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Experiments for NO2-Bn systems

• Photo product quantum yield Xenon monochomater (300 nm) and characterize the products (azo
benzene and ferrioxalate standards characterise using HPLC)—All NO2-Bn systems
O
ON S CH
3
H
O
N
O2

• Different solvent ratio (CD3CN:buffer) and pH- Products and Kinetics-


• Confirming photoprducts with authentic standards (LC-MS, NMR)-
CO O H
CHO

NO
NO 2

-
C H 3S O 2

CHO

C H 3S O 2N H 2

NO
• Reactant Concentration is independent of formation of products-Laser flash photolysis to
find intermediates finally mechanism (N-O bond cleavage methane sulphonamide and
nitro benzaldehyde are the products)
HO
M
eO N Me
O S
O
M
eO N
O2

• Mechanism-based on the products and role of –NO2 in PPG

H O
N M e
O S
O
N O 2

H O
N M e
O S
O

• HNO detection by vibrational spectroscopy DFT calculation to electron density movement and
• S0NO2(n,π) S1 or T1NO2(n,π*) based on the LFP data
• Use of TXPTS trap for (will be checked)
HO H
O
NC
F3Me
O NC
F
OS 3
O
S
O O
N
O
2 M
eO
OMe OMe
OMe

k
hv H+
H2O O
O N
NO2 N

OH O
(a) (b) (c)

OMe OMe
CHO
OH
O MeOH

N N O NO
OH
(e) (f)
(d)
s
CHO
H H O
O H

O
H
N S R hv .
O S
.N S R

H O
O
RSO2NH2
O O
O H

O
H
N S R hv
C O .. N H S R C H

O R S O 2N H 2
O O H
N O 2
N N O

O O
O
H
O O O N S CH3
H H
O N S CH3 hv O N S CH3 O
O O
O
NO2 N O
N
OH O H

NO

CH3SO2- HNO
O O
H H
O N S CF3 hv O N S CF3 CHO
O CF3SO2NH2
O
NO2 N O
NO2
O
H
Photolysis of o-NBOC-ONHSO2CH3 (24)

5%

70%

25%

Scheme 5: Proposed photolysis pathway of o-NBOC-ONHSO2CH3

8
LC-MS results

Photolysis of
CHO

NO 2

Photolysis of
O
ON S CH
3
H
O
N
O2
O
ON S CH
3
H
O
N
O2

Photolysis of NB-ONHSO2CH3

BLANK
NB-ONHSO2CH3
METHANE SULFONAMIDE didn’t show up in a
negative mode!

CH3SO2NH2

O O
H H
CHO O N S C H 3 h v O N S C H 3 C H O
Photolysis of N O
O
N O
O C H 3 S O 2 N H 2
2
NO 2 N O 2
O
H
h v

C O O H

N O