-dihydro-4H-1,4-benzoxazin-4-yl)acetate (26.0 g, 0.085 mol, 84%) as a white powder. MS (ES) m/e 304 [M+H]+.

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