Sodium hydride → 2,3-dihydro-1-methylene-1H-pyrrolizine

HRID 485373

반응식

HRID 485373 반응식
O=[C:2]1[C:9]2[N:5]([CH:6]=[CH:7][CH:8]=2)[CH2:4][CH2:3]1.[CH2:10]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[H-].[Na+]>CS(C)=O.[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:10]=[C:2]1[C:9]2[N:5]([CH:6]=[CH:7][CH:8]=2)[CH2:4][CH2:3]1

참가 물질

6

반응물 3

HCID 24758Sodium hydrideHCID 973473H-1,2-dihydro-1-pyrrolizinoneHCID 137960Methylenetriphenylphosphorane

생성물 1

HCID 202703552,3-dihydro-1-methylene-1H-pyrrolizine

시약·촉매·용매 2

HCID 74505Methyltriphenyliphosphonium bromide촉매HCID 679Dimethyl Sulfoxide용매2회

실험 절차

A solution of 2,3-dihydro-1-oxo-1H-pyrrolizine (16.1 g, 0.133 m); J. Org. Chem., 27 2468 (1962) ) in dried dimethylsulfoxide (60 ml) is added dropwise over ca. 10 minutes to a mixture of methylenetriphenylphosphorane (from methyl triphenylphosphonium bromide (57.2 g, 0.16 m), sodium hydride 60% dispersion (6.4 g, 0.16 m) and dimethylsulfoxide (256 ml) in the standard fashion (J. Org. Chem., 28 1128 (1963)) at ambient temperatures. After stirring for ca 2 hours, the mixture is heated in an oil-bath set at 70° C. for ca 30 minutes, and let cool. After stirring overnight at ambient temperatures, the mixture is poured into 1200 ml of ice-water, extracted 4×400 ml of ether, the ether layers washed 3×400 ml of water, dried and concentrated to a residue. The residue is extracted well with hexane, the filtered hexane extracts concentrated and distilled to yield 2,3-dihydro-1-methylene-1H-pyrrolizine.

후처리

  1. temperaturethe mixture is heated in an oil-bath
  2. waitset at 70° C. for ca 30 minutes
  3. temperaturelet cool
  4. stirringAfter stirring overnight at ambient temperatures
  5. extractionextracted 4×400 ml of ether
  6. washthe ether layers washed 3×400 ml of water
  7. customdried
  8. concentrationconcentrated to a residue
  9. extractionThe residue is extracted well with hexane
  10. concentrationthe filtered hexane extracts concentrated
  11. distillationdistilled

출처 및 근거

ORD 기록
ord-4158bf6627e24c25875e6801c3c29dee
출처 데이터셋
uspto-grants-1985_08
특허 번호
US04536512

연결된 노트

불러오는 중…