Hydrochloric Acid → HCID 68671827, Verbindung

HRID 2192888Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2192888
[I-].C1([P+](C2C=CC=CC=2)(C2C=CC=CC=2)[CH2:9][CH:10]2[CH2:15][CH2:14][O:13][CH2:12][CH2:11]2)C=CC=CC=1.[CH2:28]([O:30][C:31](=[O:45])[C:32]([C:34]1[CH:39]=[CH:38][C:37]([S:40][CH:41]2[CH2:43][CH2:42]2)=[C:36]([Br:44])[CH:35]=1)=O)[CH3:29].Cl>C1COCC1>[Br:44][C:36]1[CH:35]=[C:34]([C:32](=[CH:9][CH:10]2[CH2:11][CH2:12][O:13][CH2:14][CH2:15]2)[C:31]([O:30][CH2:28][CH3:29])=[O:45])[CH:39]=[CH:38][C:37]=1[S:40][CH:41]1[CH2:43][CH2:42]1

Komponenten

5

Edukt 3

HCID 313Hydrochloric AcidHCID 21094223Triphenyl[(tetrahydro-2H-pyran-4-yl)methyl]phosphonium iodideHCID 59570898Ethyl 3-bromo-4-(cyclopropylthio)-α-oxobenzeneacetate

Produkt 1

HCID 68671827HCID 68671827, VerbindungAusbeute 73,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a suspension of triphenyl(tetrahydro-2H-pyran-4-yl-methyl)phosphonium iodide (9.27 g) in THF (70 mL) was added dropwise lithium-1,1,1,3,3,3-hexamethyldisilazide (1 M THF solution, 19.0 mL) at 0° C. or lower, followed by stirring at around 0° C. for 1 hour. To the reaction mixture was added dropwise a solution of ethyl[3-bromo-4-(cyclopropylsulfanyl)phenyl](oxo)acetate (5.0 g) in THF (10 mL) at 2° C. or lower. The reaction mixture was stirred for 30 minutes under ice-cooling and then stirred at room temperature for 15 hours. 4 M Hydrochloric acid was added dropwise thereto at 10° C. or lower, adjusted to pH 7, and then concentrated under reduced pressure. To the residue was added diethyl ether and the resulting solid was separated by filtration. The filtrate was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain ethyl 2-[3-bromo-4-(cyclopropylsulfanyl)phenyl]-3-(tetrahydro-2H-pyran-4-yl)acrylate (4.57 g) as an (E)/(Z)-mixture of olefin.

Aufarbeitung

  1. additionwas added dropwise lithium-1,1,1,3,3,3-hexamethyldisilazide (1 M THF solution, 19.0 mL) at 0° C.
  2. stirringThe reaction mixture was stirred for 30 minutes under ice-
  3. temperaturecooling
  4. stirringstirred at room temperature for 15 hours
  5. customat 10° C.
  6. concentrationconcentrated under reduced pressure
  7. additionTo the residue was added diethyl ether
  8. customthe resulting solid was separated by filtration
  9. washThe filtrate was washed with water and saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated under reduced pressure
  12. customThe residue was purified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-ab831bb4367c4bb3b98bd26cbb64fea6
Quelldatensatz
uspto-grants-2012_12
Patentnummer
US08329707B2

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