تفاعل #160326

معادلة التفاعل

Binap

4-bromobenzonitrile

3-fluorobenzylamine

Cs2CO3

→

yellow solid

المردود 79.9%

4-(3-Fluorobenzylamino)benzonitrile

المردود 79.9%

المذيبات

dioxane

ظروف التفاعل

المعالجة

1. 1
   أخرىthe volatiles were evaporated
2. 2
   workup.ADDITIONCH2Cl2 (100 mL) and H2O (100 mL) were added
3. 3
   أخرىthe layers separated
4. 4
   غسيلThe aqueous layer was washed with CH2Cl2 (2×100 mL)
5. 5
   أخرىdried
6. 6
   تركيزconcentrated under vacuum
7. 7
   أخرىThe crude residue was purified by column chromatography (SiO2; EtOAc/hexanes 0/10 to 3/7)

الإجراء التجريبي

In a flame-dried Schlenk tube, Pd(OAc)2 (304 mg, 1.3 mmol), Binap (1.69 g, 2.7 mmol), and 4-bromobenzonitrile (5.00 g, 27.1 mmol) were added under Ar to a stirring solution of 3-fluorobenzylamine (3.80 g, 30.4 mmol) and Cs2CO3 (13.20 g, 40.6 mmol) in dioxane (55 mL). The mixture was stirred at 80° C. (16 h) and then the volatiles were evaporated. CH2Cl2 (100 mL) and H2O (100 mL) were added and the layers separated. The aqueous layer was washed with CH2Cl2 (2×100 mL). The organic layers were combined, dried and concentrated under vacuum. The crude residue was purified by column chromatography (SiO2; EtOAc/hexanes 0/10 to 3/7) to obtain 4.90 g (78%) of a yellow solid: Rf=0.36 (1/9 EtOAc/hexanes); mp 63-64° C.; IR (nujol mull) 2934, 2861, 2214, 1739, 1605, 1527, 1457, 1375, 1285, 1248, 1164, 915, 824, 784, 730 cm−1; 1H NMR (CDCl3) δ 4.39 (s, CH2N), 4.59-4.74 (br m, NH), 6.57 (d, J=8.8 Hz, 2H3), 6.94-7.05 (m, 2 ArH), 7.11 (d, J=7.5 Hz, H6′), 7.28-7.36 (m, 1 ArH), 7.42 (d, J=8.8 Hz, 2H2); 13C NMR (CDCl3) δ 46.8 (d, J=1.7 Hz, NCH2), 99.9 (CN), 112.4 (ArC), 113.9 (d, J=22.2 Hz, C4′ or C2′), 114.4 (d, J=21.1 Hz, C2′ or C4′), 120.3 (ArC), 122.5 (d, J=2.9 Hz, C6′), 130.3 (d, J=8.6 Hz, C5′), 133.7 (ArC), 140.6 (d, J=6.8 Hz, C1′), 150.9 (ArC), 163.1 (d, J=245.3 Hz, C3′); HRMS (M+H+) (ESI+) 227.0985 [M+H+] (calcd for C14H11FN2H+227.0984).

المصدر