Allylamine → Allyl-(2-methyl-pent-4-enyl)-amine

To a solution of 2-methyl-pent-4-enoic acid ethyl ester (7.1 g, 50 mmol) was added dropwise a solution of DIBAL (1.0 M in hexanes, 75 ml) at −78 C over 1.0 h. After the addition, the reaction mixture was stirred at −78 C for another hour. The reaction was quenched with saturated NH4Cl (10 ml) and 4% HCl, then was extracted with EtOAc (3×100 ml). The combined organic extracts were dried with MgSO4, filtered, concentrated by rotary evaporation and the crude reaction product was used in the next reaction without further purification. 2-Methyl-4-pentenal (3.3 g, 33.7 mmol) was dissolved in CH2Cl2 (100 ml). To this solution allylamine (2.9 g, 50.5 mmol) was added. Molecular sieves (5 g) were used to absorb water generated during the reaction. The mixture was stirred at room temperature over night. The reaction mixture was concentrated by rotary evaporation and the crude product was used in the next reaction without further purification. Allyl-(2-methyl-pent-4-enylidene)-amine (3.2 g, 23.4 mmol) was diluted in 50 ml MeOH. To the solution NaBH4 (1.0 g, 26.3 mmol) was added at 0° C. After addition the mixture was stirred at RT for 5 h. The reaction mixture was concentrated and the residue was partitioned between EtOAc/20% aq. NaOH. The organic layer was dried over Na2SO4, fitered and concentrated by rotary evaporation to give allyl-(2-methyl-pent-4-enyl)-amine (1.5 g 48% yield): 1H-NMR (400 Hz, CDCl3): d=5.93-5.68 (m, 2H), 5.18-4.92(m, 4H), 3.21(d, 2H), 2.60-2.40(m, 2H), 1.97-1.65(m, 2H), 0.92(d, 3H)

1. additionAfter the addition
2. customThe reaction was quenched with saturated NH4Cl (10 ml) and 4% HCl
3. extractionwas extracted with EtOAc (3×100 ml)
4. dry with materialThe combined organic extracts were dried with MgSO4
5. filtrationfiltered
6. concentrationconcentrated by rotary evaporation
7. customthe crude reaction product
8. customwas used in the next reaction without further purification
9. customto absorb water
10. customgenerated during the reaction
11. stirringThe mixture was stirred at room temperature over night
12. concentrationThe reaction mixture was concentrated by rotary evaporation
13. customthe crude product was used in the next reaction without further purification
14. additionAfter addition the mixture
15. stirringwas stirred at RT for 5 h
16. concentrationThe reaction mixture was concentrated
17. customthe residue was partitioned between EtOAc/20% aq. NaOH
18. dry with materialThe organic layer was dried over Na2SO4
19. concentrationfitered and concentrated by rotary evaporation

ORD record

ord-2987f9039b0a43ad9349673447c3b1ae

Source dataset

uspto-grants-2009_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07563784B2