Nitrogen → 1-[4-(2-Methyl-[1,3]dioxolan-2-yl)-butyl]-3-nitro-1H-pyrazole

HRID 2064935

反応式

HRID 2064935 の反応式
N#N.[N+:3]([C:6]1[NH:10][N:9]=[CH:8][CH:7]=1)([O-:5])=[O:4].C([O-])([O-])=O.[Cs+].[Cs+].Br[CH2:18][CH2:19][CH2:20][CH2:21][C:22]1([CH3:27])[O:26][CH2:25][CH2:24][O:23]1>C(C#N)(C)=O.CC(=O)OCC.O>[CH3:27][C:22]1([CH2:21][CH2:20][CH2:19][CH2:18][N:9]2[CH:8]=[CH:7][C:6]([N+:3]([O-:5])=[O:4])=[N:10]2)[O:26][CH2:25][CH2:24][O:23]1

参加物

8

反応物 4

HCID 947NitrogenHCID 10796Cesium carbonateHCID 1234193-NitropyrazoleHCID 5600132-(4-Bromobutyl)-2-methyl-1,3-dioxolane

生成物 1

HCID 669283351-[4-(2-Methyl-[1,3]dioxolan-2-yl)-butyl]-3-nitro-1H-pyrazole

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 694302-Oxopropiononitrile溶媒2 回

反応条件

温度
80 °C

実験手順

In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), a solution of 5-nitro-1H-pyrazole (2.97 g, 18.68 mmol) and Cs2CO3 (6.67 g, 26.22 mmol) in AcCN (27.0 mL) was treated with a solution of 2-(4-bromo-butyl)-2-methyl-[1,3]dioxolane (5.85 g, 26.22 mmol) in AcCN (27.0 mL). The reaction mixture was stirred at 80° C. for 2.5 h. Water (100 mL) and EA (200 mL) were added to the cooled reaction mixture. The aq. layer was extracted with EA (100 mL) and the combined org. extracts were dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (60:40 hept-EA) gave the title compound. TLC: rf (60:40 hept-EA)=0.17. LC-MS-conditions 02: tR=0.89 min; [M+H]+=256.32. 1H NMR (400 MHz, CDCl3) δ 1.31 (s, 3H), 1.39-1.50 (m, 2H), 1.67-1.75 (m, 2H), 1.92-2.02 (m, 2H), 3.88-3.94 (m, 2H), 3.94-4.00 (m, 2H), 4.22 (t, J=7.0 Hz, 2H), 6.91 (d, J=2.3 Hz, 1H), 7.46 (d, J=2.3 Hz, 1H).

後処理

  1. extractionThe aq. layer was extracted with EA (100 mL)
  2. dry with materialextracts were dried over MgSO4
  3. filtrationfiltered
  4. customthe solvents were removed under reduced pressure
  5. customPurification of the residue by FC (60:40 hept-EA)

出典と根拠

ORDレコード
ord-37768abc908d4f96b70773ef81fcb7bd
出典データセット
uspto-grants-2012_10
特許番号
US08288419B2

関連ノート

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