Water → 1-(1,4-Dioxaspiro[4.5]dec-8-yl)-4-iodo-1H-pyrazole

HRID 389441

Reaktionsgleichung

Reaktionsgleichung von HRID 389441
[H-].[Na+].[I:3][C:4]1[CH:5]=[N:6][NH:7][CH:8]=1.CS(O[CH:14]1[CH2:23][CH2:22][C:17]2([O:21][CH2:20][CH2:19][O:18]2)[CH2:16][CH2:15]1)(=O)=O.O>CN(C=O)C.CO>[O:18]1[C:17]2([CH2:22][CH2:23][CH:14]([N:6]3[CH:5]=[C:4]([I:3])[CH:8]=[N:7]3)[CH2:15][CH2:16]2)[O:21][CH2:20][CH2:19]1

Komponenten

7

Edukt 4

HCID 962Water2×HCID 24758Sodium hydrideHCID 770224-IodopyrazoleHCID 149667411,4-Dioxaspiro(4.5)decan-8-yl methanesulfonate

Produkt 1

HCID 595411251-(1,4-Dioxaspiro[4.5]dec-8-yl)-4-iodo-1H-pyrazoleAusbeute 66 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 887MethanolLösungsmittelHCID 6228DimethylformamideLösungsmittel3×

Versuchsvorschrift

A suspension of sodium hydride (72.6 mg, 1.82 mmol) in DMF (1 mL); was cooled in an ice/water bath and treated with a solution of 4-iodopyrazole (242 mg, 1.21 mmol) in DMF (2 mL) added dropwise under an atmosphere of nitrogen in 5 min. After stirring in the cold for another 30 min, a solution of 1,4-dioxaspiro[4.5]dec-8-yl methanesulfonate (321 mg, 1.33 mmol) in DMF (2 mL) was added dropwise at 0° C. The mixture was warmed to RT and was then immersed in 150° C. oil bath and stirred for 2 h. The mixture was treated with water (15 mL), extracted with EtOAc (3×20 mL). The extracts were washed with water (3×15 mL), brine (15 mL), dried over MgSO4. After concentration in vacuo, a brown solid was obtained. It was dissolved in MeOH and after water was added, a solid formed, which was filtered off to give 266 mg (66%) of the title compound as a white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 7.50 (s, 1 H), 7.49 (s, 1 H), 4.23 (tt, J=4.2, 11.2 Hz, 1 H), 2.34-2.20 (m, 1 H), 2.21-1.96 (m, 4 H), 1.95-1.81 (m, 2 H), 1.82-1.66 (m, 3 H), 1.33-1.22 (m, 2 H); MS (ESI): 334.96 [M+H]+; HPLC tR=3.26 min.

Aufarbeitung

  1. temperaturewas cooled in an ice/water bath
  2. additionadded dropwise under an atmosphere of nitrogen in 5 min
  3. customwas then immersed in 150° C.
  4. stirringstirred for 2 h
  5. extractionextracted with EtOAc (3×20 mL)
  6. washThe extracts were washed with water (3×15 mL), brine (15 mL)
  7. dry with materialdried over MgSO4
  8. concentrationAfter concentration in vacuo
  9. customa brown solid was obtained
  10. customa solid formed
  11. filtrationwhich was filtered off

Quellen und Nachweise

ORD-Eintrag
ord-93f7041281e542e897e68f041a72c992
Quelldatensatz
uspto-grants-2013_02
Patentnummer
US08378104B2

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