Benzene → HCID 90123719、化合物

HRID 633645

反応式

HRID 633645 の反応式
[CH:1]1[CH:6]=CC=C[CH:2]=1.[CH3:7][O:8][C:9]1[CH:10]=[C:11]([OH:28])[CH:12]=[C:13]([O:26][CH3:27])[C:14]=1[CH2:15][C@H:16]1[C@:18]([CH3:25])([CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])[O:17]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCCCCC>CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(=O)(OC)OCC=C.CCOC(C)=O>[CH2:6]([C:14]1([CH2:15][C@H:16]2[C@:18]([CH3:25])([CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])[O:17]2)[C:9]([O:8][CH3:7])=[CH:10][C:11](=[O:28])[CH:12]=[C:13]1[O:26][CH3:27])[CH:1]=[CH2:2]

参加物

9

反応物 4

HCID 241BenzeneHCID 8058HexaneHCID 11776TriphenylphosphineHCID 90123850HCID 90123850、化合物

生成物 1

HCID 90123719HCID 90123719、化合物収率 65%

試薬・触媒・溶媒 4

HCID 11026Titanium isopropoxide触媒HCID 167845palladium(II) acetate触媒HCID 534788Methyl 2-propen-1-yl carbonate触媒HCID 8857Ethyl Acetate溶媒

実験手順

Allyl methyl carbonate (18 μL, 0.16 mmol, 2.5 equiv.) and titanium(IV) isopropoxide (3.7 μL, 12 mmol, 0.2 equiv.) were added in sequence to a peach-colored PhH (0.5 mL) solution of 6 (19 mg, 62 mmol, 1 equiv.), triphenylphosphine (1.3 mg, 5.0 mmol, 0.08 equiv.), and palladium(II) acetate (0.3 mg, 1.2 mmol, 0.02 equiv.) at room temperature in a 10-mL heart-shaped flask, whereupon the solution turned an opaque dark red. After stirring at room temperature for 10 min, the solution was heated to 50° C. After 1 h of heating at this temperature, the solution turned clear dark red. After stirring for a total of 130 min at 50° C., the solution was cooled to room temperature and quenched with saturated aqueous NH4Cl. After diluting with PhH and stirring for 5 min, 1 N HCl was added, and the layers were separated. The aqueous layer was then extracted twice with EtOAc. The organic extracts were combined, washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to an inhomogeneous green oil. Flash column chromatography (25 mL SiO2, 4:1 to 7:3 to 1:1 hexane:EtOAc) afforded 14 mg (40 mmol, 65% yield) of 7 as a clear, colorless oil. TLC Rf 0.22 (1:1 hexane:EtOAc). 1H NMR (600 MHz; CDCl3): δ 5.59 (d, J=7.7 Hz, 2H), 5.39 (ddt, J=17.1, 10.0, 7.2 Hz, 1H), 5.00-4.92 (m, 3H), 3.73 (s, 3H), 3.70 (s, 3H), 2.61-2.54 (m, 2H), 2.40 (t, J=5.9 Hz, 1H), 2.14 (dd, J=13.9, 5.3 Hz, 1H), 2.04 (dd, J=13.9, 6.6 Hz, 1H), 1.98-1.88 (m, 2H), 1.64 (s, 3H), 1.56 (s, 3H), 1.50 (ddd, J=13.7, 9.7, 6.3 Hz, 1H), 1.27 (ddd, J=13.7, 10.0, 6.5 Hz, 1H), 1.17 (s, 3H). 13C NMR (125 MHz; CDCl3): δ 188.0, 173.1, 172.6, 132.2, 131.9, 123.6, 118.4, 103.55, 103.45, 60.7, 59.3, 56.2, 56.0, 49.7, 41.7, 38.9, 35.7, 25.8, 23.9, 17.8, 16.7. IR (NaCl, thin film, cm−1) 2928, 1654, 1592, 1384, 1233, 1206, 1144. HRMS-ESI (m/z): [M+Na]+ calculated for C21H30O4, 369.2036. found, 369.2043.

後処理

  1. temperaturethe solution was heated to 50° C
  2. temperatureAfter 1 h of heating at this temperature
  3. stirringAfter stirring for a total of 130 min at 50° C.
  4. temperaturethe solution was cooled to room temperature
  5. customquenched with saturated aqueous NH4Cl
  6. additionAfter diluting with PhH
  7. stirringstirring for 5 min
  8. addition1 N HCl was added
  9. customthe layers were separated
  10. extractionThe aqueous layer was then extracted twice with EtOAc
  11. washwashed with brine
  12. dry with materialdried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo to an inhomogeneous green oil

出典と根拠

ORDレコード
ord-3716f9686dfa4b0992cdc847009a47c1
出典データセット
uspto-grants-2016_04
特許番号
US09321713B2

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