4-Methylmorpholine → Chloro-N,N-dimethylformiminium chloride

HRID 1736357Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1736357
[C:1]([Cl:6])(=O)C([Cl:4])=O.[C:7]([S:10][C@@H:11]1[CH2:15][N:14]([C:16]([O:18][CH2:19][CH:20]=[CH2:21])=[O:17])[C@H:13]([C:22]([OH:24])=O)[CH2:12]1)(=[O:9])[CH3:8].CN1CCOCC1.[CH2:32]([O:35][C:36]1[CH:37]=[C:38]([CH:45]=[CH:46][C:47]=1[NH2:48])[C:39]([O:41][CH2:42][CH:43]=[CH2:44])=[O:40])[CH:33]=[CH2:34]>ClCCl.CN(C=O)C>[CH3:13][N+:14]([CH3:15])=[CH:1][Cl:6].[Cl-:4].[C:7]([S:10][C@@H:11]1[CH2:15][N:14]([C:16]([O:18][CH2:19][CH:20]=[CH2:21])=[O:17])[C@H:13]([C:22](=[O:24])[NH:48][C:47]2[CH:46]=[CH:45][C:38]([C:39]([O:41][CH2:42][CH:43]=[CH2:44])=[O:40])=[CH:37][C:36]=2[O:35][CH2:32][CH:33]=[CH2:34])[CH2:12]1)(=[O:9])[CH3:8]

Komponenten

8

Edukt 4

HCID 79724-Methylmorpholine2×HCID 65578Oxalyl chlorideHCID 15299255(2S,4S)-4-Acetylthio-1-allyloxycarbonyl-2-carboxypyrrolidineHCID 19432469Allyl 3-allyloxy-4-aminobenzoate

Produkt 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 56974068(2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(4-allyloxycarbonyl-2-allyloxyphenylcarbamoyl)pyrrolidine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittelHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

Vilsmeier reagent was prepared by treatment of DMF (0.56 ml, 7.2 mM) in dichloromethane (35 ml) under argon with oxalyl chloride (0.58 ml, 6.6 mM) at -10° for 30 minutes. The (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-carboxypyrrolidine was added to this in one portion, followed by N-methylmorpholine (0.87 ml, 7.9 mM) and stirring continued for 30 minutes at -10°. After cooling to -20°, allyl 3-allyloxy-4-aminobenzoate (1.54 g, 6.6 mM) plus N-methyl morpholine (0.87 ml, 7.9 mM) dissolved in dichloromethane (20 ml) were added dropwise. The temperature was allowed to rise to 5° and stirring continued for 2 hours. After dilution with dichloromethane, the mixture was washed with a 2M aqueous solution of hydrochloric acid, water and a saturated aqueous solution of sodium bicarbonate. It was dried over MgSO4 and the solvent evaporated. Crude material was purified by medium pressure chromatography using a gradient of diethyl ether (0 to 10%) in dichloromethane to give (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(4-allyloxycarbonyl-2-allyloxyphenylcarbamoyl)pyrrolidine (2.7 g).

Aufarbeitung

  1. temperatureAfter cooling to -20°
  2. additionwere added dropwise
  3. customto rise to 5°
  4. stirringstirring
  5. waitcontinued for 2 hours
  6. washAfter dilution with dichloromethane, the mixture was washed with a 2M aqueous solution of hydrochloric acid, water
  7. dry with materialIt was dried over MgSO4
  8. customthe solvent evaporated
  9. customCrude material was purified by medium pressure chromatography

Quellen und Nachweise

ORD-Eintrag
ord-34fbb43f2c664eda8175a78dc9e94f66
Quelldatensatz
uspto-grants-1996_07
Patentnummer
US05541178

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