Ethyl Acetate → (6-Chloropyridazin-3-yl)methanol

HRID 242152

反応式

HRID 242152 の反応式
[Cl:1][C:2]1[N:7]=[N:6][C:5]([C:8](O)=[O:9])=[CH:4][CH:3]=1.S(Cl)(Cl)=O.[BH4-].[Na+].C(OCC)(=O)C>C1(C)C=CC=CC=1.O>[Cl:1][C:2]1[N:7]=[N:6][C:5]([CH2:8][OH:9])=[CH:4][CH:3]=1

参加物

7

反応物 4

HCID 8857Ethyl AcetateHCID 24386Thionyl ChlorideHCID 4311764Sodium borohydrideHCID 64157626-chloropyridazine-3-carboxylic Acid

生成物 1

HCID 20557609(6-Chloropyridazin-3-yl)methanol

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 1140Toluene溶媒

反応条件

温度
60 °C

実験手順

4.3 g (21.4 mmol) of 6-chloropyridazine-3-carboxylic acid are dissolved in 60 ml of dry toluene and heated to 60° C. At this temperature, 3.8 g (32.2 mmol) of thionyl chloride are added, and the mixture is stirred at this temperature for 3 h. The mixture is then heated at reflux for 4 h. After cooling to RT, the solvent is removed on a rotary evaporator. 20 ml of toluene are added, and the mixture is again evaporated to dryness. The residue is dissolved in 40 ml of methyl tert-butyl ether and cooled to 5° C. At this temperature, a solution of 1.7 g (47.2 mmol) of sodium borohydride in 37 ml of water is added dropwise. The mixture is stirred at RT for 20 h. 50 ml of ethyl acetate are then added, and the aqueous phase is extracted three times with in each case 10 ml of ethyl acetate. The combined organic phases are washed in each case twice with in each case 10 ml of sat. sodium bicarbonate solution and water. The solvent is removed on a rotary evaporator and the residue is purified chromatographically on silica gel 60 (mobile phase: gradient dichloromethane/ethanol 100:1→20:1).

後処理

  1. temperatureThe mixture is then heated
  2. temperatureat reflux for 4 h
  3. temperatureAfter cooling to RT
  4. customthe solvent is removed on a rotary evaporator
  5. addition20 ml of toluene are added
  6. customthe mixture is again evaporated to dryness
  7. dissolutionThe residue is dissolved in 40 ml of methyl tert-butyl ether
  8. temperaturecooled to 5° C
  9. stirringThe mixture is stirred at RT for 20 h
  10. extractionthe aqueous phase is extracted three times with in each case 10 ml of ethyl acetate
  11. washThe combined organic phases are washed in each case twice with in each case 10 ml of sat. sodium bicarbonate solution and water
  12. customThe solvent is removed on a rotary evaporator
  13. customthe residue is purified chromatographically on silica gel 60 (mobile phase: gradient dichloromethane/ethanol 100:1→20:1)

出典と根拠

ORDレコード
ord-3fd82016978b4fd29e041774b9703100
出典データセット
uspto-grants-2014_02
特許番号
US08653109B2

関連ノート

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