Water → HCID 86743487、化合物

HRID 2352574ノート

反応式

HRID 2352574 の反応式
C([Li])CCC.[Br-].C1([P+](C2C=CC=CC=2)(C2C=CC=CC=2)[CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([Cl:21])[CH:16]=2)C=CC=CC=1.[CH:34]([C@H:36]1[N:40]([CH3:41])[C:39](=[O:42])[CH2:38][C@H:37]1[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)=O.O>C1(C)C=CC=CC=1>[CH3:41][N:40]1[C@H:36]([CH:34]=[CH:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([Cl:21])[CH:16]=2)[C@H:37]([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[CH2:38][C:39]1=[O:42]

参加物

6

反応物 4

HCID 962WaterHCID 13825986HCID 13825986、化合物HCID 16731599[(3-Chlorophenyl)methyl](triphenyl)phosphanium bromideHCID 178418339Butyllithium

生成物 1

HCID 86743487HCID 86743487、化合物

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

実験手順

32.8 g (77 mmol) of n-butyllithium (15% in hexane) were added dropwise under nitrogen with ice cooling to 36.0 g (77 mmol) of triphenyl-m-chlorobenzylphosphonium bromide in 150 ml of toluene in the course of 20 minutes, and the orange suspension was subsequently stirred for 15 minutes. 15.6 g (77 mmol) of cis-5-formyl-1-methyl-4- phenylpyrrolidin-2-one (German Laid-Open Application DOS 3,537,075 and 3,632,589; J. Org. Chem. 52 (1987), 4352) in 120 ml of toluene were then added dropwise and stirred in at room temperature for 3 hours (color change toward pale yellow). 200 ml of H2O were then added, the mixture was acidified with dilute HCL and filtered with suction, the phases were separated, the aqueous phase was extracted twice more with toluene, and the combined organic phases were washed with H2O, dried and concentrated. The crude product was taken up in 100 ml of methyl t-butyl ether and filtered with suction and cooling to remove precipitated triphenylphosphine oxide. The filtrate was concentrated and purified by column chromatography (silica gel, eluent: 98/2 methylene chloride/methanol); yield: 16.1 g (67%). Judging by a 1H-NMR spectrum, the styryl side chain is 90% in the trans configuration and 10% in the cis configuration.

後処理

  1. stirringstirred in at room temperature for 3 hours (color change toward pale yellow)
  2. filtrationfiltered with suction
  3. customthe phases were separated
  4. extractionthe aqueous phase was extracted twice more with toluene
  5. washthe combined organic phases were washed with H2O
  6. customdried
  7. concentrationconcentrated
  8. filtrationfiltered with suction
  9. temperaturecooling
  10. customto remove
  11. customprecipitated triphenylphosphine oxide
  12. concentrationThe filtrate was concentrated
  13. custompurified by column chromatography (silica gel, eluent: 98/2 methylene chloride/methanol)

出典と根拠

ORDレコード
ord-1a5a594f36044658abb631379f496c6e
出典データセット
uspto-grants-1989_10
特許番号
US04877807

反応ノート

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