Carbon Dioxide → HCID 178471411, Verbindung

HRID 25592

Reaktionsgleichung

Reaktionsgleichung von HRID 25592
C(Cl)(=O)C(Cl)=O.C(=O)=O.CS(C)=O.[C:14]([O:18][C:19](=[O:32])[N:20]([C@H:22]1[CH2:27][CH2:26][C@H:25]([CH2:28][CH2:29][CH2:30]O)[CH2:24][CH2:23]1)[CH3:21])([CH3:17])([CH3:16])[CH3:15].CCN(CC)CC.C(OC(=O)N(C)[C@H]1CC[C@H](CCC=O)CC1)(C)(C)C.[CH3:59][CH2:60][O:61][C:62]([CH2:64]P(OCC)(OCC)=O)=[O:63].C[O-].[Na+]>C(Cl)Cl.CCOCC.C(O)C>[CH2:60]([O:61][C:62](=[O:63])[CH:64]=[CH:30][CH2:29][CH2:28][C@H:25]1[CH2:26][CH2:27][C@H:22]([N:20]([C:19]([O:18][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:32])[CH3:21])[CH2:23][CH2:24]1)[CH3:59]

Komponenten

12

Edukt 8

HCID 280Carbon DioxideHCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 13345Triethyl phosphonoacetateHCID 65578Oxalyl chlorideHCID 10942334Sodium MethoxideHCID 178486041HCID 178486041, VerbindungHCID 178486042HCID 178486042, Verbindung

Produkt 1

HCID 178471411HCID 178471411, VerbindungAusbeute 58 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 702EthanolLösungsmittelHCID 3283Diethyl EtherLösungsmittelHCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

1.4 ml (16.24 mmol) oxalylchloride was added to a dry-ice cooled solution (−78° C.) of 1.78 ml (25 mmol) DMSO in 40 ml CH2Cl2. After 10 min. stirring at −78° C., 2.39 g (12.49 mmol) of trans-[4-(3-Hydroxy-propyl)-cyclohexyl]-methyl-carbamic acid tert-butyl ester, dissolved in 5 ml CH2Cl2, was added. 15 min later, 8.7 ml (62.4 mmol) Et3N was added and the reaction-mixture was allowed to attain RT. The mixture was diluted with Et2O and then washed with 1N HCl and water. After evaporation of the solvents, a solution of crude trans-Methyl-[4-(3-oxo-propyl)-cyclohexyl]-carbamic acid tert-butyl ester (3.24 g, 12.02 mmol) and of 2.73 ml (13.3 mmol) triethyl phosphono acetate in 30 ml ethanol, was treated under ice-cooling with 1.37 g (24.05 mmol) NaOMe. The solution was stirred for 20 h at RT, and then concentrated in vacuo. The crude residue was dissolved in Et2O and washed with water. The organic layers were concentrated in vacuo and the crude product purified by chromatography on silica gel with EtOAc/Hexane 1:4 to yield 2.46 g (58%, 2 steps) of clean trans-5-[4-(tert-Butoxycarbonyl-methyl-amino)-cyclohexyl]-pent-2-enoic acid ethyl ester, MS: 339 (M).

Aufarbeitung

  1. additionwas added
  2. customto attain RT
  3. washwashed with 1N HCl and water
  4. customAfter evaporation of the solvents
  5. stirringThe solution was stirred for 20 h at RT
  6. concentrationconcentrated in vacuo
  7. dissolutionThe crude residue was dissolved in Et2O
  8. washwashed with water
  9. concentrationThe organic layers were concentrated in vacuo
  10. customthe crude product purified by chromatography on silica gel with EtOAc/Hexane 1:4

Quellen und Nachweise

ORD-Eintrag
ord-5f96f3eaf2ac40319f944851794fe16c
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06858651B2

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