Sodium Bicarbonate → 5-((1E,4Z)-cyclohepta-1,4-dienyl)-1-methyl-4-nitro-1H-pyrazole

HRID 1915812ノート

反応式

HRID 1915812 の反応式
[CH3:1][N:2]1[C:6]([C:7]2(O)[CH2:13][CH2:12][CH:11]=[CH:10][CH2:9][CH2:8]2)=[C:5]([N+:15]([O-:17])=[O:16])[CH:4]=[N:3]1.COCCN(S(F)(F)F)CCOC.C([O-])(O)=O.[Na+]>C(Cl)Cl.C1COCC1>[C:7]1([C:6]2[N:2]([CH3:1])[N:3]=[CH:4][C:5]=2[N+:15]([O-:17])=[O:16])=[CH:8][CH2:9][CH:10]=[CH:11][CH2:12][CH2:13]1

参加物

6

反応物 3

HCID 516892Sodium BicarbonateHCID 2734690(Bis(2-methoxyethyl)amino)sulfur trifluorideHCID 86680017(Z)-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)cyclohept-4-enol

生成物 1

HCID 866800185-((1E,4Z)-cyclohepta-1,4-dienyl)-1-methyl-4-nitro-1H-pyrazole収率 42%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of (Z)-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)cyclohept-4-enol (1.35 g, 5.70 mmol) in dry DCM (60 mL) was added dropwise a solution of deoxo-Fluor® (50% in THF, 6.2 mL, 17.1 mmol) and the reaction mixture was stirred at room temperature for 90 min. The mixture was cooled to 0° C. and saturated aqueous NaHCO3 solution (70 mL) was added, dropwise initially, and extracted with DCM (100 mL). The organic layer was separated, dried over MgSO4, and concentrated under reduced pressure. Purification via silica gel column chromatography (15-20% EtOAc/hexane) gave 5-((1E,4Z)-cyclohepta-1,4-dienyl)-1-methyl-4-nitro-1H-pyrazole as a pale yellow oil (523 mg, 42%). 1H NMR (400 MHz, CDCl3) δ 8.06 (s, 1H), 5.90 (t, J=5.6 Hz, 1H), 5.88-5.79 (m, 1H), 5.71-5.63 (m, 1H), 3.82 (s, 3H), 3.14-3.08 (m, 2H), 2.62-2.55 (m, 2H), 2.44-2.37 (m, 2H).

後処理

  1. temperatureThe mixture was cooled to 0° C.
  2. extractiondropwise initially, and extracted with DCM (100 mL)
  3. customThe organic layer was separated
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customPurification via silica gel column chromatography (15-20% EtOAc/hexane)

出典と根拠

ORDレコード
ord-e224b688cd474d76b404dcf6e874832d
出典データセット
uspto-grants-2013_12
特許番号
US08614206B2

反応ノート

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