Carbon Tetrachloride → (2S,4S)-1-tert-butyl 2-methyl 4-chloropyrrolidine-1,2-dicarboxylate

HRID 1264373Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1264373
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:9][C@@H:8](O)[CH2:7][N:6]1[C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[O:4].C(Cl)[Cl:19].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Cl)(Cl)(Cl)Cl>CCCCCCC>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:9][C@H:8]([Cl:19])[CH2:7][N:6]1[C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[O:4]

Komponenten

6

Edukt 4

HCID 5943Carbon TetrachlorideHCID 6344DichloromethaneHCID 11776TriphenylphosphineHCID 2734883(2S,4R)-4-Hydroxypyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester

Produkt 1

HCID 11242503(2S,4S)-1-tert-butyl 2-methyl 4-chloropyrrolidine-1,2-dicarboxylateAusbeute 89 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8900HeptaneLösungsmittel

Reaktionsbedingungen

Temperatur
4 °C

Versuchsvorschrift

A solution of 374 g (1.48 mol) (2S,4R)-4-Hydroxy-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester in 1.61 CH2Cl2 was treated with 680 g (2.6 mol) triphenylphosphine, cooled to 3-5° C. and treated in 10 min with 1.24l (12.8 mol) CCl4, after 2 h at this temperature cooling was stopped, the reaction temperature was raised to 35° C. over a period of 2 h. It was cooled down to 20° C. and stirred for further 45 min. After addition of 4l of n-heptane, the reaction was evaporated to 2.9l, cooled to 0° C., filtered, the residue was treated twice the same way, the third time by dissolving the residue again in 2 of CH2Cl2. The solvents were evaporated and filtered through silicagel with hexane/tert.-buthyl-methylether 9:1 as eluent. Evaporation of the solvents gave 347 g (89%) of (2S,4S)-4-Chloro-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester, MS: 246 (MH+).

Aufarbeitung

  1. temperaturecooling
  2. temperaturethe reaction temperature was raised to 35° C. over a period of 2 h
  3. temperatureIt was cooled down to 20° C.
  4. customthe reaction was evaporated to 2.9l
  5. temperaturecooled to 0° C.
  6. filtrationfiltered
  7. additionthe residue was treated twice the same way
  8. dissolutionthe third time by dissolving the residue again in 2 of CH2Cl2
  9. customThe solvents were evaporated
  10. filtrationfiltered through silicagel with hexane/
  11. customEvaporation of the solvents

Quellen und Nachweise

ORD-Eintrag
ord-b1712f82bd2d4ff496d5c39282b9c66a
Quelldatensatz
uspto-grants-2003_04
Patentnummer
US06541638B2

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