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

O OH hν O OH O 1 2 azide nitrene CO2H N N HO2C O OH NH2 RH O OH N O N hν O N3 isc NH O 3

Infrared spectra of 2-azidobenzoic acid (1) and 2,1-benzisoxazol-3(1H)-one (2) in nujol mull.

90

1 2

3

500 750 1000 1250 1500 1750 2000 2500 3000 3500 1/cm

• 15

15 30 45 60 75 90 %T

2953,02 2924,09 2852,72 2131,34 2110,12 2081,19 1691,57 1597,06 1573,91 1485,19 1458,18 1267,23 1078,21 750,31

FTIR Measurement 500 750 1000 1250 1500 1750 2000 2500 3000 3500 4000 1/cm

• 20

20 40 60 80 %T

3127,12 2921,22 1743,66 1719,07 1610,09 1463,98 1377,19 1067,61 733,92

FTIR Measurement

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)

2,0E-03 2,5E-03 C, mol*l-1 6,0E-04 8,0E-04 C, mol*l-1

1

1

8,0E-05 C, mol*l-1 2,0E-05 2,5E-05 C, mol*l-1

1

3

4

0,0E+00 5,0E-04 1,0E-03 1,5E-03 2 4 6 8 10 12 14 t, min 0,0E+00 2,0E-04 4,0E-04

2 3

0,0E+00 1,0E-04 2,0E-04 3,0E-04 4,0E-04 0,5 1 1,5 2 2,5 3 t, min C, mol*l-1 0,00E+00 4,00E-05 8,00E-05 1,20E-04 C, mol*l-1

1 2 3

2

0,0E+00 2,0E-05 4,0E-05 6,0E-05 0,5 1 1,5 2 t, min 0,0E+00 5,0E-06 1,0E-05 1,5E-05

2 3

2-azidobenzoic acid (1), 2,1-benzisoxazol-3(1H)-one (2) and 2-aminobenzoic acid (3) in acetonitrile

A

5

0,0 0,4 0,8 1,2 1,6 200 250 300 350 400 λ, nm

1 2 3

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)

6,0E-04 8,0E-04 C, mol*l-1 2,00E-04 2,50E-04 C, mol*l-1

1

1

2,0E-04 2,5E-04 C, mol*l-1 6,00E-05 C, mol*l-1

1

3

6

0,0E+00 2,0E-04 4,0E-04 2 4 6 8 10 t, min 0,00E+00 5,00E-05 1,00E-04 1,50E-04

2

0,0E+00 1,0E-03 2,0E-03 3,0E-03 4,0E-03 3 6 9 12 15 18 21 t, min C, mol*l-1 0,00E+00 3,00E-04 6,00E-04 9,00E-04 1,20E-03 C, mol*l-1

1 2

2

0,0E+00 5,0E-05 1,0E-04 1,5E-04 0,5 1 1,5 2 2,5 3 t, min 0,00E+00 2,00E-05 4,00E-05

2

0,0E+00 1,0E-02 2,0E-02 3,0E-02 4,0E-02 20 40 60 80 t, min C, mol*l-1 0,00E+00 2,00E-03 4,00E-03 6,00E-03 C, mol*l-1

1 2

4

A possible mechanism of the photolysis

O 1 O 3

7

O OH NH2 hν NH O O RH O NH 1 RH isc O NH 3 isc O OH N 3 O OH N 1