Sodium hydride → 1-(4-chlorophenoxy)-3,3-dimethyl-2-(N-methyl-N-trichloromethylmercapto-carbamoyloxy)-1-(1,2,4-triazol-1-yl)-butane

HRID 1732885

反応式

HRID 1732885 の反応式
[Cl:1][C:2]1[CH:20]=[CH:19][C:5]([O:6][CH:7]([N:14]2[CH:18]=[N:17][CH:16]=[N:15]2)[CH:8]([OH:13])[C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:4][CH:3]=1.[H-].[Na+].[CH3:23][N:24]([S:28][C:29]([Cl:32])([Cl:31])[Cl:30])[C:25](F)=[O:26].[Na]>O1CCCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:6][CH:7]([N:14]2[CH:18]=[N:17][CH:16]=[N:15]2)[CH:8]([O:13][C:25](=[O:26])[N:24]([CH3:23])[S:28][C:29]([Cl:32])([Cl:31])[Cl:30])[C:9]([CH3:11])([CH3:12])[CH3:10])=[CH:19][CH:20]=1

参加物

6

反応物 4

HCID 24758Sodium hydrideHCID 41368TriadimenolHCID 5360545SodiumHCID 12836648Methyl[(trichloromethyl)sulfanyl]carbamyl fluoride

生成物 1

HCID 867373901-(4-chlorophenoxy)-3,3-dimethyl-2-(N-methyl-N-trichloromethylmercapto-carbamoyloxy)-1-(1,2,4-triazol-1-yl)-butane収率 38.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

22.3 g (0.075 mol) of 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol, in the form of the pure diastereomer, were dissolved in 200 ml of tetrahydrofuran and the solution was added dropwise to 2.3 g of 80% pure sodium hydride in 150 ml of tetrahydrofuran at room temperature, while stirring. Thereafter, the mixture was stirred at 50° C. for 12 hours. After cooling, 17 g (0.075 mol) of N-methyl-N-trichloromethylmercaptocarbamoyl fluoride were added dropwise, at room temperature, to the sodium salt thus obtained, whereupon the temperature rose to about 35° C. The mixture was then heated under reflux for 16 hours, left to cool and concentrated by distilling off the solvent. The oily residue was taken up in 500 ml of methylene chloride, washed twice with 1,000 ml of water each time, dried over sodium sulphate and concentrated. The oil which remained was taken up in 300 ml of isopropyl ether, whereupon it crystallized out. 14.5 g (37% of theory) of 1-(4-chlorophenoxy)-3,3-dimethyl-2-(N-methyl-N-trichloromethylmercapto-carbamoyloxy)-1-(1,2,4-triazol-1-yl)-butane were obtained in the form of the pure diastereomer of melting point 110°-112° C.

後処理

  1. stirringThereafter, the mixture was stirred at 50° C. for 12 hours
  2. temperatureAfter cooling
  3. customthus obtained, whereupon the temperature
  4. customrose to about 35° C
  5. temperatureThe mixture was then heated
  6. temperatureunder reflux for 16 hours
  7. waitleft
  8. temperatureto cool
  9. concentrationconcentrated
  10. distillationby distilling off the solvent
  11. washwashed twice with 1,000 ml of water each time
  12. dry with materialdried over sodium sulphate
  13. concentrationconcentrated
  14. customcrystallized out

出典と根拠

ORDレコード
ord-010e7313fce5450e928430ebe46a8d9c
出典データセット
uspto-grants-1980_12
特許番号
US04239766

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