9
52
M. DURGUN ET AL.
Found (%): C, 43.89; H, 3.08; N, 7.96; S, 8.97. FT-IR (U-ATR, tmax
/
7.32–7.30 (1H, d, J ¼ 8, Ar-H), 7.18–7.14 (1H, t, J ¼ 8, Ar-H),
ꢁ
1
cm ): 3303, 3238 (NH ), 3140–3420 (O-Hꢃ ꢃ ꢃN broad), 3064, 3038 7.10–7.08 (1H, d, J ¼ 8, Ar-H), 7.18–7.10 (2H, broad, –SO NH ), 7.02
2
2
2
(
(
Ar-C-H), 1616 (–C¼N–), 1327 (asymmetric), 1158 (symmetric) (1H, s, Ar-H), 6.93–6.91 (1H, t, J ¼ 8, Ar-H), 6.67–6.65 (1H, t, J ¼ 8,
1
13
S¼O). H-NMR (DMSO-d , TMS, 400 MHz, d ppm): 14.06 (1H, s, Ar- Ar-H), 6.62–6.59 (1H, t, J ¼ 8, Ar-H), 4.29 (2H, s, Ar-CH ). C-NMR
6
2
OH), 9.04 (1H, s, -CH¼N–), 7.42 (2H, s, –SO NH ), 7.89–7.87 (2H, d, (DMSO-d , TMS, 100 MHz, d ppm): 153.59 (Ar-C-OH), 149.26 (Ar-C-
2
2
6
J ¼ 8, Ar-H), 7.76–7,74(1H, d, J ¼ 8, Ar-H), 7.68–7.66 (1H, d, J ¼ 8, N), 145.13, 131.79, 130.25, 129.23, 128.03, 120.14, 114.52, 113.62,
Ar-H), 7.63–7.61 (2H, d, J ¼ 8, Ar-H), 6.97–6.93 (1H, t, J ¼ 8, Ar-H). 112.43, 109.74 (Other Aromatic Carbons), 42.81 (Ar-CH -N). LC-MS
2
1
3
þ
C-NMR (DMSO-d
6
, TMS, 100 MHz, d ppm): 165.88 (–C¼N–), Mass (m/z): Monoisotopic Mass: 355.98; [M þ H] : 357.00
1
2 2
57.78 (Ar-C-OH), 149.96 (Ar-C-N), 142.96 (Ar-C–SO NH ), 137.13,
1
33.28, 127.55, 123.03, 121.84, 120.19, 110.49 (Other Aromatic
Carbons). LC-MS Mass (m/z): Monoisotopic Mass: 353.97; 2.4.2. 3-((3-Chloro-2-hydroxybenzyl)amino)benzenesulfonamide (6)
þ
[M þ H] : 355.00
2
.3.4. 4-((3-Chloro-2-hydroxybenzylidene)amino)benzenesulfona-
mide (4)
ꢂ
Yield: % 60; Colour: White; Melting Point: 121–122 C; Anal. Calcd
for C13 13ClN S (312.77 g/mol) (%): C, 49.92; H, 4.19; N, 8.96; S,
0.25, Found (%): C, 50.01; H, 4.12; N, 9.01; S, 10.16. FT-IR (U-ATR,
H
2 3
O
1
ꢁ
1
t
max/cm ): 3344, 3324 (NH, NH
2
), 3253 (OH), 3111, 3078 (Ar-C-H),
2
1
860–2995 (Aliphatic –C–H), 1617 (–C¼N–) (disappeared), 1325,
ꢂ
Yield: % 85; Colour: Red; Melting Point: 207–209 C; Anal. Calcd for
11ClN S (310.76 g/mol) (%): C, 50.24; H, 3.57; N, 9.01; S,
0.32, Found (%): C, 50.18; H, 3.52; N, 9.10; S, 10.24. FT-IR (U-ATR,
1
315 (asymmetric), 1153, 1138 (symmetric) (S¼O). H-NMR (DMSO-
C
1
13
H
2 3
O
d , TMS, 400 MHz, d ppm): 3.00–5.00 (2H, broad, Ar-OH and N-H),
6
7
.22–7.16 (4H, m, Ar-H and –SO NH ), 7.11–7.09 (1H, d, J ¼ 8, Ar-
2
2
ꢁ
1
tmax/cm ): 3311, 3230 (NH
2
), 3140–3400 (O-Hꢃ ꢃ ꢃN broad), 3064,
H), 7.02 (1H, s, Ar-H), 6.96–6.94 (1H, t, J ¼ 8, Ar-H), 6.78–6.74 (1H, t,
3
(
032 (Ar-C-H), 1616 (–C¼N–), 1330 (asymmetric), 1162 (symmetric)
13
J ¼ 8, Ar-H), 6.68–6.66 (1H, t, J ¼ 8, Ar-H), 4.27 (2H, s, Ar-CH ). C-
2
1
S¼O). H-NMR (DMSO-d , TMS, 400 MHz, d ppm): 13.89 (1H, s, Ar-
6
NMR (DMSO-d , TMS, 100 MHz, d ppm): 151.03(Ar-C-OH), 149.20
6
OH), 9.04 (1H, s, -CH¼N–), 7.41 (2H, s, –SO NH ), 7.90–7.88 (2H, d,
2
2
(Ar-C-N), 145.17, 130.28, 129.00, 127.46, 121.10, 119.83, 114.52,
J ¼ 8, Ar-H), 7.63–7.58 (4H, m, Ar-H) , 7.02–6.98 (1H, t, J ¼ 8, Ar-H).
1
13.34, 112.31, 109.62 (Other Aromatic Carbons), 42.18 (Ar-CH -N).
2
1
3
C-NMR (DMSO-d , TMS, 100 MHz, d ppm): 165.85 (–C¼N–),
þ
6
LC-MS Mass (m/z): Monoisotopic Mass: 312.03; [M þ H] : 313.00
1
56.83 (Ar-C-OH), 150.09 (Ar-C-N), 142.96 (Ar-C–SO
2 2
NH ), 134.52,
1
31.96, 127.42, 122.99, 121.92, 120.64, 119.40 (Other Aromatic
Carbons). LC-MS Mass (m/z): Monoisotopic Mass: 310.02;
2.4.3. 4-((3-Bromo-2-hydroxybenzyl)amino)benzenesulfonamide (7)
þ
[M þ H] : 311.00
2.4. General procedure for the synthesis of amine
derivatives (5–8)
ꢂ
Yield: % 60; Colour: White; Melting Point: 170–172 C; Anal. Calcd
To synthesise amino-derivatives (5–8), sodium borohydride
(
NaBH
4
) (70 mmol) was added in small portions to imino-com-
2 3
for C13H13BrN O S (357.22 g/mol) (%):C, 43.71; H, 3.67; N, 7.84; S,
ꢂ
pounds (1–4) (10 mmol) dissolved in methanol (60 ml) at 0 C, 8.98, Found (%): C, 43.62; H, 3.58; N, 7.93; S, 8.93. FT-IR (U-ATR,
ꢁ1
over 1 h. The mixture was left under stirring for 24 more hours at
room temperature and reductions were monitored through IR 2840–2985 (Aliphatic –C–H), 1616 (–C¼N–) (disappeared), 1338
2
tmax/cm ): 3368, 3348 (NH, NH ), 3254 (OH), 3116, 3066 (Ar-C-H),
1
spectroscopy and TLC. After the reduction was complete, half of (asymmetric), 1135 (symmetric) (S¼O). H-NMR (DMSO-d
the solvent in the reaction mixture was evaporated and the 400 MHz, d ppm): 3.50–5.00 (2H, broad, Ar-OH and N-H), 6.87 (2H,
remaining mixture was poured on ice than the precipitate was fil- s, –SO NH
), 7.45–7.43 (2H, d, J ¼ 8, Ar-H), 7.32–7.30 (1H, d, J ¼ 8,
tered and extracted with DCM and chloroform. The solvent was Ar-H), 7.07–7.05 (1H, d, J ¼ 8, Ar-H), 6.61–6.56 (3H, m, Ar-H), 4.32
6
, TMS,
2
2
1
3
then evaporated and the obtained products were recrystallized (2H, s, Ar-CH
2 6
). C-NMR (DMSO-d , TMS, 100 MHz, d ppm): 153.97
from ethanol/methanol (30/70) and dried under vacuum.
(Ar-C-OH), 151.65 (Ar-C-N), 131.76,.130.48, 129.06, 128.32, 127.15,
1
19.84, 112.65, 111.12 (Other Aromatic Carbons), 42.47 (Ar-CH
2
-N).
þ
LC-MS Mass (m/z): Monoisotopic Mass: 355.98; [M þ H] : 357.00
2
.4.1. 3-((3-Bromo-2-hydroxybenzyl)amino)benzenesulfonamide (5)
2.4.4. 4-((3-Chloro-2-hydroxybenzyl)amino)benzenesulfonamide (8)
ꢂ
Yield: % 60; Colour: White; Melting Point: 123–124 C; Anal. Calcd
for C H BrN O S (357.22 g/mol) (%): C, 43.71; H, 3.67; N, 7.84; S,
1
3
13
2 3
ꢂ
8
.98, Found (%): C, 43.63; H, 3.58; N, 7.93; S, 8.91. FT-IR (U-ATR, Yield: % 60; Colour: White; Melting Point: 180–182 C; Anal. Calcd
ꢁ
1
tmax/cm ): 3355, 3335 (NH, NH
), 3255 (OH), 3114, 3066 (Ar-H), for C13
2
2 3
H13ClN O S (312.77 g/mol) (%): C, 49.92; H, 4.19; N, 8.96; S,
2
1
840–2985 (Aliphatic –C–H), 1611 (–C¼N–) (disappeared), 1330, 10.25, Found (%):C, 50.01; H, 4.10; N, 9.01; S, 10.16. FT-IR (U-ATR,
1
ꢁ1
315 (asymmetric), 1155 (symmetric) (S¼O). H-NMR (DMSO-d
6
,
2
tmax/cm ): 3362 3347 (NH, NH ), 3254 (OH), 3125, 3075 (Ar-C-H),
TMS, 400 MHz, d ppm): 3.00–5.50 (2H, broad, Ar-OH and N-H), 2880–2960 (Aliphatic -C-H), 1616 (–C¼N–) (disappeared), 1308