Azetidine → Azetidin-1-yl(2-methyl-4-nitro-2H-pyrazol-3-yl)methanone

HRID 467765

Reaktionsgleichung

Reaktionsgleichung von HRID 467765
[CH3:1][N:2]1[C:6]([C:7]([OH:9])=O)=[C:5]([N+:10]([O-:12])=[O:11])[CH:4]=[N:3]1.[NH:13]1[CH2:16][CH2:15][CH2:14]1.C(N(C(C)C)CC)(C)C.CCCP1(OP(CCC)(=O)OP(CCC)(=O)O1)=O>C(OCC)(=O)C>[N:13]1([C:7]([C:6]2[N:2]([CH3:1])[N:3]=[CH:4][C:5]=2[N+:10]([O-:12])=[O:11])=[O:9])[CH2:16][CH2:15][CH2:14]1

Komponenten

6

Edukt 4

HCID 10422AzetidineHCID 81531DiisopropylethylamineHCID 111923Propylphosphonic anhydrideHCID 5926231-Methyl-4-nitro-1H-pyrazole-5-carboxylic acid

Produkt 1

HCID 70096944Azetidin-1-yl(2-methyl-4-nitro-2H-pyrazol-3-yl)methanoneAusbeute 73,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To a suspension of 2-methyl-4-nitro-2H-pyrazole-3-carboxylic acid (300 mg, 1.75 mmol), azetidine (354 μl, 5.25 mmol) and diisopropylethylamine (920 μl, 5.26 mmol) in ethyl acetate (7.5 ml) was added 1-propanephosphonic acid cyclic anhydride (3.68 ml, 6.13 mmol; 50% in ethyl acetate) at 0° C. The ice bath was removed and stirring at r.t. was continued for 40 h. The reaction mixture was poured into ethyl acetate (100 ml) and extracted with sodium bicarbonate (saturated aqueous solution) water and brine. The aqueous layer was back-extracted with ethyl acetate, the combined organic phases were dried, evaporated, and the product was purified by silica gel chromatography using an amine phase and a heptane/ethyl acetate gradient to yield a white solid (269 mg, 73%).

Aufarbeitung

  1. customThe ice bath was removed
  2. additionThe reaction mixture was poured into ethyl acetate (100 ml)
  3. extractionextracted with sodium bicarbonate (saturated aqueous solution) water and brine
  4. extractionThe aqueous layer was back-extracted with ethyl acetate
  5. customthe combined organic phases were dried
  6. customevaporated
  7. customthe product was purified by silica gel chromatography

Quellen und Nachweise

ORD-Eintrag
ord-c2cf414c53c4417d83812f8997482572
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08623866B2

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