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

HRID 242152

반응식

HRID 242152 반응식
[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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 1140Toluene용매

반응 조건

온도
60 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-3fd82016978b4fd29e041774b9703100
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08653109B2

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