Sodium hydride → 4-(3,5-Dibenzyloxyphenyl)-1-phenoxypent-3-ene

HRID 435136노트

반응식

HRID 435136 반응식
[CH3:1][C:2]([C:4]1[CH:9]=[C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:7]=[C:6]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:5]=1)=O.[Br-].[O:27]([CH2:34][CH2:35][CH2:36][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.[H-].[Na+]>O1CCCC1.CS(C)=O>[CH2:19]([O:18][C:6]1[CH:5]=[C:4]([C:2]([CH3:1])=[CH:36][CH2:35][CH2:34][O:27][C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[CH:9]=[C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:7]=1)[C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1

참가 물질

6

반응물 3

HCID 24758Sodium hydrideHCID 120098Ethanone, 1-(3,5-bis(phenylmethoxy)phenyl)-HCID 3048782(3-Phenoxypropyl)(triphenyl)phosphanium bromide

생성물 1

HCID 544983714-(3,5-Dibenzyloxyphenyl)-1-phenoxypent-3-ene수율 75%

시약·촉매·용매 2

HCID 679Dimethyl Sulfoxide용매HCID 8028Tetrahydrofuran용매

실험 절차

Under a nitrogen atmosphere a mixture of 3,5-dibenzyloxyacetophenone (50.0 g., 0.15 M) in tetrahydrofuran (175 ml.) and 3-phenoxypropyltriphenylphosphonium bromide (7.18 g., 0.15 M) in dimethylsulfoxide (450 ml.) is added dropwise over 1.75 hours to a suspension of 50% sodium hydride (7.89 g., 0.165 M) (previously washed with pentane) in tetrahydrofuran (75 ml.) maintained at 0°-5° C. After stirring for 4 hours at 0°-5° C. the reaction is allowed to warm to room temperature and is then carefully stirred into ice water (2000 ml.), acidified with concentrated hydrochloric acid, and extracted with ethyl acetate (5×400 ml.). The combined organic phases are washed with saturated sodium chloride solution (3×300 ml.), dried over sodium sulfate and concentrated under vacuum to yield an oil which is triturated with ether to precipitate triphenylphosphine oxide. Filtration, followed by concentration of the filtrate, gives an oily residue which is chromatographed over silica gel (1300 g.) eluting with benzene-hexane consisting of 30% to 100% benzene. From the middle fractions 51 g. (75%) of 4-(3,5-dibenzyloxyphenyl)-1-phenoxypent-3-ene is isolated as an oil; Rf =0.8 (silica gel, 2-benzene:1-hexane); m/e--450 (m+).

후처리

  1. washpreviously washed with pentane) in tetrahydrofuran (75 ml.)
  2. temperaturemaintained at 0°-5° C
  3. stirringis then carefully stirred into ice water (2000 ml.)
  4. extractionextracted with ethyl acetate (5×400 ml.)
  5. washThe combined organic phases are washed with saturated sodium chloride solution (3×300 ml.)
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under vacuum
  8. customto yield an oil which
  9. customis triturated with ether
  10. customto precipitate triphenylphosphine oxide
  11. filtrationFiltration
  12. customgives an oily residue which
  13. customis chromatographed over silica gel (1300 g.)
  14. washeluting with benzene-hexane

출처 및 근거

ORD 기록
ord-fa7edd4fffc04874a620f3a8df9978eb
출처 데이터셋
uspto-grants-1983_08
특허 번호
US04400385

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