Benzene → (2R,3R)-2,3-diphenyl-1,4-dioxaspiro[4.5]dec-6-ene

HRID 1423827

반응식

HRID 1423827 반응식
[C:1]1([C@@H:7]([OH:16])[C@@H:8]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[OH:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:17]1(=O)[CH2:22][CH2:21][CH2:20][CH:19]=[CH:18]1.C1C=CC=CC=1.O>CCOCC.CC1C=CC(S([O-])(=O)=O)=CC=1.C1C=C[NH+]=CC=1.CCCCCC>[C:1]1([C@@H:7]2[C@@H:8]([C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=3)[O:9][C:22]3([CH2:21][CH2:20][CH2:19][CH:18]=[CH:17]3)[O:16]2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

참가 물질

8

반응물 4

HCID 241Benzene2회HCID 962WaterHCID 135942-Cyclohexen-1-oneHCID 853019(R,R)-Hydrobenzoin

생성물 1

HCID 14267881(2R,3R)-2,3-diphenyl-1,4-dioxaspiro[4.5]dec-6-ene수율 82.8%

시약·촉매·용매 3

HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)촉매HCID 3283Diethyl Ether용매HCID 8058Hexane용매

반응 조건

온도
115 °C

실험 절차

To a 2 L flask was added (1R,2R)-1,2-diphenyl-1,2-ethanediol (200 g, 924 mmol), 2-cyclohexen-1-one (101 g, 1017 mmol), benzene (1232 mL) and PPTS (11.61 g, 46.2 mmol). The flask was fitted with a condenser and a dean-stark trap filled with benzene. The reaction was heated to 115° C. for 18 h (meanwhile trap contained 16.8 mL water indicating reaction completion). The reaction was cooled to RT and diluted with ether. The mixture was washed with saturated aq NaHCO3. The organic layer was dried over MgSO4, filtered and concentrated to give an orange liquid. This was passed over a silica gel plug eluting with 100% hexane (500 mL), then 5% EtOAc/Hexane (2 L), then 10% EtOAc/Hexane (500 mL), then 25% EtOAc/Hexane (500 mL). The product eluted in the first ˜2.5 L of solvent. Removal of solvent afforded a light yellow oil. To this residue was added ˜275 mL of hexane and the solution was let stand and crystals started to rapidly form. After about 1 h at RT, the solution was cooled in the freezer overnight. The next day, the hexane was decanted off, the solids washed with cold hexane. The solids were dried under reduced pressure at 75° C., and 223.75 g of (2R,3R)-2,3-diphenyl-1,4-dioxaspiro[4.5]dec-6-ene was obtained. The hexane solution was concentrated and purified by silica gel (ISCO, 330 g column, 100 mL/min, 0-10% EtOAc/Hexane over 40 min). Concentration of the pure fractions afforded (2R,3R)-2,3-diphenyl-1,4-dioxaspiro[4.5]dec-6-ene as an oil that solidified on sitting (30.47 g).

후처리

  1. customThe flask was fitted with a condenser and a dean-stark trap
  2. temperatureThe reaction was cooled to RT
  3. washThe mixture was washed with saturated aq NaHCO3
  4. dry with materialThe organic layer was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give an orange liquid
  8. washeluting with 100% hexane (500 mL)
  9. washThe product eluted in the first ˜2.5 L of solvent
  10. customRemoval of solvent
  11. customafforded a light yellow oil
  12. customto rapidly form
  13. temperaturethe solution was cooled in the freezer overnight
  14. customThe next day, the hexane was decanted off
  15. washthe solids washed with cold hexane
  16. customThe solids were dried under reduced pressure at 75° C.

출처 및 근거

ORD 기록
ord-9f348c35710146818173c0853a3f15e0
출처 데이터셋
uspto-grants-2015_01
특허 번호
US08927585B2

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