Iodine → tert-Butyl (6-chloro-4-iodopyridin-3-yl)carbamate

HRID 859772

Reaktionsgleichung

Reaktionsgleichung von HRID 859772
[Li]CCCC.[C:6]([O:10][C:11](=[O:20])[NH:12][C:13]1[CH:14]=[N:15][C:16]([Cl:19])=[CH:17][CH:18]=1)([CH3:9])([CH3:8])[CH3:7].CN(CCN(C)C)C.[I:29]I>CCOCC>[C:6]([O:10][C:11](=[O:20])[NH:12][C:13]1[CH:14]=[N:15][C:16]([Cl:19])=[CH:17][C:18]=1[I:29])([CH3:9])([CH3:7])[CH3:8]

Komponenten

6

Edukt 4

HCID 807IodineHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 7330593(6-Chloro-pyridin-3-yl)-carbamic acid tert-butyl esterHCID 178418339Butyllithium

Produkt 1

HCID 53415320tert-Butyl (6-chloro-4-iodopyridin-3-yl)carbamateAusbeute 56 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel2×

Reaktionsbedingungen

Temperatur
-10 °C

Versuchsvorschrift

n-BuLi (52.4 mL, 0.12 mol, 2.5 M soln in hexanes) was added dropwise over 30 mins to a cooled −78° C. solution of (6-chloro-pyridin-3-yl)-carbamic acid tert-butyl ester (10.0 g, 43.7 mmol) and TMEDA (19.8 mL, 0.13 mol) dissolved in ether. The solution was warmed to −10° C., stirred for 2 hours and then recooled to −78° C. A solution of iodine (22.75 g, 90 mmol) in ether (100 mL) was added via an addition funnel and the reaction was warmed to room temperature and stirred for 16 hours. The reaction was quenched with sat NH4Cl and sodium thiosulfite was added. The mixture was stirred for 30 mins and then extracted with ether. The organic extracts were washed with sodium thiosulfite, dried over MgSO4, filtered and concentrated. Purification by silica gel chromatography (0% to 15% EtOAc in hexanes) gave the product (8.6 g, 56%). 1H NMR (300 MHz, CDCl3): δ 1.52 (s, 9 H), 6.58 (s, 1 H), 7.26 (d, J=8.6 Hz, 1 H), 7.96 (m, 1 H), 8.23 (d, J=2.8 Hz, 1 H).

Aufarbeitung

  1. customrecooled to −78° C
  2. temperaturethe reaction was warmed to room temperature
  3. stirringstirred for 16 hours
  4. customThe reaction was quenched with sat NH4Cl and sodium thiosulfite
  5. additionwas added
  6. stirringThe mixture was stirred for 30 mins
  7. extractionextracted with ether
  8. washThe organic extracts were washed with sodium thiosulfite
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by silica gel chromatography (0% to 15% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-97754ac5224947b7add1b40b8f41b7e0
Quelldatensatz
uspto-grants-2006_12
Patentnummer
US07151105B2

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