Diisopropylamine → HCID 14097595, Verbindung

Temperatur

-10 °C

Diisopropylamine (2.34 ml, 16.7 mmoles) is added to anhydrous THF (75 ml) and cooled to -10° C. At this point 2.24M n-BuLi (6.8 ml, 15.2 mmoles) is added slowly. After complete addition the reaction mixture is stirred for 10 minutes before being cooled to -78° C. At that temperature ethyl N-benzylideneglycinate (4) (2.9 g, 15.2 mmoles) is added and stirring is allowed to proceed for 15 minutes before aldehyde (8) (4.0 g, 15.2 mmoles), dissolved in anhydrous THF (25 ml), is added dropwise to the yellow anion. After complete addition the reaction is stirred another 11/2 hours before being poured into cold 5% aqueous NH4Cl. This mixture is extracted with CHCl3 (3×100 ml). The combined extracts are washed with saturated aqueous NaCl, dried over MgSO4, filtered and evaporated to dryness. The oily residue is taken up in THF (300 ml) and shaken with 5% aqueous HCl (200 ml) in a separatory funnel. This mixture is washed with Et2O (3×100 ml), basified with solid NaHCO3 and extracted with CHCl3 (3×150 ml). The combined extracts are washed with saturated aqueous NaCl (1×150 ml), dried over MgSO4, filtered and evaporated to dryness in vacuo to yield 4.0 g (72% yield) of the desired compound as a yellow glass. 'H-N.M.R. (CHCl3 /TMS): δ=1.20 (t, 3H, --CH2CH3); 1.28 (t, 3H, --CH2CH3 ); 1.45-2.20 (m, 4H, --CH2CH2 --); 2.46 (broad s, 2H, --NH2); 3.18-4.00 (m, 2H, >CH--NH2, CHOH); 4.19 (q, 2H, --CH2CH3); 4.25 (q, 2H, --CH2CH3); 4.53-5.08 (m, 1H, >CH--NH--); 7.05-7.97 ppm (m, 5H, Ph).

1. additionAfter complete addition the reaction mixture
2. temperaturebefore being cooled to -78° C
3. stirringstirring
4. additionis added dropwise to the yellow anion
5. additionAfter complete addition the reaction
6. stirringis stirred another 11/2 hours
7. extractionThis mixture is extracted with CHCl3 (3×100 ml)
8. washThe combined extracts are washed with saturated aqueous NaCl
9. dry with materialdried over MgSO4
10. filtrationfiltered
11. customevaporated to dryness
12. stirringshaken with 5% aqueous HCl (200 ml) in a separatory funnel
13. washThis mixture is washed with Et2O (3×100 ml)
14. extractionextracted with CHCl3 (3×150 ml)
15. washThe combined extracts are washed with saturated aqueous NaCl (1×150 ml)
16. dry with materialdried over MgSO4
17. filtrationfiltered
18. customevaporated to dryness in vacuo

ORD-Eintrag

ord-8f7e2e5eece04d45b1fdba7b28e9c393

Quelldatensatz

uspto-grants-1988_03

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US04730006