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Carbon tetrabromide → t-butyl (1R)-2-bromo-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate

HRID 1874624
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1874624
O[CH2:2][C@H:3]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH:12]([CH3:16])[CH2:13][CH2:14][CH3:15])=[CH:6][CH:5]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)[Br:45]>O1CCCC1>[Br:45][CH2:2][C@H:3]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH:12]([CH3:16])[CH2:13][CH2:14][CH3:15])=[CH:6][CH:5]=1
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Komponenten

5

Edukt 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 67433195t-butyl (1R)-2-hydroxy-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate

Produkt 1

HCID 86658396t-butyl (1R)-2-bromo-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamateAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028
Tetrahydrofuran
Lösungsmittel

Versuchsvorschrift

To a solution of t-butyl (1R)-2-hydroxy-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate (15 g, 44.5 mmol), prepared according to the procedure described in example 1, in anhydrous tetrahydrofuran (200 mL) was added triphenylphosphine (17.49 g, 66.7 mmol) and carbon tetrabromide (22.11 g, 66.7 mmol). The reaction mixture was stirred at room temperature for 2 h. The mixture was filtered through a pad of diatomaceous earth (Celite®) and the filtrate was concentrated to afford yellow residue which was purified by column chromatography on silica gel (20→30% ethyl acetate in hexanes) to afford t-butyl (1R)-2-bromo-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate (17.8 g, 100% yield) as a colorless solid: 1H NMR (400 MHz, CDCl3) δ 7.18 (d, J=8.8 Hz, 2H), 6.86 (d, J=8.6 Hz, 2H), 5.05 (br. s., 1H), 4.91 (br. s., 1H), 3.78 (dd, J=8.8, 5.8 Hz, 1H), 3.68 (dd, J=9.1, 6.8 Hz, 1H), 3.65 (d, J=5.0 Hz, 1H), 1.86-1.97 (m, 1H), 1.60 (d, J=7.3 Hz, 1H), 1.42 (s, 9H), 1.14-1.51 (m, 4H), 0.99 (d, J=6.5 Hz, 3H), 0.90 (t, J=7.3 Hz, 3H); LRMS (ESI) m/e 400.2 [(M+H)+, calcd for C19H31NO3Br 400.1].

Aufarbeitung

  1. filtrationThe mixture was filtered through a pad of diatomaceous earth (Celite®)
  2. concentrationthe filtrate was concentrated
  3. customto afford yellow residue which
  4. customwas purified by column chromatography on silica gel (20→30% ethyl acetate in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-1da0129d7e714e038833bb70344968c4
Quelldatensatz
uspto-grants-2012_11
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08304577B2

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