(+)-Epichlorohydrin → (2S,9S)-2-[(tert-Butoxycarbonyl)amino]-10-chloro-9-hydroxy-7-azadecanoic Acid tert-Butyl Ester

HRID 1068073Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1068073
Cl.[C:2]([O:6][C:7](=[O:22])[C@H:8]([CH2:17][CH2:18][CH2:19][CH2:20][NH2:21])[NH:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])([CH3:5])([CH3:4])[CH3:3].[CH2:23]([C@H:25]1[O:27][CH2:26]1)[Cl:24]>C(Cl)(Cl)Cl.C([O-])(O)=O.[Na+].O>[C:2]([O:6][C:7](=[O:22])[C@@H:8]([NH:9][C:10]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:11])[CH2:17][CH2:18][CH2:19][CH2:20][NH:21][CH2:26][C@H:25]([OH:27])[CH2:23][Cl:24])([CH3:5])([CH3:3])[CH3:4]

Komponenten

6

Edukt 2

HCID 149428(+)-EpichlorohydrinHCID 51358437(S)-tert-Butyl 6-amino-2-((tert-butoxycarbonyl)amino)hexanoate hydrochloride

Produkt 1

HCID 10810670(2S,9S)-2-[(tert-Butoxycarbonyl)amino]-10-chloro-9-hydroxy-7-azadecanoic Acid tert-Butyl EsterAusbeute 39 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6212ChloroformLösungsmittelHCID 516892Sodium BicarbonateLösungsmittel

Versuchsvorschrift

A solution of 3 (4.83 g, 14.3 mmol) in chloroform (100 mL) was extracted with saturated NaHCO3 solution (2×100 mL) and water (100 mL). The organic layer was dried, concentrated, and further dried in vacuo. The resulting oil was dissolved in cyclohexane (26 mL), and (S)-(+)-epichlorohydrin (1.58 g, 17.1 mmol) was added under an Ar atmosphere. The precipitated product was filtered after 27 h, washed with cold cyclohexane, and dried in vacuo to give 12a (2.20 g, 39%) as a fine, white powder: mp 87-88° C.; 1H NMR δ 1.30-1.83 (m, 6H), 1.44 (s, 9H), 1.46 (s, 9H), 2.57-2.66 (m, 3H), 2.77 (dd, 1H, J=12.2, 3.9), 3.51 (dd, 1H, J=11.2, 5.7), 3.56 (dd, 1H, J=11.2, 5.2), 3.84-3.91 (m, 1H), 3.94 (dd, 1H, J=8.6, 5.3); 13C NMR 6 24.6, 28.3, 28.7, 30.0, 32.6, 48.2, 50.3, 53.5, 55.8, 71.1, 80.4, 82.5, 158.1, 173.8; HRMS m/z calcd for C18H36ClN2O5 395.2313, found 395.2303. Anal. calcd. for C18H35ClN2O5: C54.74, H 8.93, Cl 8.98, N 7.09. Found: C 54.80, H. 8.99, Cl 9.02, N 7.08 [α]22D−26.1° (c 1.00, CH3OH).

Aufarbeitung

  1. customThe organic layer was dried
  2. concentrationconcentrated
  3. customfurther dried in vacuo
  4. dissolutionThe resulting oil was dissolved in cyclohexane (26 mL)
  5. filtrationThe precipitated product was filtered after 27 h
  6. washwashed with cold cyclohexane
  7. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-447e88a649b64535b55e347f884d4418
Quelldatensatz
uspto-grants-2001_06
Patentnummer
US06248866B1

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