반응 #522633

반응 방정식

diisopropylamine

NH4Cl

3-(3,4-diphenylmethylenedioxybenzyl)-1-trimethylsilyl-N-benzylidene-3-aminoprop-1-yne

n-butyllithium

methyl chloroformate

→

3-carbomethoxy-3-(3,4-diphenylmethylenedioxybenzyl)-1-trimethylsilyl-N-benzylidene-3-aminoprop-1-yne

수율 96.6%

용매

tetrahydrofuran

tetrahydrofuran

water

tetrahydrofuran

반응 조건

후처리

1. 1
   workup.WAITAfter an additional 5 minutes
2. 2
   온도After 40 minutes at -78° the solution was warmed to 0°
3. 3
   workup.WAITAfter 10 minutes at 0°
4. 4
   기타The layers were separated
5. 5
   건조dried over Na2SO4
6. 6
   농축concentrated to dryness

실험 절차

To diisopropylamine (700 mg.) in 15 ml. tetrahydrofuran at -78° under N2 was added 3.8 ml. of 1.64 M n-butyllithium dropwise. After 5 minutes, 3-(3,4-diphenylmethylenedioxybenzyl)-1-trimethylsilyl-N-benzylidene-3-aminoprop-1-yne (3.378 g.; 6.74 mmol) in 15 ml. tetrahydrofuran was added dropwise (10 minutes). After an additional 5 minutes, methyl chloroformate (680 mg.) in tetrahydrofuran (10 ml.) was added dropwise (5 minutes). After 40 minutes at -78° the solution was warmed to 0° and the color lightened from deep red to orange. After 10 minutes at 0°, water (5 ml.) was added dropwise followed by 10% aqueous NH4Cl (30 ml.). The layers were separated and the mixture extracted as in the previous example, dried over Na2SO4 and concentrated to dryness to give 3-carbomethoxy-3-(3,4-diphenylmethylenedioxybenzyl)-1-trimethylsilyl-N-benzylidene-3-aminoprop-1-yne (3.645 g.) as an orange foam; Mass spectrum M/e 559, large fragmentation peaks at 287 (base peak) and 272. ##STR13##

출처