Diethyl Sulfate → tert-Butylisobutylethylamine

Temperatur

70 °C

A mixture of tert-butylisobutylamine (25.84 g, 0.2 mol) and diethyl sulfate (46.26 g, 0.3 mol) was warmed to 70° C. with stirring. An exothermic reaction started and in a few minutes the temperature rose to 150° C. with vigorous boiling of the mixture. After cooling to ˜50° C., 5 M aqueous potassium hydroxide (100 ml, 0.5 mol) was added. The organic layer was separated and dried over anhydrous magnesium sulfate. Diethyl sulfate (10 ml) was added and the mixture was stirred at 100° C. for 1 h. Aqueous 5 M potassium hydroxide (100 ml) was added and the mixture was stirred at 80° C. for 1 h. The organic layer was separated and the aqueous layer was extracted with diethyl ether (50 ml). The organic solutions were combined, dried over anhydrous magnesium sulfate and the product was isolated by distillation. A small amount (1-2%) of tert-butylisobutylamine which was removed by the addition of 2.5 M n-butyllithium in hexane (5.0 ml, 10 mmol) and the product distilled to yield 22.56 g, (72%) of product, bp 68-70° C./40 mm Hg; 1H NMR (CDCl3) δ0.85 (d, J=6.5 Hz, 6H, CH3), 0.98 (t, J=6.5 Hz, 3H, CH3), 1.01 (s, 9H, CH3), 1.66 (n, J=6.5 Hz, 1H, CH), 2.04 (d, J=6.57 Hz, 2H, CH2), 2.51 (q, J=6.5 Hz, 2H, CH2).

1. customAn exothermic reaction
2. waitstarted and in a few minutes
3. customrose to 150° C. with vigorous boiling of the mixture
4. temperatureAfter cooling to ˜50° C.
5. customThe organic layer was separated
6. dry with materialdried over anhydrous magnesium sulfate
7. additionDiethyl sulfate (10 ml) was added
8. stirringthe mixture was stirred at 100° C. for 1 h
9. additionAqueous 5 M potassium hydroxide (100 ml) was added
10. stirringthe mixture was stirred at 80° C. for 1 h
11. customThe organic layer was separated
12. extractionthe aqueous layer was extracted with diethyl ether (50 ml)
13. dry with materialdried over anhydrous magnesium sulfate
14. customthe product was isolated by distillation
15. distillationthe product distilled

ORD-Eintrag

ord-34b25f9e93fc43feb5b9c968548cab3e

Quelldatensatz

uspto-grants-2001_06

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06248885B1