Diethyl Oxalate → Ethyl 2-(2,2-dimethylbenzo[1,2-d]-1,3-dioxan-6-yl)2-hydroxyacetate

HRID 367332

反応式

HRID 367332 の反応式
Br[C:2]1[CH:13]=[CH:12][C:5]2[O:6][C:7]([CH3:11])([CH3:10])[O:8][CH2:9][C:4]=2[CH:3]=1.C([Li])CCC.[C:19](OCC)(=[O:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21].[BH4-].[Na+].C(=O)(O)[O-].[K+]>O1CCCC1.CCCCCC.C(O)C.O.C(O)(=O)C>[CH3:10][C:7]1([CH3:11])[O:6][C:5]2[CH:12]=[CH:13][C:2]([CH:19]([OH:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:3][C:4]=2[CH2:9][O:8]1

参加物

11

反応物 5

HCID 7268Diethyl OxalateHCID 516893Potassium BicarbonateHCID 4311764Sodium borohydrideHCID 145203386-Bromo-2,2-dimethyl-4H-benzo[d][1,3]dioxineHCID 178418339Butyllithium

生成物 1

HCID 57088882Ethyl 2-(2,2-dimethylbenzo[1,2-d]-1,3-dioxan-6-yl)2-hydroxyacetate収率 76.4%

試薬・触媒・溶媒 5

HCID 176Acetic Acid溶媒HCID 702Ethanol溶媒2 回HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

反応条件

温度
-80 °C

実験手順

6-Bromo-2,2-dimethylbenzo[1,2-d]-1,3-dioxane (30.0 g) was dissolved in 610 ml of tetrahydrofuran, 136 ml of 1.56 M n-butyl lithium in hexane was added to the solution with stirring at -80° C., and the mixture was subjected to 15 minutes of reaction. With stirring at -80° C., the reaction solution was added to a solution of 21.6 g of diethyl oxalate in 200 ml of tetrahydrofuran, and the mixture was subjected to 1 hour of reaction. Then, 100 ml of ethanol and a solution of 1.40 g of sodium borohydride in 100 ml of ethanol were added in that order. The reaction solution was stirred at -30° C. for 30 minutes, 8.26 ml of acetic acid was added, and the mixture was stirred for 5 minutes. Then, a solution of 14.8 g of potassium bicarbonate in 50 ml of water was added, and the reaction solution was concentrated under reduced pressure. Water was added to the residue, and the mixture was extracted with ethyl acetate. The extract was washed with brine and then dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the resulting residue was purified by silica gel medium pressure liquid column chromatography (eluent: hexane/ethyl acetate=5/1) to give 25.1 g of ethyl 2-(2,2-dimethylbenzo[1,2-d]-1,3-dioxan-6-yl)2-hydroxyacetate in an oily form.

後処理

  1. customthe mixture was subjected to 15 minutes of reaction
  2. stirringWith stirring at -80° C.
  3. customthe mixture was subjected to 1 hour of reaction
  4. stirringThe reaction solution was stirred at -30° C. for 30 minutes
  5. stirringthe mixture was stirred for 5 minutes
  6. concentrationthe reaction solution was concentrated under reduced pressure
  7. additionWater was added to the residue
  8. extractionthe mixture was extracted with ethyl acetate
  9. washThe extract was washed with brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customThe solvent was evaporated under reduced pressure
  12. customthe resulting residue was purified by silica gel medium pressure liquid column chromatography (eluent: hexane/ethyl acetate=5/1)

出典と根拠

ORDレコード
ord-fe5e2df9f1d94de6b885cc30d822f08f
出典データセット
uspto-grants-2000_10
特許番号
US06133266

関連ノート

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