Dimethylformamide → 1-Amino-3,3-diethoxypropane

Temperature

60 °C

To 500 ml of dimethylformamide (DMF) containing NaN3 (26.0 g, 400 mmol) was added 3-chloropropionaldehyde diethyl acetal (33.3 g, 200 mmol). The solution was warmed to 60° C., and the reaction was monitored by GC (50° C., 1 min to 250° C. at 15° C./min, DB5-15 m). (Retention time (tR) of starting material 5.1 min, product 6.5 min). The reaction mixture was diluated with 1 L of ice water and extracted with ether (3×500 mL). The combined ether extracts were washed with water (2×500 mL) and then dried over MgSO4. Removal of solvent afforded a crude product, which was dissolved in 500 mL of ethanol containing Pd/C (10%, 2.03 g, 2 mmol). The suspension was degassed, saturated with H2, and stirred under an H2 balloon for four days at which time GC analysis of the product amine (tR 5.4 min) indicated a complete reaction. The solution was degassed and filtered through Celite 545, and the solvent was removed under reduced pressure. The residue was diluted with 25 mL of 12N KOH and extracted with ether (2×50 mL). The ether layer was filtered through glass wool/Na2CO3 and dried over Na2CO3. The solvent was removed under water aspirator vacuum, and the residue was distilled to yield 3-aminopropanal diethylacetal (18.6 g, 126 mmol, 63%): bp17 80°-81.5° C. bp20 68°-70° C. agreed with b.p. in Becke, F. German Patent 845,348, 1952, Chem. Abstr. 47 (1952) 542); 1H--NMR (200 MHz CDCl3) δ 1.21 (t, 6 H, CH3), 1.58 (s, 2 H, NH2), 1.78 (q, 2 H CH2), 2.81 (t, 2 H, NCH2), 3.53 and 3.66 (m, 4 H, OCH2), 4.62 (t, 1 H, CH). Anal. Calcd for C7H17NO2 : C, 57.1; H, 11.6. Found: C, 57.1; H, 11.5.

1. custom50° C., 1 min to 250° C.
2. custom(Retention time (tR) of starting material 5.1 min, product 6.5 min)
3. extractionextracted with ether (3×500 mL)
4. washThe combined ether extracts were washed with water (2×500 mL)
5. dry with materialdried over MgSO4
6. customRemoval of solvent
7. customafforded a crude product, which
8. customThe suspension was degassed, saturated with H2
9. customa complete reaction
10. customThe solution was degassed
11. filtrationfiltered through Celite 545
12. customthe solvent was removed under reduced pressure
13. additionThe residue was diluted with 25 mL of 12N KOH
14. extractionextracted with ether (2×50 mL)
15. filtrationThe ether layer was filtered through glass wool/Na2CO3
16. dry with materialdried over Na2CO3
17. customThe solvent was removed under water
18. distillationthe residue was distilled

ORD record

ord-42195cb8398a4a3f85da866486b19fdf

Source dataset

uspto-grants-1996_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05576426