Hydrogen Peroxide → (+)-1-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazole

HRID 1618081

反応式

HRID 1618081 の反応式
[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([S:9][CH2:10][C:11]([F:14])([F:13])[F:12])=[CH:4][C:3]=1[N:15]1[CH:19]=[N:18][C:17]([C:20]([F:23])([F:22])[F:21])=[N:16]1.C(C1C=C(C(C)(C)C)C=C(/C=N/C(C(C)(C)C)C[OH:42])C=1O)(C)(C)C.OO.S([O-])([O-])(=O)=S>C(Cl)(Cl)Cl.C/C(/O)=C/C(C)=O.C/C(/O)=C/C(C)=O.C/C(/O)=C/C(C)=O.[V].O>[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([S:9]([CH2:10][C:11]([F:12])([F:14])[F:13])=[O:42])=[CH:4][C:3]=1[N:15]1[CH:19]=[N:18][C:17]([C:20]([F:22])([F:23])[F:21])=[N:16]1

参加物

8

反応物 4

HCID 784Hydrogen PeroxideHCID 1084Thiosulfate ionHCID 581526941-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazoleHCID 178441014HCID 178441014、化合物2 回

生成物 1

HCID 44178229(+)-1-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazole収率 98%

試薬・触媒・溶媒 3

HCID 5377225Vanadium(III) acetylacetonate触媒2 回HCID 962Water溶媒HCID 6212Chloroform溶媒3 回

実験手順

In a three-neck flask, 10.3 g (27.54 mmol, 95% pure) of 1-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazole and 145.8 mg (0.55 mmol) of vanadium acetylacetonate were dissolved in 36 ml of chloroform and stirred for 10 minutes. Subsequently, 275.8 mg (0.825 mmol) of (S)-(2,4-di-tert-butyl-6-{(E)-[(1-hydroxy-3,3-dimethylbutan-2-yl)imino]methyl}phenol were added. After 10 minutes, 5.66 g (50 mmol) of 30% H2O2 were metered in over 6 hours. The progress of the conversion was monitored by means of HPLC. After 4 h of reaction time, a further 145.8 mg (0.55 mmol) of vanadium acetylacetonate and 275.8 mg of (2,4-di-tert-butyl-6-{(E)-[(1-hydroxy-3,3-dimethylbutan-2-yl)imino]methyl}phenol in 4 ml of chloroform were metered in. Subsequently, 40 ml of chloroform, 20 ml of water and 20 ml of thiosulphate solution were added successively. After the aqueous phase had been removed, the organic phase was washed with water and dried over Na2SO4, and the solvent was evaporated under reduced pressure. This gave 10.84 g of grey-brown crystals of (+)-1-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazole (98% yield, 93.1% HPLC purity) with 2.81% sulphone content. The enantiomeric excess was determined by means of HPLC on a chiral phase (Daicel Chiracel OJ-RH 150) with a ratio of 16.34:83.66.

後処理

  1. waitAfter 10 minutes
  2. customwere metered in over 6 hours
  3. customAfter 4 h of reaction time
  4. customAfter the aqueous phase had been removed
  5. washthe organic phase was washed with water
  6. dry with materialdried over Na2SO4
  7. customthe solvent was evaporated under reduced pressure

出典と根拠

ORDレコード
ord-4fd0adec4294404eabc37e88e72e5656
出典データセット
uspto-grants-2014_07
特許番号
US08765970B2

関連ノート

読み込み中…