反応 #80409

反応方程式

tosyl azide

N,N-diethyl-3-(N',N'-diethylthiocarbamoyloxy)picolinamide

n-butyllithium

2,2,6,6-tetramethylpiperidine

NH4Cl

→

N,N-diethyl-4-azido-3-(N',N'-diethylthiocarbamoyloxy)picolinamide

溶媒

THF

THF

THF

反応条件

後処理

1. 1
   その他does not exceed -90° C
2. 2
   workup.STIRRINGAfter the mixture has been stirred at -95° C for 1 hour
3. 3
   温度it is again cooled to -102° C
4. 4
   workup.ADDITIONis added in the course of 30 seconds
5. 5
   workup.STIRRINGAfter the mixture has been stirred at -80° C. for 15 minutes
6. 6
   温度the mixture is heated to 0° C.
7. 7
   その他the aqueous phase is separated off
8. 8
   洗浄washed with 500 ml of diethyl ether
9. 9
   洗浄the organic phases are washed once with 200 ml of saturated NH4Cl solution and twice with in each case 150 ml of saturated NaCl solution
10. 10
    乾燥dried over Na2SO4
11. 11
    濃縮concentrated in vacuo
12. 12
    温度the mixture is slowly cooled to 0° C.
13. 13
    workup.STIRRINGwith stirring
14. 14
    ろ過the solid substance is filtered off
15. 15
    その他dried

実験手順

378 ml of n-butyllithium (1.6M in hexane) are added to a solution of 88.2 g (0.624 mol) of 2,2,6,6-tetramethylpiperidine in 11 of THF at -20° C. under argon and the mixture is stirred at this temperature for 1 hour. The mixture is then cooled to -100° C., and a solution of 104.4 g (0.337 mol) of N,N-diethyl-3-(N',N'-diethylthiocarbamoyloxy)picolinamide in 300 ml of THF is added dropwise in such a way that the temperature does not exceed -90° C. After the mixture has been stirred at -95° C for 1 hour, it is again cooled to -102° C, and a solution of 119.3 g (0.605 mol) of tosyl azide in 200 ml of THF, cooled to -20° C., is added in the course of 30 seconds. After the mixture has been stirred at -80° C. for 15 minutes, 400 ml of a saturated NH4Cl solution are added, the mixture is heated to 0° C., and the aqueous phase is separated off and washed with 500 ml of diethyl ether and the organic phases are washed once with 200 ml of saturated NH4Cl solution and twice with in each case 150 ml of saturated NaCl solution, dried over Na2SO4 and concentrated in vacuo. The brown oil is taken up in 1.2 l of hexane under hot conditions, the mixture is slowly cooled to 0° C., with stirring, and the solid substance is filtered off and dried. Yield: 109.0 g of beige-brown crystals which are employed directly in the subsequent step.

出典