p-Toluenesulfonic acid → (-)-(4R,trans)-1-[2-(2,4-dichlorophenyl)-4,5-dimethyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole

HRID 971645

반응식

HRID 971645 반응식
CC1C=CC(S(O)(=O)=O)=CC=1.[Cl:12][C:13]1[CH:18]=[C:17]([Cl:19])[CH:16]=[CH:15][C:14]=1[C:20](OC)(OC)[CH2:21][N:22]1[CH:26]=[N:25][CH:24]=[N:23]1.[CH3:31][C@@H:32]([OH:36])[C@H:33]([OH:35])[CH3:34].CC1C=CC(S(O)(=O)=O)=CC=1.[OH-].[Na+]>CC1C=CC=CC=1>[Cl:12][C:13]1[CH:18]=[C:17]([Cl:19])[CH:16]=[CH:15][C:14]=1[C:20]1([CH2:21][N:22]2[CH:26]=[N:25][CH:24]=[N:23]2)[O:36][C@H:32]([CH3:31])[C@@H:33]([CH3:34])[O:35]1

참가 물질

6

반응물 4

HCID 6101p-Toluenesulfonic acidHCID 14798Sodium HydroxideHCID 225936(2R,3R)-ButanediolHCID 230442891-[2-(2,4-dichlorophenyl)-2,2-dimethoxyethyl]-1H-1,2,4-triazole 4-methylbenzenesulfonate

생성물 1

HCID 53665691(-)-(4R,trans)-1-[2-(2,4-dichlorophenyl)-4,5-dimethyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole수율 50%

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

A mixture of 9.5 parts of 1-[2(2,4-dichlorophenyl)-2,2-dimethoxyethyl]-1H-1,2,4-triazole 4-methylbenzenesulfonate, 2 parts of (2R, 3R)(-)-2,3-butanediol, 1 part of 4-methylbenzenesulfonic acid and 90 parts of methylbenzene is stirred and refluxed for 3 days. The reaction mixture is cooled and alkalized with a sodium hydroxide solution 20%. The whole is poured onto water and the product is extracted with dichloromethane. The extract is dried, filtered and evaporated. The residue is purified by column-chromatography over silica gel using ethyl acetate as eluent. The pure fractions are collected and the eluent is evaporated. The residue is crystallized from a mixture of 2,2'oxybispropane and petroleumether (1:1 by volume). The product is filtered off and dried, yielding 3.2 parts (50%) of (-)-(4R,trans)-1-[2-(2,4-dichlorophenyl)-4,5-dimethyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole; mp. 82.5° C.; [α]D =-30.26° (c=0.5% CHCl3)

후처리

  1. temperaturerefluxed for 3 days
  2. temperatureThe reaction mixture is cooled
  3. additionThe whole is poured onto water
  4. extractionthe product is extracted with dichloromethane
  5. customThe extract is dried
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue is purified by column-chromatography over silica gel
  9. customThe pure fractions are collected
  10. customthe eluent is evaporated
  11. customThe residue is crystallized from a mixture of 2,2'oxybispropane and petroleumether (1:1 by volume)
  12. filtrationThe product is filtered off
  13. customdried

출처 및 근거

ORD 기록
ord-8418095d445b44b6a8a233742033e674
출처 데이터셋
uspto-grants-1979_07
특허 번호
US04160838

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