Ammonia → 4-tert-Butyl-3,6-dichloropyridazine

HRID 986912

反応式

HRID 986912 の反応式
S(=O)(=O)(O)O.[Cl:6][C:7]1[N:8]=[N:9][C:10]([Cl:13])=[CH:11][CH:12]=1.[CH3:14][C:15](C)([CH3:19])[C:16](O)=O.S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+].N>O.[N+]([O-])([O-])=O.[Ag+]>[Cl:6][C:7]1[N:8]=[N:9][C:10]([Cl:13])=[CH:11][C:12]=1[C:15]([CH3:19])([CH3:16])[CH3:14]

参加物

8

反応物 5

HCID 222AmmoniaHCID 1118Sulfuric AcidHCID 6417Pivalic acidHCID 62648Ammonium PersulfateHCID 673313,6-Dichloropyridazine

生成物 1

HCID 898464-tert-Butyl-3,6-dichloropyridazine収率 53.5%

試薬・触媒・溶媒 2

HCID 24470Silver Nitrate触媒HCID 962Water溶媒3 回

反応条件

温度
70 °C

実験手順

Concentrated sulphuric acid (53.6 ml, 1.0 mol) was added carefully to a stirred suspension of 3,6-dichloropyridazine (50.0 g, 0.34 mol) in water (1.25 l). This mixture was then heated to 70° C. (internal temperature) before the addition of trimethylacetic acid (47.5 ml, 0.41 mol). A solution of silver nitrate (11.4 g, 0.07 mol) in water (20 ml) was then added over approximately one minute. This caused the reaction mixture to become milky in appearance. A solution of ammonium persulphate (230 g, 1.0 mol) in water (0.63 l) was then added over 20-30 minutes. The internal temperature rose to approximately 85° C. During the addition the product formed as a sticky precipitate. Upon complete addition the reaction was stirred for an additional 10 minutes, then allowed to cool to room temperature. The mixture was then poured onto ice and basified with concentrated aqueous ammonia, with the addition of more ice as required to keep the temperature below 10° C. The aqueous was extracted with dichloromethane (3×300 ml). The combined extracts were dried (MgSO4), filtered and evaporated to give 55.8 g of crude product as an oil. This was purified by silica gel chromatography using 0-15% ethyl acetate in hexane as eluent to give 37.31 g (53%) of the desired compound. Data for the title compound: 1H NMR (360 MHz, d6-DMSO) δ1.50 (9H, s), 7.48 (1H, s); MS (ES+) m/e 205 [MH]+, 207 [MH]+.

後処理

  1. customrose to approximately 85° C
  2. additionDuring the addition the product
  3. customformed as a sticky precipitate
  4. additionUpon complete addition the reaction
  5. temperatureto cool to room temperature
  6. customthe temperature below 10° C
  7. extractionThe aqueous was extracted with dichloromethane (3×300 ml)
  8. dry with materialThe combined extracts were dried (MgSO4)
  9. filtrationfiltered
  10. customevaporated
  11. customto give 55.8 g of crude product as an oil
  12. customThis was purified by silica gel chromatography

出典と根拠

ORDレコード
ord-885c3d0eabf14797a277326d95d201e0
出典データセット
uspto-grants-2003_10
特許番号
US06630471B1

関連ノート

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