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

HRID 443627ノート

反応式

HRID 443627 の反応式
[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

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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+).

後処理

  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

出典と根拠

ORDレコード
ord-6b75c880aaba4519bc8136f9087e3b65
出典データセット
uspto-grants-1981_04
特許番号
US04260764

反応ノート

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