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

HRID 1878938

반응식

HRID 1878938 반응식
[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

참가 물질

8

반응물 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, 화합물2회

생성물 1

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

시약·촉매·용매 3

HCID 5377225Vanadium(III) acetylacetonate촉매2회HCID 962Water용매HCID 6212Chloroform용매3회

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-d5871d77eefb4ee99b9c01a768af553c
출처 데이터셋
uspto-grants-2012_11
특허 번호
US08314133B2

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