Hydrochloric Acid → HCID 131736073, Verbindung

HRID 1050651Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1050651
[C:1]1([C:7]2[C:19]([C:20]([CH3:23])([CH3:22])[CH3:21])=[CH:18][C:17]3[C:16]4[C:11](=[CH:12][C:13]([C:28]5[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=5)=[C:14]([C:24]([CH3:27])([CH3:26])[CH3:25])[CH:15]=4)[CH2:10][C:9]=3[CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:34]([Li])[CH2:35][CH2:36][CH3:37].[CH2:39]([C:43]([CH2:49][CH2:50][CH2:51][CH3:52])=C1C=CC=C1)[CH2:40][CH2:41][CH3:42].Cl.O1CCC[CH2:55]1>C(OCC)C.CCCCCC>[CH2:49]([C:43]([CH2:39][CH2:40][CH2:41][CH3:42])=[C:15]1[C:16]2[C:11]([CH:10]=[C:9]3[C:17]=2[CH:18]=[C:19]([C:20]([CH3:21])([CH3:22])[CH3:23])[C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)=[CH:8]3)=[C:12]([CH:34]2[CH:55]=[CH:37][CH:36]=[CH:35]2)[C:13]([C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)=[C:14]1[C:24]([CH3:26])([CH3:27])[CH3:25])[CH2:50][CH2:51][CH3:52]

Komponenten

8

Edukt 5

HCID 313Hydrochloric AcidHCID 8028Tetrahydrofuran3×HCID 190333046,6-Di(n-butyl)fulveneHCID 219826953,6-DI-Tert-butyl-2,7-diphenyl-9H-fluoreneHCID 178418339Butyllithium

Produkt 1

HCID 131736073HCID 131736073, VerbindungAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

Under a nitrogen atmosphere, 30 mL of dehydrated tetrahydrofuran was added to 1.51 g (3.51 mmol) of 2,7-diphenyl-3,6-ditert-butyl-fluorene synthesized in Synthesis Example 1-1 (ii), and the mixture was stirred. This solution was cooled in an ice bath, and 2.50 mL (3.90 mmol) of a 1.56 mol/L hexane solution of n-butyllithium was added. The mixture was stirred at room temperature for 2 hours. The resulting dark red solution was cooled to −78° C. in a dry ice/methanol bath, and a tetrahydrofuran solution prepared by dissolving 0.757 g (3.98 mmol) of 6,6-di(n-butyl)fulvene in 15 mL of tetrahydrofuran was added dropwise over 15 minutes. Subsequently, the mixture was stirred for 18 hours while gradually warming to room temperature. 50 mL of 1 N hydrochloric acid was added to the resulting red solution to terminate the reaction. 100 mL of diethyl ether was added to perform liquid-liquid phase separation, and the soluble fraction was extracted. This organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water and once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from hexane to obtain a target product as a white powder (yield 1.54 g (70%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Aufarbeitung

  1. temperatureThis solution was cooled in an ice bath
  2. stirringThe mixture was stirred at room temperature for 2 hours
  3. additionwas added dropwise over 15 minutes
  4. stirringSubsequently, the mixture was stirred for 18 hours
  5. temperaturewhile gradually warming to room temperature
  6. customto terminate
  7. customthe reaction
  8. customliquid-liquid phase separation
  9. extractionthe soluble fraction was extracted
  10. washThis organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  11. dry with materialonce with saturated brine, and dried over magnesium sulfate
  12. distillationThe solvent was distilled off
  13. customthe residue was recrystallized from hexane

Quellen und Nachweise

ORD-Eintrag
ord-fc9aa85b28ac46e7ab11f54218c579e7
Quelldatensatz
uspto-grants-2016_07
Patentnummer
US09382356B2

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