Methane, dichloromethoxy- → 5-Hydroxy-7-isopropyl-4-oxo-3,4-dihydrospiro[chromen-2,1'-cyclobutane]-6-carbaldehyde

HRID 1516715Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1516715
[OH:1][C:2]1[CH:14]=[C:13]([CH:15]([CH3:17])[CH3:16])[CH:12]=[C:11]2[C:3]=1[C:4](=[O:18])[CH2:5][C:6]1([O:10]2)[CH2:9][CH2:8][CH2:7]1.[CH3:19][O:20]C(Cl)Cl>[Ti](Cl)(Cl)(Cl)Cl.ClCCl>[OH:1][C:2]1[C:14]([CH:19]=[O:20])=[C:13]([CH:15]([CH3:16])[CH3:17])[CH:12]=[C:11]2[C:3]=1[C:4](=[O:18])[CH2:5][C:6]1([O:10]2)[CH2:7][CH2:8][CH2:9]1

Komponenten

5

Edukt 2

HCID 21004Methane, dichloromethoxy-HCID 58002934HCID 58002934, Verbindung

Produkt 1

HCID 580029765-Hydroxy-7-isopropyl-4-oxo-3,4-dihydrospiro[chromen-2,1'-cyclobutane]-6-carbaldehyde

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24193Titanium TetrachlorideKatalysatorHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
-70 °C

Versuchsvorschrift

Under argon, 9.60 g (39 mmol) of 5-hydroxy-7-isopropylspiro[chromen-2,1′-cyclobutan]-4(3H)-one (Example 46A) are dissolved in 400 ml of abs. dichloromethane and cooled to −70° C. At this temperature, 97.44 ml (97.44 mmol) of titanium(IV) chloride (1 M solution in dichloromethane) are added dropwise such that the temperature does not exceed −65° C. The mixture is stirred briefly at −70° C., 3.88 ml (42.87 mmol) of dichloromethyl methyl ether are then added and the mixture is subsequently warmed to 0° C. After 3 hours at this temperature, the reaction mixture is added carefully to ice-water and extracted four times with dichloromethane. The combined organic phases are washed three times with saturated sodium chloride solution, dried over magnesium sulfate, filtered and evaporated to dryness. The crude product obtained is adsorbed on silica gel and purified on a silica gel column (mobile phase: cyclohexane→cyclohexane/ethyl acetate 30:1). This gives 8.1 g (76% of theory) of the title compound in a purity of 77%.

Aufarbeitung

  1. customdoes not exceed −65° C
  2. temperaturethe mixture is subsequently warmed to 0° C
  3. extractionextracted four times with dichloromethane
  4. washThe combined organic phases are washed three times with saturated sodium chloride solution
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated to dryness

Quellen und Nachweise

ORD-Eintrag
ord-6585295027b24077a02f7e0b265ae83c
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08227511B2

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