Triphenylphosphonium bromide → 3-Phenyl-3-cyclopentenecarboxylic acid

HRID 1034202노트

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HRID 1034202 반응식
[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

참가 물질

6

반응물 3

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

생성물 1

HCID 200766803-Phenyl-3-cyclopentenecarboxylic acid수율 67.3%

시약·촉매·용매 2

HCID 679Dimethyl Sulfoxide용매HCID 8028Tetrahydrofuran용매

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온도
170 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-e2d748d07b92476195091ac3fb50ba58
출처 데이터셋
uspto-grants-1994_05
특허 번호
US05314896

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