Methyl chloroformate → N,N-Diethyl-N'-methyl-1,3-propanediamine

To a solution of N,N-diethyl-1,3-propanediamine (10.0 ml) and triethylamine (10.0 ml) in tetrahydrofuran (150 ml) was added dropwise methyl chloroformate (5.15 ml) in an ice bath, followed by stirring at room temperature for 30 min. To the reaction mixture was added a saturated aqueous solution of sodium hydrogencarbonate (10 ml) to partition. The organic layer was dried over anhydrous sodium sulfate, and concentrated under a reduced pressure. The residue was dissolved in ethyl acetate (200 ml) again, dried over potassium carbonate, and concentrated under a reduced pressure to provide a pale yellow oil (8.90 g, ESI-MS (m/z):189). This residue was dissolved in tetrahydrofuran (200 ml), and then lithium aluminium hydride (2.00 g, 0.826 mmol) was gradually added thereto while cooling in an ice bath and stirring, followed by stirring under a nitrogen atmosphere at room temperature for 15 min and then at 65° C. for 1.5 hrs. The reaction mixture was cooled in an ice bath, and then supplied with water (2.0 mL), an 5 N aqueous solution of sodium hydroxide (2.0 mL) and water (10.0 mL), followed by stirring in an ice bath for 1 hr. The insoluble portion was filtered and washed with tetrahydrofuran to give a filtrate, which was concentrated under a reduced pressure to provide a crude product of the titled compound (9.2 g, 72.3%) as a pale yellow oil.

1. customto partition
2. dry with materialThe organic layer was dried over anhydrous sodium sulfate
3. concentrationconcentrated under a reduced pressure
4. dissolutionThe residue was dissolved in ethyl acetate (200 ml) again
5. dry with materialdried over potassium carbonate
6. concentrationconcentrated under a reduced pressure
7. customto provide a pale yellow oil (8.90 g, ESI-MS (m/z):189)
8. temperaturewhile cooling in an ice bath
9. stirringstirring
10. stirringby stirring under a nitrogen atmosphere at room temperature for 15 min
11. waitat 65° C. for 1.5 hrs
12. temperatureThe reaction mixture was cooled in an ice bath
13. stirringby stirring in an ice bath for 1 hr
14. filtrationThe insoluble portion was filtered
15. washwashed with tetrahydrofuran
16. customto give a filtrate, which
17. concentrationwas concentrated under a reduced pressure

ORD record

ord-bc5cd27b77c64caca521ebec8a8f5178

Source dataset

uspto-grants-2009_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07531532B2