Acetic Acid → {2-[4-(4-tert-Butoxycarbonylaminobutyl)phenoxy]ethylamino}acetic acid ethyl ester

HRID 1509866Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1509866
[C:1]([OH:4])(=[O:3])[CH3:2].[C:5]([O:9][C:10](=[O:26])[NH:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]1[CH:21]=[CH:20][C:19]([O:22][CH2:23][CH2:24][NH2:25])=[CH:18][CH:17]=1)([CH3:8])([CH3:7])[CH3:6].C([BH3-])#N.[Na+].O1CC[CH2:33][CH2:32]1>O>[CH2:32]([O:3][C:1](=[O:4])[CH2:2][NH:25][CH2:24][CH2:23][O:22][C:19]1[CH:18]=[CH:17][C:16]([CH2:15][CH2:14][CH2:13][CH2:12][NH:11][C:10]([O:9][C:5]([CH3:8])([CH3:6])[CH3:7])=[O:26])=[CH:21][CH:20]=1)[CH3:33]

Komponenten

6

Edukt 4

HCID 176Acetic AcidHCID 8028TetrahydrofuranHCID 5003444Sodium cyanoborohydrideHCID 588097964-[4-(2-Aminoethoxy)phenyl]-butylcarbamic acid tert-butyl ester

Produkt 1

HCID 58809798{2-[4-(4-tert-Butoxycarbonylaminobutyl)phenoxy]ethylamino}acetic acid ethyl esterAusbeute 38 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

Dimethylacetone dicarboxylate (1.43 mL, 9.69 mmol) and glacial acetic acid (0.56 mL, 9.70 mmol) were added sequentially to a solution of {4-[4-(2-aminoethoxy)phenyl]-butylcarbamic acid tert-butyl ester (1) (1.0 g, 3.24 mmol) in tetrahydrofuran (20 mL). The reaction was stirred for 2 hours at ambient temperature, then cooled to −30° C. Sodium cyanoborohydride (0.61 g, 9.70 mmol) was added in three portions and the reaction slowly warmed to room temperature over 12 hours. After this time, the reaction was quenched by the addition of water (5 mL). The volatiles was then removed under vacuum to give an oil. This oil was diluted with water (10 mL) and extracted with ethyl acetate (3×10 mL). The combined organics were washed with water (3×10 mL) and then brine (3×10 mL), dried over anhydrous sodium sulfate and concentrated to give 2 (0.576 g, 38% yield) as a clear oil: 1H NMR (500 MHz, CDCl3) δ 1.44 (s, 9H), 1.46-1.52 (m, 2H), 1.55-1.64 (m, 2H), 2.56-2.58 (m, 4H), 2.64-2.65 (m, 2H), 2.72-2.79 (m, 2H), 2.88-2.93 (m, 2H), 3.74 (d, 6H), 3.88-3.93 (m, 1H), 4.44-4.49 (m, 2H), 6.40 (br, 1H), 6.85 (d, 2H), 7.09 (d, 2H); m/z (ESI) 467.

Aufarbeitung

  1. temperaturecooled to −30° C
  2. customthe reaction
  3. temperatureslowly warmed to room temperature over 12 hours
  4. customAfter this time, the reaction was quenched by the addition of water (5 mL)
  5. customThe volatiles was then removed under vacuum
  6. customto give an oil
  7. extractionextracted with ethyl acetate (3×10 mL)
  8. washThe combined organics were washed with water (3×10 mL)
  9. dry with materialbrine (3×10 mL), dried over anhydrous sodium sulfate
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-dbf556f17ff24b839b75b7a030abf43c
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08211895B2

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