Triphenylphosphonium bromide → 3-Phenyl-3-cyclopentenecarboxylic acid

HRID 1034202ノート

反応式

HRID 1034202 の反応式
[C:1]([CH2:9][CH:10]1[CH2:14][CH2:13][O:12][C:11]1=[O:15])(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C2CC(C(O)=O)CCC=2)C=CC=CC=1>CS(C)=O.O1CCCC1>[C:2]1([C:1]2[CH2:9][CH:10]([C:11]([OH:12])=[O:15])[CH2:14][CH:13]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

6

反応物 3

HCID 80811Triphenylphosphonium bromideHCID 117889393-(benzoylmethyl)-4,5-dihydro-2(3H)-furanoneHCID 156418093-Phenyl 3 cyclohexenecarboxylic acid

生成物 1

HCID 200766803-Phenyl-3-cyclopentenecarboxylic acid収率 67.3%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
170 °C

実験手順

3-(Benzoylmethyl)-4,5-dihydro-2(3H)-furanone (5.00 g, Step A) and triphenylphosphine hydrobromide (8.41g) are mixed and heated to 170° C. in an oil bath under nitrogen for 1 hour. The mixture is cooled and powdered. The powder is dissolved in dimethylsulfoxide (50 mL) and diluted with tetrahydrofuran (30 mL). The solution is stirred under nitrogen and cooled in an ice.bath. Dimsyl sodium (25 mL of 2M, see Example D, Step C) is added dropwise over 20 minutes keeping the internal temperature below 14° C. The mixture is stirred at 25° C. for 2 hours and the solvents evaporated. The residue is treated with water (80 mL) containing saturated aqueous sodium bicarbonate (10 mL) and extracted with dichloromethane (3×50 mL). The extracts are washed with dilute aqueous sodium bicarbonate. The aqueous layers are washed with dichloromethane (30 mL) and acidified with concentrated hydrochloric acid. The aqueous layers are extracted with dichloror:ethane (3×50 mL), the extracts dried over magnesium sulfate, filtered, and evaporated to a brown oil. The oil is washed through silica gel (30 g) with 2:1 chloroform:ethyl acetate to give 3.1 g of 3-phenyl-3-cyclopentenecarboxylic acid as a brown solid.

後処理

  1. temperatureThe mixture is cooled
  2. customthe internal temperature below 14° C
  3. stirringThe mixture is stirred at 25° C. for 2 hours
  4. customthe solvents evaporated
  5. additionThe residue is treated with water (80 mL)
  6. additioncontaining saturated aqueous sodium bicarbonate (10 mL)
  7. extractionextracted with dichloromethane (3×50 mL)
  8. washThe extracts are washed with dilute aqueous sodium bicarbonate
  9. washThe aqueous layers are washed with dichloromethane (30 mL)
  10. extractionThe aqueous layers are extracted with dichloror
  11. dry with materialethane (3×50 mL), the extracts dried over magnesium sulfate
  12. filtrationfiltered
  13. customevaporated to a brown oil
  14. washThe oil is washed through silica gel (30 g) with 2:1 chloroform

出典と根拠

ORDレコード
ord-e2d748d07b92476195091ac3fb50ba58
出典データセット
uspto-grants-1994_05
特許番号
US05314896

反応ノート

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