Diethyl Malonate → Diethyl [([1,1'-biphenyl]-2-yl)methyl]propanedioate

HRID 67811

Reaktionsgleichung

Reaktionsgleichung von HRID 67811
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[H][H].Br[CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>CN(C)C=O.O.C1C=CC=CC=1>[C:24]1([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=2[CH2:17][CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:3]([O:11][CH2:12][CH3:13])=[O:10])[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

Komponenten

8

Edukt 4

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 2633651-(Bromomethyl)-2-phenylbenzeneHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 12942384Diethyl [([1,1'-biphenyl]-2-yl)methyl]propanedioateAusbeute 97,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 241BenzeneLösungsmittelHCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A stirred mixture of 12.5 g (0.54 mole) of sodium hydride (25 g of a 50% dispersion in mineral oil) in 300 ml of dimethylformamide and 900 ml of benzene was placed under a nitrogen atmosphere and cooled to 0° C. To this mixture, 104.3 g (0.9 moles) of diethyl malonate was added dropwise during a 5 minute period and the mixture was stirred until hydrogen evolution ceased. 2-(Bromomethyl)biphenyl (117 g, 0.47 mole) was then added at 0° C. Upon complete addition the reaction mixture was stirred at 0° C. for 30 minutes, then was allowed to warm to ambient temperature with stirring for one hour. The reaction mixture was poured into 500 ml of water, the layers separated, and the aqueous layer washed with two portions of 250 ml each of diethyl ether. The organic layer was combined with the ether washings, and the whole was washed with one portion of 500 ml of aqueous 5% hydrochloric acid, one portion of 500 ml of water, one portion of 300 ml of a solution saturated with sodium bicarbonate, and finally, one portion of 500 ml of water. The organic layer was dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to an oil residue. The oil was distilled under reduced pressure to give 149.0 g of diethyl (2-phenylbenzyl)malonate; b.p. 175°-180° C./0.8-0.9 mm. The nmr spectrum was consistent with the proposed structure.

Aufarbeitung

  1. additionUpon complete addition the reaction mixture
  2. temperatureto warm to ambient temperature
  3. stirringwith stirring for one hour
  4. customthe layers separated
  5. washthe aqueous layer washed with two portions of 250 ml each of diethyl ether
  6. washthe whole was washed with one portion of 500 ml of aqueous 5% hydrochloric acid, one portion of 500 ml of water, one portion of 300 ml of a solution saturated with sodium bicarbonate
  7. dry with materialThe organic layer was dried with magnesium sulfate
  8. filtrationfiltered
  9. concentrationthe filtrate concentrated under reduced pressure to an oil residue
  10. distillationThe oil was distilled under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-1410d8e26cce40e88ea0a306d2e1de5d
Quelldatensatz
uspto-grants-1982_08
Patentnummer
US04346251

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