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

HRID 389441

反応式

HRID 389441 の反応式
[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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6228Dimethylformamide溶媒3 回

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-93f7041281e542e897e68f041a72c992
出典データセット
uspto-grants-2013_02
特許番号
US08378104B2

関連ノート

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