Diisopropylamine → HCID 13704268, Verbindung

HRID 231129

Reaktionsgleichung

Reaktionsgleichung von HRID 231129
C(NC(C)C)(C)C.C([Li])CCC.[CH2:13]([O:15][C:16](=[O:26])[CH2:17][O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[CH3:14].[Cl:27][C:28]1[CH:29]=[CH:30][C:31]([O:38][CH2:39][C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)=[C:32]([CH:37]=1)[C:33](OC)=[O:34]>C1COCC1>[Cl:27][C:28]1[CH:29]=[CH:30][C:31]([O:38][CH2:39][C:40]2[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=2)=[C:32]([C:33](=[O:34])[CH:17]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:16]([O:15][CH2:13][CH3:14])=[O:26])[CH:37]=1

Komponenten

6

Edukt 4

HCID 7912DiisopropylamineHCID 290299Ethyl 2-(benzyloxy)acetateHCID 13704267HCID 13704267, VerbindungHCID 178418339Butyllithium

Produkt 1

HCID 13704268HCID 13704268, VerbindungAusbeute 56 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

In a flame-dried flask were placed dry THF (4 ml) and diisopropylamine (1.21 g, 0.012 mol). n-Butyllithium (1.55M in hexane, 7.7 ml, 0.012 mol) was added dropwise at -10° C. under argon. After stirring for 0.5 h at 0° C., a solution of ethylphenylmethoxyacetate (2.33 g, 0.012 mol) in dry THF (4 ml) was added dropwise at -78° C. After one h methyl 5-chloro-2-phenylmethoxybenzoate (2.21 g, 0.008 mol) in dry THF (4 ml) was added. Stirring was continued for an additional 2 h at -78° C. and the reaction mixture was quenched with 2 ml of EtOH at -20° C. The quenched mixture was poured into 50 ml of 10% aqueous HCl solution and extracted with ether. The ether layer was washed with water, dried (Na2SO4), filtered and concentrated under reduced pressure affording a light yellow oil. Purification by flash chromatography (silica gel) using toluene-CHCl3 (5:1) as eluent afforded 1.96 g (56%) of ethyl 5-chloro-β-oxo-α,2-bis(phenylmethoxy)benzenepropanoate as white crystals (EtOH): mp 64°-65° C.; IR (KBr) 1735 (ester) and 1685 (conjugated carbonyl) cm-1 ; NMR (CDCl3, 90 MHz) δ 1.16 (t, 3H, OCH2CH3) 4.13 (q, 2H, OCH2CH3), 4.55 (dd, 1H, OCH2Ph, JAB =12.6 Hz), 4.60 (dd, 1H, OCH2Ph, JAB =12.6 Hz), 5.07 (s, 2H, OCH2Ph), 5.28 (s, 1H, CHCO2Et), 6.85 (d, 1H, ArH, J=8.9 Hz), 7.05-7.50 (m, 11H, ArH), 7.64 (d, 1H, ArH, J=2.5 Hz). Anal calcd. for C25H23ClO5 : C, 68.41; H, 5.28; Cl, 8.07. Found: C, 68.14; H, 5.28; Cl, 8.09.

Aufarbeitung

  1. customIn a flame-dried flask were placed dry
  2. stirringStirring
  3. waitwas continued for an additional 2 h at -78° C.
  4. customthe reaction mixture was quenched with 2 ml of EtOH at -20° C
  5. additionThe quenched mixture was poured into 50 ml of 10% aqueous HCl solution
  6. extractionextracted with ether
  7. washThe ether layer was washed with water
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customaffording a light yellow oil
  12. customPurification by flash chromatography (silica gel)

Quellen und Nachweise

ORD-Eintrag
ord-dcd15100919b4ae7934807a29b9b5c3e
Quelldatensatz
uspto-grants-1989_07
Patentnummer
US04845121

Verknüpfte Notizen

Wird geladen…