Page 15 of 20
The Journal of Physical Chemistry
dimethoxyphenyl)benzo[c][1,2,5]thiadiazole (0.549 g,
then water. The organic extract was dried over MgSO4,
and the solvent removed under reduced pressure. The
residue was purified using preparative column chroma-
1
1
2
3
4
5
6
7
8
96%) as a white solid. H NMR (500 MHz, CDCl3): δ
8.00 (dd, 1.5, 0.8 Hz, 1H, H4),
J
=
7.98 (dd, J = 9.0, 0.8 Hz, 1H, H7), 7.61 (dd, J = 9.0, 1.6
Hz, 1H, H6), 6.84 (s, 2H, H3′), 3.80 (s, 6H, OMe),
tography
(SiO2,
CH2Cl2)
to
afford
BTD-
(OMe)2TPA (0.367 g, 50%) as a yellow crystalline solid.
1H NMR (500 MHz, CDCl3): δ 8.02 (dd, J = 1.4, 0.7 Hz,
1H, H4), 7.96 (dd, J = 9.1, 0.7 Hz, 1H, H7), 7.64 (dd, J =
9.1, 1.5 Hz, 1H, H6), 7.31 (dd, J = 8.4, 7.4 Hz, 4H, H3″),
13
0.36 (s, 9H, SiMe3) ppm. C NMR (126 MHz, CDCl3): δ
157.12 (C2′), 155.20 (C3a), 154.22 (C7a), 142.95 (C4′),
136.12 (C5), 134.03 (C6), 123.14 (C4), 119.97 (C7), 118.57
(C1′), 108.74 (C3′), 56.05 (OMe), 0.92 (SiMe3) ppm.
MS (MALDI-TOF) calcd for C17H20N2O2SSi ([M]+): m/z
344.10. Found: m/z 344.08. Elemental analysis calcd for
C17H20N2O2SSi: C, 59.27; H, 5.85; N, 8.13.
Found: C, 59.10; H, 5.92; N, 8.02.
7.21 (dd,
J
=
8.6,
1.0
Hz,
4H,
H2″),
9
7.08 (tt, J = 7.3, 1.0 Hz, 2H, H4″), 6.38 (s, 2H, H3′), 3.58
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
13
(OMe) ppm. C NMR (126 MHz, CDCl3): δ 158.15 (C2′),
155.30 (C3a), 154.11 (C7a), 149.55 (C4′), 147.51 (C1″), 136.07
(C5), 134.48 (C6), 129.43 (C3″), 125.04 (C2″), 123.51 (C4″),
123.18 (C4), 119.76 (C7), 112.11 (C1′), 99.87 (C3′), 55.97
(OMe) ppm. HRMS (ESI) calcd for C26H22N3O2S
([M+H]+): m/z 440.143. Found: m/z 440.143. Elemental
analysis calcd for C26H21N3O2S: C, 71.05; H, 4.82; N,
9.56. Found: C, 71.05; H, 4.86; N, 9.62.
5-(4-Iodo-2,6-
dimethoxyphenyl)benzo[c][1,2,5]thiadiazole
A
solution
of
5-(4-trimethylsilyl-2,6-
dimethoxyphenyl)benzo[c][1,2,5]thiadiazole (0.549 g,
1.59 mmol) in CH2Cl2 (100 mL) was cooled to -78 °C
using a dry ice/acetone bath under an argon atmos-
phere. ICl (2.5 mL, 1 M in CH2Cl2) was added dropwise
and the resultant mixture stirred at -78 °C under an
argon atmosphere for 2 h. The dry ice/acetone bath
was removed, excess ICl quenched by dropwise addi-
tion of aqueous Na2S2O4 (sat., 20 mL), and the mixture
allowed to warm to rt. The product was extracted into
CH2Cl2 and washed with aqueous NH4Cl (sat.), then
water. The organic extract was dried over MgSO4, and
the solvent removed under reduced pressure. The resi-
due was purified using preparative column chromatog-
raphy (SiO2, CH2Cl2) to afford 5-(4-Iodo-2,6-
dimethoxyphenyl)benzo[c][1,2,5]thiadiazole (0.505 g,
4-Methyl-1,2-di(tosylamino)benzene
A mixture of 4-methyl-1,2-phenylenediamine (8.01 g,
65.5 mmol) and pyridine (20 mL, 250 mmol) in CH2Cl2
(150 mL) was cooled to 0 °C using an ice bath.
TsCl (30.0 g, 157 mmol) was added in small portions,
the reaction mixture warmed to rt, and stirred for 3 h
at rt. The product was extracted into CH2Cl2, and
washed with NH4Cl solution (sat.), then water. The
organic extract was dried over MgSO4, and the solvent
removed under reduced pressure. The residue was re-
crystallised from EtOH to afford 4-methyl-1,2-
di(tosylamino)benzene (26.8 g, 95%) as a white solid.
1H NMR (500 MHz, CDCl3): δ 7.60 (d, J = 8.3 Hz, 2H,
1
80%) as a white solid. H NMR (500 MHz, CDCl3): δ
H2′/2″), 7.53 (d, J = 8.3 Hz, 2H, H2′/2″), 7.22 (dd, J = 8.6,
7.97 (d, J = 9.1 Hz, 1H, H7), 7.94 (s, 1H, H4),
7.53 (d, J = 9.0, 1.4 Hz, 1H, H6), 7.03 (s, 2H, H3′), 3.75 (s,
6H, OMe) ppm. 13C NMR (126 MHz, CDCl3): δ 157.92
(C2′), 155.07 (C3a), 154.22 (C7a), 135.13 (C5), 133.58 (C6),
0.6 Hz, 2H, H3′/3″), 7.21 (dd, J = 8.6, 0.6 Hz, 2H, H3′/3″),
7.02 (s, 1H, NH), 6.93 (d, J = 1.4 Hz, 1H, H3), 6.79 (ddd,
J = 8.1, 2.0, 0.7 Hz, 1H, H5), 6.67 (d, J = 8.1 Hz, 1H, H6),
6.43 (s, 1H, NH), 2.39 (s, 6H, Ts-Me), 2.19 (s, 3H, Me)
ppm. 13C NMR (126 MHz, CDCl3): δ 144.31 (C4′/4″),
144.16 (C4′/4″), 138.45 (C4), 135.97 (C1′/1″), 135.44 (C1′/1″),
131.97 (C2), 129.75 (C3′/3″), 129.69 (C3′/3″), 127.80 (C5),
127.70 (C2′/2″), 127.64 (C2′/2″), 127.20 (C1), 127.08 (C6),
126.41 (C3), 21.75 (Ts-Me), 21.73 (Ts-Me), 21.16 (Me)
ppm. HRMS (ESI) calcd for C21H22N2NaO4S2 ([M+Na]+):
m/z 453.091. Found: m/z 453.093. Elemental analysis
calcd for C21H22N2O4S2: C, 58.58; H, 5.15; N, 6.51.
Found: C, 58.48; H, 5.14; N, 6.66.
123.16 (C4),
120.17 (C7),
117.81 (C1′),
114.23 (C3′),
93.92 (C4′), 56.30 (OMe) ppm. MS (MALDI-TOF) calcd
for C14H11IN2O2S ([M]+): m/z 397.96. Found: m/z 397.92.
Elemental analysis calcd for C14H11IN2O2S: C, 42.23; H,
2.78; N, 7.03. Found: C, 42.35; H, 2.76; N, 7.11.
5-(4-Diphenylamino-2,6-
dimethoxyphenyl)benzo[c][1,2,5]thiadiazole
(BTD-
(OMe)2TPA)
A
mixture
of
5-(4-iodo-2,6-
4-Bromo-5-methyl-1,2-di(tosylamino)benzene
dimethoxyphenyl)benzo[c][1,2,5]thiadiazole (0.292 g,
0.733 mmol), diphenylamine (0.229 g, 1.35 mmol) and
t-BuOK (0.264 g, 2.35 mmol) in toluene (20 mL) was
bubbled with argon for 15 min. [t-Bu3PH]BF4 (0.032 g,
0.112 mmol) and Pd2(dba)3 (0.060 g, 0.065 mmol) were
added and the reaction mixture heated at reflux for 15
h under an argon atmosphere. The reaction mixture
was allowed to cool to rt, and the product extracted
into CHCl3, and washed with NH4Cl solution (sat.),
A mixture of 4-methyl-1,2-di(tosylamino)benzene
(23.0 g) and AcONa (8.00 g, 98.0 mmol) in
AcOH (200 mL) was cooled to 0 °C using an ice bath.
Br2 (3.5 mL, 68.0 mmol) was added dropwise, and the
reaction mixture heated at reflux for 3 h. Water was
added, and the precipitate filtered and washed with
water. The residue was recrystallised from EtOH to
afford
4-bromo-5-methyl-1,2-
15
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