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Ethyl butyrate → 5-[(2'-Cyanobiphenyl-4-yl)methyl]-4,6-dioxononane

HRID 274108
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 274108
[O:1]=[C:2]([CH2:6][C:7](=[O:11])[CH2:8][CH2:9][CH3:10])[CH2:3][CH2:4][CH3:5].C(C(C)=O)CC.C(OCC)(=O)CCC.[NH2-].[Li+].[H-].[Na+].Br[CH2:31][C:32]1[CH:37]=[CH:36][C:35]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][C:39]=2[C:44]#[N:45])=[CH:34][CH:33]=1>CN(C=O)C>[C:44]([C:39]1[CH:40]=[CH:41][CH:42]=[CH:43][C:38]=1[C:35]1[CH:34]=[CH:33][C:32]([CH2:31][CH:6]([C:7](=[O:11])[CH2:8][CH2:9][CH3:10])[C:2](=[O:1])[CH2:3][CH2:4][CH3:5])=[CH:37][CH:36]=1)#[N:45]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 6

HCID 7762Ethyl butyrateHCID 78952-PentanoneHCID 24532Lithium amideHCID 24758Sodium hydrideHCID 264544,6-NonanedioneHCID 15019124'-(Bromomethyl)-2-cyanobiphenyl

Produkt 1

HCID 20092863
5-[(2'-Cyanobiphenyl-4-yl)methyl]-4,6-dioxononane
Ausbeute 104,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel2×

Versuchsvorschrift

15.6 g of 4,6-dioxononane, prepared from methyl propyl ketone and ethyl butyrate in the presence of lithium amide (according to CA 42: 4129 f), are dissolved in 160 ml of anhydrous DMF. 4 g of 60% NaH are added in portions. When the exothermic effect has subsided, the mixture is cooled to room temperature and a solution of 27.2 g of 4'-bromomethyl-2-cyanobiphenyl, prepared in Example 4, in 90 ml of DMF is introduced dropwise. The mixture is stirred for 30 min at room temperature and then heated at 60° C. for 2 h. It is concentrated under vacuum and the concentrate is taken up in a water/dichloromethane mixture and acidified with a dilute solution of HCl. After decantation, the aqueous phase is extracted twice with dichloromethane. The organic phases are washed with water, dried and then concentrated to give 36.3 g of an oil, which is purified by chromatography twice in succession (eluent: chloroform, then cyclohexane 90%/ethyl acetate 10% respectively) to give a solid identified by NMR as being the enol tautomer melting at 105° C., and an oil corresponding to the diketone tautomeric form.

Aufarbeitung

  1. additionis introduced dropwise
  2. temperatureheated at 60° C. for 2 h
  3. concentrationIt is concentrated under vacuum
  4. extractionAfter decantation, the aqueous phase is extracted twice with dichloromethane
  5. washThe organic phases are washed with water
  6. customdried
  7. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-a6ea9ab70fd8457486dfddc7c339a6ba
Quelldatensatz
uspto-grants-1995_02
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US05387747

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