Thioacetamide → 1,2-Diethyl 4-(aminothioxomethyl)tetrahydro-1,2-pyridazinedicarboxylate

HRID 75171Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 75171
[C:1]([CH:3]1[CH2:8][CH2:7][N:6]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[N:5]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:4]1)#[N:2].C(N)(=[S:21])C>FC(F)(F)C(O)=O>[NH2:2][C:1](=[S:21])[CH:3]1[CH2:8][CH2:7][N:6]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[N:5]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:4]1

Komponenten

4

Edukt 2

HCID 2723949ThioacetamideHCID 710737831,2-Diethyl 4-cyanotetrahydro-1,2-pyridazinedicarboxylate2×

Produkt 1

HCID 866744641,2-Diethyl 4-(aminothioxomethyl)tetrahydro-1,2-pyridazinedicarboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6422Trifluoroacetic acidLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

A mixture of 1,2-diethyl 4-cyanotetrahydro-1,2-pyridazinedicarboxylate (i.e the product of Step E) (5.5 g, 0.024 mol) and thioacetamide (5.5 g, 0.073 mol) in trifluoroacetic acid (about 10 mL) was heated at 50° C. for 20 h. The reaction mixture was cooled, and then partitioned between water and diethyl ether (about 30 mL). The layers were separated and the aqueous layer was extracted with diethyl ether (2×). The combined organic extracts were washed with water (about 30 mL), dried magnesium sulfate, filtered and concentrated under reduce pressure to an orange oil. The oil was adsorbed onto Celite® (diatomaceous filter aid), and then purified by silica gel column chromatography (25% to 60% gradient of ethyl acetate in petroleum ether as eluant) to provide the title compound as a yellow solid (3.97 g).

Aufarbeitung

  1. temperatureThe reaction mixture was cooled
  2. custompartitioned between water and diethyl ether (about 30 mL)
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with diethyl ether (2×)
  5. washThe combined organic extracts were washed with water (about 30 mL), dried magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified by silica gel column chromatography (25% to 60% gradient of ethyl acetate in petroleum ether as eluant)

Quellen und Nachweise

ORD-Eintrag
ord-773be965097747278da923c4f415f9ce
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08835427B2

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