반응 #7304

반응 방정식

dimethyl carbonate

4-Methyl-pyridin-3-ylamine

potassium t-butoxide

THF

→

(4-Methyl-pyridin-3-yl)-carbamic acid methyl ester

수율 89.0%

반응 조건

후처리

1. 1
   기타at 0° C
2. 2
   기타stayed below 0° C
3. 3
   기타the red slurry was quenched with 50 ml water (25 volumes)
4. 4
   추출extracted in 50 ml ethyl acetate (25 volumes)
5. 5
   추출The aqueous layer was extracted with 50 ml ethyl acetate (25 volumes)
6. 6
   농축the orange organic layers were concentrated to an orange solid
7. 7
   농축concentrated to dryness
8. 8
   기타to give very clean light orange solids

실험 절차

The synthesis was carried out by charging 2 grams (1 equiv., 18.5 mmol) 4-Methyl-pyridin-3-ylamine to a solution of 6.55 grams potassium t-butoxide (3 equiv., 55.5 mmol) in 10 ml THF (6.66 euiv., 123 mmol) at 0° C. Upon anion formation, 2.34 ml dimethyl carbonate (1.5 equiv., 27.7 mmol) were charged to the reaction at a rate so that the temperature stayed below 0° C. The reaction was complete within 30 minutes and the red slurry was quenched with 50 ml water (25 volumes) and extracted in 50 ml ethyl acetate (25 volumes). The aqueous layer was extracted with 50 ml ethyl acetate (25 volumes) and then the orange organic layers were concentrated to an orange solid. NMR data showed that t-butanol existed in the product so the solids were slurried in 10 ml toluene (5 volumes) and then concentrated to dryness. This operation was performed three times in order to give very clean light orange solids. (89% yield). 1H NMR: δ8.90 (1 H, brs), 8.28 (1 H, d, J=4.8), 7.16-7.14 (1 H, m), 6.54 (1 H, brs), 3.80 (3 H, s), 2.29 (3 H, s).

출처