반응 #2175449

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2,7-di(Boc-amino)fluorene

THF

→

9-formyl-2,7-di(Boc-amino)fluorene

용매

ethyl formate

반응 조건

후처리

1. 1
   기타(Note: ethyl formate was stored over K2CO3 to remove formic acid.) The solution
2. 2
   온도was cooled in an ice bath
3. 3
   workup.ADDITIONsodium hydride 60% in mineral oil was added portion-wise (5.5 eq, 69 mmol, 2.75 g)
4. 4
   온도heated to 50° C.
5. 5
   기타after fitting with a reflux condenser
6. 6
   온도the reaction was cooled in an ice bath
7. 7
   기타quenched by the slow addition of deionized water (50 mL)
8. 8
   추출extracted with ethyl acetate (2×400 mL)
9. 9
   건조The combined organic layers were dried with Na2SO4
10. 10
    여과filtered
11. 11
    기타evaporated under reduced pressure
12. 12
    기타The crude product (dark brown solid) was purified by flash chromatography
13. 13
    세척silica gel 60 Å step-wise gradient elution 1-5% methanol in chloroform
14. 14
    기타Yield (4.8 g, ˜90%) of a yellow to brown solid

실험 절차

Purified 2,7-di(Boc-amino)fluorene (5 g, 12.5 mmol) (prepared from step A, above), was dissolved in ethyl formate (50 mL) and anhydrous THF (60 mL) with gentle heating. (Note: ethyl formate was stored over K2CO3 to remove formic acid.) The solution was cooled in an ice bath and sodium hydride 60% in mineral oil was added portion-wise (5.5 eq, 69 mmol, 2.75 g). The reaction was slowly warmed to room temperature and then heated to 50° C. after fitting with a reflux condenser. After two hours, the reaction was cooled in an ice bath and quenched by the slow addition of deionized water (50 mL). The aqueous layer was adjusted to pH 5 with glacial acetic acid and extracted with ethyl acetate (2×400 mL). The combined organic layers were dried with Na2SO4, filtered and evaporated under reduced pressure. The crude product (dark brown solid) was purified by flash chromatography: silica gel 60 Å step-wise gradient elution 1-5% methanol in chloroform. Yield (4.8 g, ˜90%) of a yellow to brown solid, depending on purity. 1H-NMR (d6-DMSO): δ (ppm) 11.0 (s, 0.9H, enol); 9.3 (2 s, 1.9H, NH urethane); 7.2-8.3 (m, Ar, C10 H enol); 6.5 (2 s, 0.1H, NH urethane); 4.1 (m, 0.3H, CH); 1.5 (s, 18H, Boc).

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