Andrei Budruev*, Darja Sinjagina and Olga Kuzmicheva Nizhnii - PowerPoint PPT Presentation

Andrei Budruev*, Darja Sinjagina and Olga Kuzmicheva Nizhnii Novgorod State University, Gagarin Ave., 23, Nizhnii Novgorod, 603950, Russia. E-mail: budruev@gmail.com 1

The mechanism of formation 2,1-benzisoxazol-3(1H)-one and 2-aminobenzoic acid the photolysis 2-azidobenzoic acid OH OH O 1 O O O O h ν h ν O NH N 3 N isc OH OH 3 O O RH N NH 2 CO 2 H azide nitrene N N HO 2 C 2

Infrared spectra of 2-azidobenzoic acid (1) and 2,1-benzisoxazol-3(1H)-one (2) in nujol mull. 1 2 90 90 %T 80 75 %T 60 60 1078,21 1573,91 750,31 1610,09 45 40 1485,19 1597,06 2131,34 2081,19 1067,61 1377,19 3127,12 1458,18 733,92 30 2110,12 1743,66 1719,07 1267,23 1691,57 20 1463,98 15 2852,72 2953,02 0 2924,09 0 2921,22 -20 -15 3500 3000 2500 2000 1750 1500 1250 1000 750 500 4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500 FTIR Measurement 1/cm FTIR Measurement 1/cm 3

Concentration of azide 2.5×10 -3 mol×l -1 (1), 4.2×10 -4 mol×l -1 (2) and 9.3×10 -5 mol×l -1 (3) (HP Hg-lamp DRK-120) C, mol*l -1 C, mol*l -1 C, mol*l -1 C, mol*l -1 1 8,0E-04 3 1 2,5E-03 2,5E-05 1 8,0E-05 2,0E-03 2,0E-05 6,0E-04 6,0E-05 2 1,5E-03 1,5E-05 4,0E-04 4,0E-05 1,0E-03 1,0E-05 2 2,0E-04 2,0E-05 5,0E-04 5,0E-06 3 3 0,0E+00 0,0E+00 0,0E+00 0,0E+00 0 2 4 6 8 10 12 14 0 0,5 1 1,5 2 t, min t, min C, mol*l -1 C, mol*l -1 2 1 4,0E-04 1,20E-04 3,0E-04 8,00E-05 2,0E-04 2 4,00E-05 1,0E-04 3 0,0E+00 0,00E+00 0 0,5 1 1,5 2 2,5 3 t, min 4

2-azidobenzoic acid (1), 2,1-benzisoxazol-3(1H)-one (2) and 2-aminobenzoic acid (3) in acetonitrile A 1,6 1,2 0,8 1 0,4 3 2 0,0 λ , nm 200 250 300 350 400 5

Concentration of azide 7.7×10-4 mol×l -1 (1), 4.0×10 -3 mol×l -1 (2), 2.6×10 -4 mol×l -1 (3) and 4.1×10 -2 mol×l -1 (4) (LP Hg-lamp BUF-30) C, mol*l -1 C, mol*l -1 C, mol*l -1 C, mol*l -1 8,0E-04 1 3 2,5E-04 1 6,00E-05 2,50E-04 1 2,0E-04 2,00E-04 6,0E-04 4,00E-05 1,5E-04 1,50E-04 2 4,0E-04 2 1,0E-04 1,00E-04 2,00E-05 2,0E-04 5,0E-05 5,00E-05 0,0E+00 0,00E+00 0,0E+00 0,00E+00 0 2 4 6 8 10 0 0,5 1 1,5 2 2,5 3 t, min t, min C, mol*l -1 C, mol*l -1 C, mol*l -1 C, mol*l -1 2 4,0E-03 1 4 4,0E-02 1 1,20E-03 6,00E-03 3,0E-03 3,0E-02 9,00E-04 4,00E-03 2,0E-03 2,0E-02 6,00E-04 2 2,00E-03 1,0E-03 2 1,0E-02 3,00E-04 0,0E+00 0,00E+00 0,0E+00 0,00E+00 0 3 6 9 12 15 18 21 0 20 40 60 80 t, min t, min 6

A possible mechanism of the photolysis O O 3 3 1 1 isc O O NH NH OH O RH O h ν O NH NH 2 RH OH OH 1 3 isc O O N N 7