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

反応式

HRID 971645 の反応式
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

参加物

6

反応物 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

生成物 1

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

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

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)

後処理

  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

出典と根拠

ORDレコード
ord-8418095d445b44b6a8a233742033e674
出典データセット
uspto-grants-1979_07
特許番号
US04160838

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