Dimethylformamide → 7-Bromo-9,9-diethylfluorene-2-carboxaldehyde

HRID 1188740Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1188740
[CH2:1]([C:3]1([CH2:18][CH3:19])[C:15]2[CH:14]=[C:13](Br)[CH:12]=[CH:11][C:10]=2[C:9]2[C:4]1=[CH:5][C:6]([Br:17])=[CH:7][CH:8]=2)[CH3:2].C([Li])CCC.CN([CH:28]=[O:29])C>C1COCC1.C(=O)=O.C(O)C.Cl.C1(C)C=CC=CC=1>[CH2:1]([C:3]1([CH2:18][CH3:19])[C:15]2[CH:14]=[C:13]([CH:28]=[O:29])[CH:12]=[CH:11][C:10]=2[C:9]2[C:4]1=[CH:5][C:6]([Br:17])=[CH:7][CH:8]=2)[CH3:2]

Komponenten

8

Edukt 3

HCID 6228DimethylformamideHCID 35310452,7-Dibromo-9,9-diethylfluoreneHCID 178418339Butyllithium

Produkt 1

HCID 154763497-Bromo-9,9-diethylfluorene-2-carboxaldehydeAusbeute 78,4 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 313Hydrochloric AcidLösungsmittelHCID 1140TolueneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 19604758Methanedione--ethanol (1/1)Lösungsmittel

Reaktionsbedingungen

Temperatur
5 °C

Versuchsvorschrift

To a mechanically stirred solution of 9,9-diethyl-2,7-dibromofluorene (Example 2; 59.38 g, 0.1563 mol) in THF (325 mL) cooled in dry ice-ethanol bath, n-butyl lithium (104 mL of 1.6M solution in hexanes, 0.1664 mol, 1.06 eq.) was added dropwise over 25 minutes. After 20 minutes, DMF (17 mL, 0.22 mol) in THF (30 mL) was added, and the mixture was stirred in the cooling bath for 1.5 hours, and outside the bath for 1 hour. The reaction was then cooled to 5° C. and treated with hydrochloric acid (12.5 of concentrated hydrochloric acid diluted with 50 mL water). The mixture was diluted with 200 mL of toluene, and the aqueous phase was separated and extracted with 200 mL of toluene. The combined organic phase was washed with dilute sodium bicarbonate solution, dried over magnesium sulfate and concentrated. The residual solids were recrystallized from heptane-ethyl acetate (9:1) mixture, to get colorless solids, 40.29 g (78.4% yield), m.p. 126-128° C. The mother liquor after chromatography over 150 g of silica gel, elution with 1:1 heptane-toluene mixture, and trituration of residual solids in hexanes gave additional product, 6.56 g (12.8% yield, total 91% yield), m.p. 126-128° C. Mass Spec: m/z 328, 330, (M+). A sample for analysis was prepared by recrystallization from hexanes, m.p. 127-129° C. Analysis: Calculated for C18H17BrO: C, 65.55%; H, 5.20%; Br, 24.27%. Found: C, 65.60%; H, 5.51%; Br, 24.71%.

Aufarbeitung

  1. waitoutside the bath for 1 hour
  2. customthe aqueous phase was separated
  3. extractionextracted with 200 mL of toluene
  4. washThe combined organic phase was washed with dilute sodium bicarbonate solution
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. customThe residual solids were recrystallized from heptane-ethyl acetate (9:1) mixture
  8. customto get colorless solids, 40.29 g (78.4% yield), m.p. 126-128° C
  9. washThe mother liquor after chromatography over 150 g of silica gel, elution with 1:1 heptane-toluene mixture, and trituration of residual solids in hexanes
  10. customgave additional product, 6.56 g (12.8% yield, total 91% yield), m.p. 126-128° C

Quellen und Nachweise

ORD-Eintrag
ord-80a5eb039ecd45d0a7bc104bbafaa973
Quelldatensatz
uspto-grants-2014_03
Patentnummer
US08674057B1

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