Hexamethylenetetramine → ethyl 2-[(1R)-1-(2-tert-butoxy-2-oxoethyl)-4-cyclohexylbutyl]-1,3-oxazole-4-carboxylate

HRID 2183024Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2183024
C1N2CN3CN(C2)CN1C3.N12CCCN=C1CCCCC2.[C:22]([O:26][C:27](=[O:49])[CH2:28][C@H:29]([C:39]1[O:40][CH2:41][C@@H:42]([C:44]([O:46][CH2:47][CH3:48])=[O:45])[N:43]=1)[CH2:30][CH2:31][CH2:32][CH:33]1[CH2:38][CH2:37][CH2:36][CH2:35][CH2:34]1)([CH3:25])([CH3:24])[CH3:23]>ClCCl.[Cu](Br)Br>[C:22]([O:26][C:27](=[O:49])[CH2:28][C@H:29]([C:39]1[O:40][CH:41]=[C:42]([C:44]([O:46][CH2:47][CH3:48])=[O:45])[N:43]=1)[CH2:30][CH2:31][CH2:32][CH:33]1[CH2:38][CH2:37][CH2:36][CH2:35][CH2:34]1)([CH3:25])([CH3:24])[CH3:23]

Komponenten

6

Edukt 3

HCID 4101HexamethylenetetramineHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 59909855Ethyl (4S)-2-{(1R)-1-[2-(tert-butoxy)-2-oxoethyl]4-cyclohexylbutyl}-4,5-dihydro-1,3-oxazole-4-carboxylate

Produkt 1

HCID 59110691ethyl 2-[(1R)-1-(2-tert-butoxy-2-oxoethyl)-4-cyclohexylbutyl]-1,3-oxazole-4-carboxylateAusbeute 64,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24611Copper bromide (CuBr2)KatalysatorHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

A suspension of copper (II) bromide (2.08 g, 9.31 mmol) and hexamethylenetetramine (1.30 g, 9.31 mmol) in degassed dichloromethane (25 ml) was treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (1.39 ml, 9.31 mmol) and then cooled in a cold water bath and stirred for 5 minutes. This suspension was then treated dropwise with a solution of ethyl (4S)-2-{(1R)-1-[2-(tert-butoxy)-2-oxoethyl]-4-cyclohexylbutyl}-4,5-dihydro-1,3-oxazole-4-carboxylate (Preparation 61) (0.92 g, 2.33 mmol) in dichloromethane (5 ml) and the resulting mixture was stirred at room temperature under a nitrogen atmosphere for 17 hours. The solvent was removed under reduced pressure and the residue partitioned between ethyl acetate and a solution of 0.88 ammonia:saturated aqueous solution of ammonium chloride (1:1, 100 mls). The layers were separated and the aqueous layer was extracted with ethyl acetate (×2). The organic layers were combined, washed sequentially with hydrochloric acid (2M), saturated aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous magnesium sulphate, filtered and the solvent removed under reduced pressure. The residue was purified by column chromatography on silica gel eluting with ethyl acetate:pentane (10:90) to afford the title compound as a pale yellow oil (0.59 g).

Aufarbeitung

  1. temperaturecooled in a cold water bath
  2. stirringthe resulting mixture was stirred at room temperature under a nitrogen atmosphere for 17 hours
  3. customThe solvent was removed under reduced pressure
  4. customthe residue partitioned between ethyl acetate
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with ethyl acetate (×2)
  7. washwashed sequentially with hydrochloric acid (2M), saturated aqueous sodium hydrogen carbonate solution and brine
  8. dry with materialdried over anhydrous magnesium sulphate
  9. filtrationfiltered
  10. customthe solvent removed under reduced pressure
  11. customThe residue was purified by column chromatography on silica gel eluting with ethyl acetate:pentane (10:90)

Quellen und Nachweise

ORD-Eintrag
ord-68ee65c8c3554702bb2447c8c9ee67b7
Quelldatensatz
uspto-grants-2005_05
Patentnummer
US06897306B2

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