4-Nitrobenzoic Acid → (S)-1-(4-Dimethylaminophenethyl)-3-(4-nitrobenzoyloxy)pyrrolidine

HRID 1859450ノート

反応式

HRID 1859450 の反応式
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+:20]([C:23]1[CH:31]=[CH:30][C:26]([C:27]([OH:29])=[O:28])=[CH:25][CH:24]=1)([O-:22])=[O:21].[CH3:32][N:33]([CH3:48])[C:34]1[CH:47]=[CH:46][C:37]([CH2:38][CH2:39][N:40]2[CH2:44][CH2:43][C@@H:42](O)[CH2:41]2)=[CH:36][CH:35]=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1.C1(C)C=CC=CC=1.CCOCC>[CH3:48][N:33]([CH3:32])[C:34]1[CH:35]=[CH:36][C:37]([CH2:38][CH2:39][N:40]2[CH2:44][CH2:43][C@H:42]([O:28][C:27](=[O:29])[C:26]3[CH:25]=[CH:24][C:23]([N+:20]([O-:22])=[O:21])=[CH:31][CH:30]=3)[CH2:41]2)=[CH:46][CH:47]=1

参加物

8

反応物 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 69902796(R)-1-(4-dimethylaminophenethyl)-3-hydroxypyrrolidine

生成物 1

HCID 69900132(S)-1-(4-Dimethylaminophenethyl)-3-(4-nitrobenzoyloxy)pyrrolidine

試薬・触媒・溶媒 3

HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Triphenylphosphine (1.72 g, 5.13 mmol) and 4-nitrobenzoic acid (0.86 g, 5.13 mmol) were added to a solution of (R)-1-(4-dimethylaminophenethyl)-3-hydroxypyrrolidine in anhydrous tetrahydrofuran (20 ml) under argon atmosphere. 40% solution (2.32 ml, 5.13 mmol) of diethyl azodicarboxylate in toluene was added dropwise in the obtained mixture under stirring at room temperature. After stirring at room temperature for 2 hours, 60 ml of ether was added to the reaction liquid. The reaction mixture was washed with water, then with saturated aqueous sodium hydrogencarbonate solution and finally with saturated aqueous sodium chloride solution. The organic layer was dried, and the solvent was evaporated under reduced pressure. Ethyl acetate and hexane were added to the obtained residue, and the crystals thus formed were taken by the filtration. The filtrate was evaporated under reduced pressure, and the residue was distributed in dichloromethane and 1 M-HCl. 4M-NaOH was added to the aqueous layer to make it strongly alkaline. After the extraction with dichloromethane, the organic layer was dried and the solvent was distilled under reduced pressure. The residue was subjected to silica gel column chromatography. The product was eluted with hexane and ethyl acetate (10:1), then with a mixture of the same solvents (3:1) and finally with a mixture of the same solvents (1:1). The appropriate fractions were combined, and the solvent was evaporated under reduced pressure to obtain the title compound in the form of a light yellow oil (860 mg, 64%).

後処理

  1. stirringAfter stirring at room temperature for 2 hours
  2. washThe reaction mixture was washed with water
  3. customThe organic layer was dried
  4. customthe solvent was evaporated under reduced pressure
  5. additionEthyl acetate and hexane were added to the obtained residue
  6. customthe crystals thus formed
  7. filtrationwere taken by the filtration
  8. customThe filtrate was evaporated under reduced pressure
  9. addition4M-NaOH was added to the aqueous layer
  10. extractionAfter the extraction with dichloromethane
  11. customthe organic layer was dried
  12. distillationthe solvent was distilled under reduced pressure
  13. washThe product was eluted with hexane and ethyl acetate (10:1)
  14. additionwith a mixture of the same solvents (3:1)
  15. additionfinally with a mixture of the same solvents (1:1)
  16. customthe solvent was evaporated under reduced pressure

出典と根拠

ORDレコード
ord-08a50287e680462692bf6cf01c0d2b73
出典データセット
uspto-grants-2003_03
特許番号
US06528504B2

反応ノート

読み込み中…