Triethylamine → Benzeneacetonitrile, alpha-hydroxy-3-phenoxy-, (alphaR)-

HRID 1680798

Reaktionsgleichung

Reaktionsgleichung von HRID 1680798
C1([C@H](NC(=O)[O:15][C@@H:16]([C:30]#[N:31])[C:17]2[CH:22]=[CH:21][CH:20]=[C:19]([O:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[CH:18]=2)C)C2C(=CC=CC=2)C=CC=1.C(N(CC)CC)C.Cl[SiH](Cl)Cl.[Cl-].[NH4+]>C1C=CC=CC=1.ClC(Cl)Cl.CCOCC>[C:30]([C@H:16]([OH:15])[C:17]1[CH:22]=[CH:21][CH:20]=[C:19]([O:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH:18]=1)#[N:31]

Komponenten

8

Edukt 4

HCID 8471TriethylamineHCID 24811TrichlorosilaneHCID 25517Ammonium ChlorideHCID 13388456(R)-alpha-cyano-3-phenoxybenzyl (R)-N-1-(1-naphthyl)ethylcarbamate

Produkt 1

HCID 156232Benzeneacetonitrile, alpha-hydroxy-3-phenoxy-, (alphaR)-

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 241BenzeneLösungsmittelHCID 3283Diethyl EtherLösungsmittelHCID 6212ChloroformLösungsmittel

Versuchsvorschrift

To 1.99 g (4.7 mmol) of (R)-α-cyano-3-phenoxybenzyl (R)-N-1-(1-naphthyl)ethylcarbamate in 20 ml of benzene is added 725 μl (525 mg, 5.2 mmol) of triethylamine. The solution, under nitrogen, is stirred while 505 μl (675 mg, 5.0 mmol) of trichlorosilane is added. The reaction is warmed to 50° for 2.5 hours, and is then poured into saturated ammonium chloride and ether. The organic fraction is washed again with saturated ammonium chloride and then with brine (3×), and is dried over sodium sulfate overnight in the freezer. Solvent is removed by rotoevaporation, and the residue is washed repeatedly with hexane to remove the isocyanate. The urea contamination is removed by dissolving the product in ether/hexane (~1:1), and the solvent is then removed. Purification by thin layer chromatography (tlc) on silica gel plates developed in 30% ethylacetate/hexane yields the product, which is then dissolved in trichloromethane. The solvent is removed, giving (R)-α-cyano-3-phenoxybenzyl alcohol, specific rotation [α]D =+15.2° (c=10 mg/ml in acetone).

Aufarbeitung

  1. additionis added
  2. temperatureThe reaction is warmed to 50° for 2.5 hours
  3. washThe organic fraction is washed again with saturated ammonium chloride
  4. dry with materialwith brine (3×), and is dried over sodium sulfate overnight in the freezer
  5. customSolvent is removed by rotoevaporation
  6. washthe residue is washed repeatedly with hexane
  7. customto remove the isocyanate
  8. customThe urea contamination is removed
  9. dissolutionby dissolving the product in ether/hexane (~1:1)
  10. customthe solvent is then removed
  11. customPurification by thin layer chromatography (tlc) on silica gel plates
  12. customyields the product, which
  13. customThe solvent is removed

Quellen und Nachweise

ORD-Eintrag
ord-0c19282b87684f1b87326a6acb72b8e0
Quelldatensatz
uspto-grants-1981_06
Patentnummer
US04276230

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