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

HRID 75171ノート

反応式

HRID 75171 の反応式
[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

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6422Trifluoroacetic acid溶媒

反応条件

温度
50 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-773be965097747278da923c4f415f9ce
出典データセット
uspto-grants-2014_09
特許番号
US08835427B2

反応ノート

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