반응 #70822

ord-9b74e036973a41e4be89156d2b6cabaf

반응 방정식

[Li][CH2]CCC
n-butyllithium
c1ccc(COCn2ncnn2)cc1
2-(benzyloxymethyl)-2H-tetrazole
CN(C)CCN(C)C
tetramethylethylenediamine
CCC[CH2][Sn]([Cl])([CH2]CCC)[CH2]CCC
tributyltin chloride
CCC[CH2][Sn]([CH2]CCC)([CH2]CCC)[c]1nnn(COCc2ccccc2)n1
2-(benzyloxymethyl)-5-(tributylstannyl)-2H-tetrazole
수율 60.0%

반응 조건

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

후처리

  1. 1
    workup.ADDITIONUpon completion of addition
  2. 2
    workup.STIRRINGUpon completion of the transfer, the reaction was stirred for 45 minutes
  3. 3
    기타quenched with saturated ammonium chloride solution
  4. 4
    기타to come to room temperature
  5. 5
    기타the aqueous and organic layers were separated
  6. 6
    추출The aqueous phase was extracted 3× with ethyl acetate
  7. 7
    세척the combined organic phases were washed with brine
  8. 8
    건조dried over sodium sulfate
  9. 9
    농축concentrated in vacuo
  10. 10
    기타to yield a residue
  11. 11
    기타The residue was purified over silica gel
  12. 12
    세척eluting with 1%

실험 절차

In a flame-dried three-neck flask, a solution of 2-(benzyloxymethyl)-2H-tetrazole (2.01 g, 10.57 mmol) and tetramethylethylenediamine (3.16 mL, 21.4 mmol) in diethyl ether (30 mL) was cooled to −78° C. Once at the prescribed temperature, the mixture was treated with the dropwise addition of n-butyllithium (1.6 M in hexanes, 7.3 mL, 11.62 mmol), which caused the color of the solution to turn dark red. Upon completion of addition, the mixture was stirred for 10 minutes, and then transferred via cannula to a solution of tributyltin chloride (2.9 mL, 10.57 mmol) in diethyl ether (20 mL) which had been pre-cooled to −78° C. Upon completion of the transfer, the reaction was stirred for 45 minutes, and then quenched with saturated ammonium chloride solution. The mixture was allowed to come to room temperature, and the aqueous and organic layers were separated. The aqueous phase was extracted 3× with ethyl acetate, and the combined organic phases were washed with brine, dried over sodium sulfate, and concentrated in vacuo to yield a residue. The residue was purified over silica gel, eluting with 1% then 5% then 10% ethyl acetate/hexanes to yield 2-(benzyloxymethyl)-5-(tributylstannyl)-2H-tetrazole (3.0 g, 60% yield) as a colorless oil.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US08536198B2uspto-grants-2013_09