tert-Butanol → (S)-1-(2-Bromo-6-methyl-4-nitrophenyl)ethane-1,2-diol

HRID 879269Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 879269
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([CH3:11])[C:3]=1C=C.[C:14]([O-:17])([O-])=O.[K+].[K+].CS(N)(=O)=O.[O-]S([O-])=O.[Na+].[Na+].C[C:32]([OH:35])(C)C>O.CC[C@H]1[C@H]2C[C@H]([C@H](OC3C4C(=CC=CC=4)C(O[C@H](C4C=CN=C5C=4C=C(OC)C=C5)[C@@H]4N5C[C@H](CC)[C@@H](CC5)C4)=NN=3)C3C=CN=C4C=3C=C(OC)C=C4)N(CC2)C1>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([CH3:11])[C:3]=1[C@H:14]([OH:17])[CH2:32][OH:35]

Komponenten

8

Edukt 5

HCID 6386tert-ButanolHCID 11430Potassium CarbonateHCID 24437Sodium SulfiteHCID 72879MethanesulfonamideHCID 866997861-Bromo-3-methyl-5-nitro-2-vinylbenzene

Produkt 1

HCID 70982486(S)-1-(2-Bromo-6-methyl-4-nitrophenyl)ethane-1,2-diolAusbeute 50 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 510036741-((1R)-((2R,4R,5S)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)-4-((1R)-((2R,4S,5R)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)phthalazineKatalysatorHCID 962WaterLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

The reaction mixture of 1-Bromo-3-methyl-5-nitro-2-vinylbenzene (30.0 g, 0.124 mol), AD-mix α (173.5 g: 0.104 g of K2OsO4.2H2O; 1.389 g of (DHQ)2PHAL; 51.038 g of K2CO3 and 120.99 g of K4Fe(CN)6), MeSO2NH2 (11.8 g, 0.124 mol) in t-BuOH (250 mL) and H2O (250 mL) was stirred at 0° C. for 3 days. Na2SO3 (15 g) was added and stirred at room temperature for 40 min to quench the reaction. The reaction mixture was treated with water (1 L) and the resulting mixture was extracted with EtOAc (3×200 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered, concentrated in vacuo, and purified by silica gel column (Petroleum Ether:EtOAc (2:1), isocratic) to afford (S)-1-(2-Bromo-6-methyl-4-nitrophenyl)ethane-1,2-diol (17 g, 50%) as yellow solid. 1H-NMR: 400 MHz, (CDCl3) δ: 8.26 (s, 1H), 7.99 (s, 1H), 5.56-5.54 (m, 1H), 3.94-3.92 (m, 1H), 3.81-3.78 (m, 1H), 2.82 (d, broad, 1H), 2.67 (s, 3H), 2.18-2.15 (m, 1H).

Aufarbeitung

  1. stirringstirred at room temperature for 40 min
  2. customto quench
  3. customthe reaction
  4. extractionthe resulting mixture was extracted with EtOAc (3×200 mL)
  5. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. custompurified by silica gel column (Petroleum Ether:EtOAc (2:1), isocratic)

Quellen und Nachweise

ORD-Eintrag
ord-b119e15b0a6a48178b356afbe37ac2e5
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08987250B2

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