Carbon Dioxide → Lithium 3-oxo-4-phenylmorpholine-2-carboxylate

温度

-78 °C

A dry 100 mL Schlenk-type flask was fitted with a nitrogen/vacuum line and charged with 2-bromo-1,3,5-tri-tert-butylbenzene (0.521 g, 1.601 mmol), 20 mL dry THF, and a stirbar. The solution was cooled to −78° C. and treated with 2.5M butyllithium (0.582 ml, 1.456 mmol). The reaction was stirred for 15 min and treated with 4-phenylmorpholin-3-one (0.258 g, 1.456 mmol) dissolved in 2 mL dry THF dropwise over 5 min. The reaction was stirred for 2 h at −78° C. The side arm compartment of the Schlenk-type flask was charged with ˜1 g dry ice. The system was sealed, and the dry ice was allowed to sublime into the solution. After 30 min, a nitrogen needle was fitted to the flask, and a solid was noted in the solution. The cooling bath was removed, which caused the solids to bubble (presumably dry ice). The solution was allowed to warm to RT overnight. The solution was diluted with 40 mL water and extracted with dichloromethane (2×10 mL). The water was concentrated in vacuo and dried at 60° C. and 0.15 mmHg to afford lithium 3-oxo-4-phenylmorpholine-2-carboxylate (0.200 g, 60.5% yield). 1H NMR (400 MHz, D2O) 3.72 (t, J=5.23 Hz, 2 H), 3.99 (dt, J=12.10, 5.29 Hz, 1 H), 4.08 (dt, J=12.15, 5.22 Hz, 1 H), 4.61 (s, 1 H), 7.24-7.28 (m, 2 H), 7.32 (tt, 1 H), 7.38-7.44 (m, 2 H).

1. customA dry 100 mL Schlenk-type flask was fitted with a nitrogen/vacuum line
2. stirringThe reaction was stirred for 2 h at −78° C
3. customThe system was sealed
4. waitAfter 30 min
5. customa nitrogen needle was fitted to the flask
6. customThe cooling bath was removed
7. customto bubble (presumably dry ice)
8. temperatureto warm to RT overnight
9. additionThe solution was diluted with 40 mL water
10. extractionextracted with dichloromethane (2×10 mL)
11. concentrationThe water was concentrated in vacuo
12. customdried at 60° C.

ORDレコード

ord-6664b86ae59042108c87371889990079

出典データセット

uspto-grants-2012_01

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08088794B2