反应详情

To a magnetically stirred solution of 4-iodophenol (15 grams, 0.068 mol) in 100 mL THF was sequentially added triphenylphosphine (19.67 grams, 0.075 mol), diethyl azodicarboxylate (13.06 grams, 0.073 mol), and 2-azidoethanol (5.93 grams, 0.068 mol). The mixture was stirred overnight, concentrated in vacuo, diluted with 90 mL ethyl acetate and diluted with hexane (400 mL), and the resulting solids filtered away. The filtrate was concentrated in vacuo, diluted with diethyl ether, and extracted with 1N NaOH and water. Pentane was added to induce precipitation of a white solid that was again filtered away. The filtrate was concentrated in vacuo, and dissolved in methanol (60 mL). Triethylamine (27 grams, 0.267 mol) and propanedithiol (23 grams, 0.215 mol) were added and the mixture stirred at room temperature overnight. The solution was diluted with 100 mL water and partitioned between methylene chloride and 1N NaOH. The organic layer was extracted with 2×200 mL 1N HCl and the aqueous layer washed with 100 mL methylene chloride, made basic with 2N NaOH and extracted 3×75 mL methylene chloride. The combined organics were dried over sodium carbonate, filtered and concentrated in vacuo to yield 12.97 grams of 2-(4-iodophenoxy)ethyl amine (72%). 1NMR (CDCl3, dTMS) 7.56 (2H, d, 3JHH =9 Hz, Ar-H), 6.63 (2H, d, 3JHH =9 Hz, Ar-H), 4.03 (2H, t, 3JHH =5 Hz, CH2N3), 3.57 (2H, t, 3JHH =5 Hz, OCH2). 13C NMR (CDCl3) 158.0, 138.2, 116.9, 83.4, 66.9, 49.9. IR (NaCl, cm-1) 2930, 2107 (s), 1589, 1483, 1284, 1237, 1058, 819.

1. concentrationconcentrated in vacuo
2. additiondiluted with 90 mL ethyl acetate
3. additiondiluted with hexane (400 mL)
4. filtrationthe resulting solids filtered away
5. concentrationThe filtrate was concentrated in vacuo
6. additiondiluted with diethyl ether
7. extractionextracted with 1N NaOH and water
8. additionPentane was added
9. customprecipitation of a white solid
10. filtrationthat was again filtered away
11. concentrationThe filtrate was concentrated in vacuo
12. dissolutiondissolved in methanol (60 mL)
13. stirringthe mixture stirred at room temperature overnight
14. custompartitioned between methylene chloride and 1N NaOH
15. extractionThe organic layer was extracted with 2×200 mL 1N HCl
16. washthe aqueous layer washed with 100 mL methylene chloride
17. extractionextracted 3×75 mL methylene chloride
18. dry with materialThe combined organics were dried over sodium carbonate
19. filtrationfiltered
20. concentrationconcentrated in vacuo