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) while stirring in an ice bath. After stirring at room temperature for 30 min, a saturated aqueous solution of sodium hydrogencarbonate (10 ml) was added to the reaction mixture, and liquid-liquid separation was carried out. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was dissolved again in ethyl acetate (200 ml), dried over potassium carbonate, and concentrated under reduced pressure to provide a pale yellow oil (8.90 g, ESI-MS (m/z): 189). The residue was dissolved in tetrahydrofuran (200 ml), and lithium aluminum hydride (2.00 g) was gradually added thereto while stirring in an ice bath. The reaction mixture was stirred under a nitrogen atmosphere at room temperature for 15 min, then at 65° C. for 1.5 hr. The reaction mixture was cooled in an ice bath, water (2.0 ml), a 5N aqueous solution of sodium hydroxide (2.0 ml) and water (10.0 ml) were added thereto in this order, followed by stirring in an ice bath for 1 hr. Insoluble matter was removed by filtration and washed with tetrahydrofuran, and the filtrate was concentrated under reduced pressure to provide the titled compound as a pale yellow oil (9.2 g, 72%).

1. stirringAfter stirring at room temperature for 30 min
2. dry with materialThe organic layer was dried over anhydrous sodium sulfate
3. concentrationconcentrated under reduced pressure
4. dissolutionThe residue was dissolved again in ethyl acetate (200 ml)
5. dry with materialdried over potassium carbonate
6. concentrationconcentrated under reduced pressure
7. customto provide a pale yellow oil (8.90 g, ESI-MS (m/z): 189)
8. stirringwhile stirring in an ice bath
9. stirringThe reaction mixture was stirred under a nitrogen atmosphere at room temperature for 15 min
10. temperatureThe reaction mixture was cooled in an ice bath
11. stirringby stirring in an ice bath for 1 hr
12. customInsoluble matter was removed by filtration
13. washwashed with tetrahydrofuran
14. concentrationthe filtrate was concentrated under reduced pressure

ORD record

ord-b5ced1fafe944938ba7378e95ffcde95

Source dataset

uspto-grants-2012_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08288538B2