Sulfuric Acid → 3,6-Dichloro-4-(2,2-dichloro-1-methylcyclopropyl)pyridazine

HRID 414215

反応式

HRID 414215 の反応式
[Cl:1][C:2]1[N:3]=[N:4][C:5]([Cl:8])=[CH:6][CH:7]=1.[Cl:9][C:10]1([Cl:17])[CH2:12][C:11]1(C)[C:13](O)=O.S(=O)(=O)(O)O.S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+].[OH-].[NH4+]>[N+]([O-])([O-])=O.[Ag+].O>[Cl:1][C:2]1[N:3]=[N:4][C:5]([Cl:8])=[CH:6][C:7]=1[C:11]1([CH3:13])[CH2:12][C:10]1([Cl:17])[Cl:9]

参加物

8

反応物 5

HCID 1118Sulfuric AcidHCID 14923Ammonium HydroxideHCID 62648Ammonium PersulfateHCID 673313,6-DichloropyridazineHCID 1026212,2-Dichloro-1-methylcyclopropanecarboxylic acid

生成物 1

HCID 143498363,6-Dichloro-4-(2,2-dichloro-1-methylcyclopropyl)pyridazine

試薬・触媒・溶媒 2

HCID 24470Silver Nitrate触媒HCID 962Water溶媒3 回

実験手順

A 3.5 g. portion of 3,6-dichloropyridazine was slurried with 4.0 g. of 2,2-dichloro-1-methylcyclopropanecarboxylic acid, 15 ml. of water, 3.4 g. of concentrated sulfuric acid in 20 ml. of water, and 4.0 g. of silver nitrate, and the mixture was heated to 65° with rapid stirring. To it was added 11.9 g. of ammonium persulfate in 20 ml. of water, over 20 minutes, while the temperature was held at 70°-76°. The mixture was stirred 15 minutes after the addition and cooled to 10°. Its pH was adjusted to 8.0 with ammonium hydroxide, and the water layer was then decanted off. The remaining solids were washed twice with 100 ml. portions of diethyl ether, and that ether was then used to extract the water layer. The organic layer was washed with 1N sodium hydroxide and with brine, and dried. The solvent was removed under vacuum, and the residue was purified by chromatography, eluting with 3:1 heptane:ethyl acetate. The product-containing fractions were combined and evaporated, and the residue was recrystallized from heptane, to obtain 0.52 g. of the desired product, m.p. 78°-79°.

後処理

  1. additionTo it was added 11.9 g
  2. customwas held at 70°-76°
  3. additionafter the addition
  4. temperaturecooled to 10°
  5. customthe water layer was then decanted off
  6. washThe remaining solids were washed twice with 100 ml
  7. extractionto extract the water layer
  8. washThe organic layer was washed with 1N sodium hydroxide and with brine
  9. customdried
  10. customThe solvent was removed under vacuum
  11. customthe residue was purified by chromatography
  12. washeluting with 3:1 heptane
  13. customevaporated
  14. customthe residue was recrystallized from heptane
  15. customto obtain 0.52 g

出典と根拠

ORDレコード
ord-8520f1702dc845749ca8922d1996b242
出典データセット
uspto-grants-1988_12
特許番号
US04791110

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