Laali et al.
: Isolated as a yellow solid; yield, 3.6 mg (53%); TLC (R
f
7
.75 (t, J ) 8.0 Hz, 1H), 3.39 (s, 3H); ES-MS (ESI+) m/z 298.9
5NO
2
+
+
-
1
[14Me ], 685.0 [14Me ]
2
[BF
4
]; MS/MS m/z 298.9 f 283.9
0.56, 30% EtOAc/hexane); mp 140.0-142.0 °C; H NMR (500
(methyl loss), m/z 685 f 583.0, 298.9, and 283.9.
MHz, CDCl ) δ 8.67 (s, 1H), 8.48 (s, 1H), 8.40 (d, J ) 8.5 Hz,
3
+
-
1
1
4Et BF
4
: H NMR (400 MHz, CD
3
CN) δ 8.88 (d, J ) 8.4
1H), 8.20 (d, J ) 9.5 Hz, 1H), 8.05 (d, J ) 9.5 Hz, 1H), 7.78 (d,
Hz, 1H), 8.44 (d, J ) 8.4 Hz, 1H), 8.40 (d, J ) 8.4 Hz, 1H), 8.36
J ) 5.5 Hz, 1H), 7.68 (d, J ) 5.5 Hz, 1H), 7.44 (m, 1H), 4.18 (s,
3H); 13C NMR (125 MHz, CDCl
(
1
3
d, J ) 8.0 Hz, 1H), 8.23 (d, J ) 8.0 Hz, 1H), 8.14 (d, J ) 8.0 Hz,
3
) δ 132.3 (CH), 126.9 (CH), 124.8
H), 8.02 (d, J ) 8.8 Hz, 1H), 8.00-7.80 (m, 5H), 4.01 (m, 1H),
(CH), 124.6 (CH), 124.4 (CH), 120.4 (CH), 118.4 (CH), 126.7 (CH),
107.5 (CH), 55.9 (CH ) (quaternary carbons not detectable due to
very low quantity of this product); IR (KBr) 2964, 1522, 1262,
1099, 803 cm-1; ES-MS (ESI+) m/z 416.0/418.0 (M + Ag)
.80 (m, 1H), 0.50 (t, J ) 7.0 Hz, 3H); ES-MS (ESI+) m/z 312.3
3
+
[14Et ]; MS/MS m/z 312.3 f 284.2.
+
-
1
+
.
1
5Me BF
4
: obtained as light-brown solid ( H NMR showed
ca. 40% unreacted 15); yield, 3.8 mg (crude, approximately 60%);
8NO : Isolated as a yellow solid; yield, 3.1 mg (42%); TLC (R
2
f
1
1
H NMR (400 MHz, CD
J ) 8.4 Hz, 1H), 8.31 (d, J ) 7.6 Hz, 1H), 8.28 (d, J ) 8.4 Hz,
3
CN) δ 8.62 (d, J ) 9.2 Hz, 1H), 8.34 (d,
0.27, 15% CH Cl /hexane); mp 124.0-126.0 °C; H NMR (500
2
2
MHz, CDCl
3
) δ 9.15 (d, J ) 8.5 Hz, 1H), 8.57 (d, J ) 5.5 Hz,
H), 8.37 (dd, J ) 7.0, 1.0 Hz, 1H), 8.15 (d, J ) 8.5 Hz, 1H), 7.86
t, J ) 8.5 Hz, 1H), 7.79 (t, J ) 8.5 Hz, 1H), 7.82 (d, J ) 5.5 Hz,
1
2
H), 8.24 (d, J ) 8.0 Hz, 1H), 7.95 (t, J ) 8.0 Hz, 1H), 7.91 (s,
1
(
1
H), 7.88 (d, J ) 8.0 Hz, 1H), 7.54 (d, J ) 2.8 Hz, 1H), 7.49 (dd,
1
J ) 8.8, 2.8 Hz, 1H), 4.00 (s, 3H), 3.18 (s, 3H); H NMR (400
13
H), 7.63 (d, J ) 8.5 Hz, 1H), 4.15 (s, 3H); C NMR (125 MHz,
) δ 145.0 (C), 140.6 (C), 134.7 (C), 131.9 (CH), 128.7 (CH),
28.0 (CH), 127.4 (CH), 127.1 (CH), 126.7 (C), 125.2 (CH), 124.6
MHz, CDCl
Hz, 1H), 8.18 (d, J ) 8.0 Hz, 2H), 7.89 (t, J ) 8.0 Hz, 1H), 7.82
s, 2H), 7.75 (br s, 1H), 7.70 (br s, 1H), 7.38 (s, 1H), 4.02 (s, 3H),
3
) δ 8.95 (br s, 1H), 8.62 (br s, 1H), 8.29 (d, J ) 8.0
CDCl
3
1
(
(
3
C), 123.9 (CH), 123.4 (CH), 121.8 (C), 117.9 (CH), 63.8 (CH );
+
3
.38 (s, 3H); ES-MS (ESI+) m/z 329.1 [15Me ], 745.2
-1
IR (KBr) 1528, 1400, 1092, 773, 705 cm ; ES-MS (ESI+) m/z
+
-
[15Me ]
2
[BF
4
]; MS/MS m/z 329 f 314.0 (methyl loss), m/z 745
+
4
16.0/417.9 (M + Ag) .
f 329.1, 314.1, and 270.9.
Model Nitration of Thia-PAHs (For a Typical Procedure, see
1
f
1NO
0.33, 30% CH
MHz, CDCl ) δ 9.10 (d, J ) 9.5 Hz, 1H), 8.73 (d, J ) 8.5 Hz,
H), 8.02 (d, J ) 8.5 Hz, 1H), 8.00 (d, J ) 9.0 Hz, 1H), 7.67 (d, J
2
: Isolated as a yellow solid; yield, 6.8 mg (49%); TLC
1
(R
2 2
Cl /hexane); mp 193.0-195.0 °C; H NMR (500
Supporting Information): 1NO
2
(bright yellow solid); yield, 6.4
0.57, 20% CH Cl /hexane); mp
97.0-199.0 °C; H NMR (500 MHz, CDCl ) δ 8.94 (s, 1H), 8.74
3
mg (76% isolate yield); TLC (R
1
f
2
2
1
)
7
1
3
9.0 Hz, 1H), 7.62 (t, J ) 8.5 Hz, 1H), 7.55 (t, J ) 8.5 Hz, 1H),
(
(
(
(
1
(
d, J ) 8.5 Hz, 1H), 8.23 (m, 1H), 8.21 (d, J ) 8.5 Hz, 1H), 7.97
.53 (d, J ) 9.5 Hz, 1H), 4.09 (s, 3H); 13C NMR (125 MHz, CDCl
3
)
m, 1H), 7.77 (t, J ) 8.5 Hz, 1H), 7.72 (t, J ) 8.5 Hz, 1H), 7.59
m, 2H); 13C NMR (CDCl
3
, 125 MHz) δ 144.7 (C),143.9 (C), 139.0
δ 147.3 (C), 140.3 (C), 137.6 (C), 135.8 (C), 128.9 (C), 126.8 (CH),
1
1
1
25.9 (CH), 125.2 (C, CH), 124.5 (2CH), 124.3 (C), 123.5 (CH),
C), 135.7 (C), 130.4 (C), 129.2 (CH, C), 128.1 (CH), 127.4 (CH),
25.5 (CH), 125.0 (CH), 124.8 (CH), 123.7 (C), 123.1 (CH), 121.8
CH), 118.5 (CH); IR (KBr) 1533, 1482, 1373, 1143, 1031, 715
19.5 (CH), 113.4 (CH), 57.0 (CH
3
); IR (KBr) 1527, 1358, 1271,
079, 799 cm 1; ES-MS (ESI+) m/z 416.1/418.1 (M)+.
-
-
1
+
cm ; ES-MS (ESI+) m/z 386.0/387.9 (M + Ag) .
NO and 2aNO : The isomeric mixture was isolated after TLC
separation (R 0.27-0.29, streaks, 20% CH Cl /hexane) as a bright
yellow solid; combined yield, 6.8 mg (73%). 2NO
MHz, CDCl ) δ 9.02 (s, 1H), 8.23 (d, J ) 7.5 Hz, 1H), 8.13 (d, J
9 Hz, 1H), 8.22 (d, J ) 2.5 Hz, 1H), 7.95 (d, J ) 7.5 Hz, 1H),
.58-7.52 (m, 2H), 7.37 (dd, J ) 9.0, 2.5 Hz, 1H), 4.02 (s, 3H);
Model Bromination of Thia-PAHs (For a Typical Procedure,
See Supporting Information). 4Br: TLC (R
f
0.56, 40% CH
hexane); mp 138.0-140.0 °C; H NMR (400 MHz, CDCl ) δ 8.95
(d, J ) 8.4 Hz, 1H), 8.52 (dd, J ) 8.4, 0.8 Hz, 1H), 7.86 (d, J )
.4 Hz, 1H), 7.85 (m, 1H), 7.77 (d, J ) 8.4 Hz, 1H), 7.71 (m, 1H),
2 2
Cl /
2
2
2
1
3
f
2
2
1
2
: H NMR (500
8
3
13
)
7.55 (s, 1H), 7.13 (s, 1H), 4.14 (s, 3H); C NMR (125 MHz,
CDCl
7
3
) δ 153.3 (C), 137.6 (C), 136.0 (C), 131.5 (C), 130.0 (C),
13
C NMR (CDCl
3
, 125 MHz) δ 127.1 (CH), 126.7 (CH), 125.5
127.6 (CH), 127.0 (CH), 126.9 (C), 126.2 (CH), 125.7 (CH), 125.6
(CH), 123.0 (CH), 121.6 (CH), 120.4 (CH), 119.4 (CH), 103.8 (CH).
(CH), 122.9 (CH), 122.1 (CH), 121.5 (C), 113.2 (C), 103.2 (CH),
1
-1
2
aNO
2
: H NMR (500 MHz, CDCl
3
) δ 8.26-8.20 (m, 3H), 7.67
55.6 (CH
(ESI+) m/z 449.1/451.0/ 453.0 (M + Ag) .
Br and 6Br : The isomeric mixture was obtained after TLC
separation (R 0.53, 40% CH Cl /hexane) as a white solid (3.8 mg,
7% combined isolated yield). 6Br (major product): H NMR (500
3
); IR (KBr) 1604, 1253, 1127, 1104, 847 cm ; ES-MS
+
(
1
d, J ) 9 Hz, 1H), 7.44 (d, J ) 9 Hz, 1H), 7.95 (d, J ) 7.5 Hz,
13
3
H), 7.58-7.52 (m, 2H), 4.08 (s, 3H); C NMR (CDCl , 125 MHz)
6
2
δ 128.2 (CH), 126.7 (CH), 125.0 (CH), 122.9 (CH), 122.9 (CH),
1
f
2
2
21.7 (CH), 117.8 (CH), 113.5 (CH); ES-MS (ESI+) for 2NO
2
/
1
3
+
2
aNO
NO
separation (R
2
m/z 415.6/417.6 (M + Ag) .
and 3aNO : The isomeric mixture was isolated after TLC
0.6, 50% CH Cl /hexane) as a bright yellow solid;
: H NMR (400 MHz, CDCl ) δ 9.33 (d, J )
MHz, CDCl ) δ 9.20 (d, J ) 8.5 Hz, 1H), 8.35 (d, J ) 9.0 Hz,
3
3
2
2
1
H), 8.04 (d, J ) 8.5 Hz, 1H), 7.98 (d, J ) 9.0 Hz, 1H), 7.89 (d,
f
2
2
J ) 8.5 Hz, 1H), 7.69 (d, J ) 5.5 Hz, 1H), 7.61 (d, J ) 5.5 Hz,
1
2
8
8
7
.9 mg (38%). 3NO
.4 Hz, 1H), 8.67 (d, J ) 8.4 Hz, 1H), 8.66 (s, 1H), 8.16 (d, J )
2
3
13
1
H), 7.50 (d, J ) 8.5 Hz, 1H), 4.12 (s, 3H); C NMR (125 MHz,
CDCl ) δ 154.0 (C), 139.8 (C), 134.2 (C), 132.8 (C), 129.9 (CH),
26.6 (CH), 126.3 (CH), 126.1 (CH), 125.3 (C), 124.8 (CH), 124.7
CH), 122.7 (CH), 121.9 (C), 120.0 (C), 112.1 (CH), 110.7 (C),
3
.0 Hz, 1H), 8.00 (d, J ) 8.0 Hz, 1H), 7.94 (t, J ) 8.4 Hz, 1H),
1
(
5
8
9
7
.85 (d, J ) 5.2 Hz, 1H), 7.84 (t, J ) 8.4 Hz, 1H), 7.68 (d, J ) 5.2
1
Hz, 1H). 3aNO
2
: H NMR (400 MHz, CDCl
3
) δ 9.01 (d, J ) 8.4
(minor product): 1H NMR (500 MHz, CDCl
3 2 3
6.8 (CH ). 6Br ) δ
Hz, 1H), 8.44 (s, 1H), 8.08 (d, J ) 8.4 Hz, 1H), 8.08 (d, J ) 8.4
Hz, 1H), 7.99 (d, J ) 8.4 Hz, 1H), 7.99 (d, J ) 8.4 Hz, 1H), 7.93
.87 (d, J ) 8.5 Hz, 1H), 8.34 (d, J ) 9.0 Hz, 1H), 7.91 (d, J )
.0 Hz, 1H), 7.88 (d, J ) 8.5 Hz, 1H), 7.83 (d, J ) 8.5 Hz, 1H),
(
d, J ) 8.4 Hz, 1H), 7.90 (t, J ) 8.4 Hz, 1H), 7.77 (d, J ) 8.4 Hz,
13
.57 (s, 1H), 7.47 (d, J ) 8.5 Hz, 1H), 4.11 (s, 3H); C NMR
+
1
H); ES-MS (ESI+) for 3NO
NO : Isolated as bright yellow solid; yield, 3.6 mg (58%); TLC
0.33, 40% CH
MHz, CDCl ) δ 9.30 (d, J ) 8.5 Hz, 1H), 8.43 (d, J ) 8.5 Hz,
H), 8.15 (d, J ) 9 Hz, 1H), 7.98 (t, J ) 8.5 Hz, 1H), 7.83 (t, J )
.5 Hz, 1H,), 7.76 (d, J ) 5 Hz, 1H), 7.71 (d, J ) 9 Hz, 1H), 7.65
2 2
/3aNO m/z 386.0/387.9 (M + Ag) .
(
(
3
125 MHz, CDCl ) δ 129.8 (CH), 129.4 (CH), 127.3 (CH), 126.6
4
2
3
CH), 125.0 (CH), 121.6 (CH), 112.1 (CH), 56.7 (CH ) (quaternary
1
(R
f
2 2
Cl /hexane); mp 125.0-126.0 °C; H NMR (500
carbons not detectable due to very small quantity of this product);
3
+
ES-MS (ESI+) m/z 449.1/451.0/452.9 (M + Ag) .
1
8
(
d, J ) 5 Hz, 1H), 4.16 (s, 3H); 1 C NMR (125 MHz, CDCl
3
Acknowledgment. Support of this study under “reactive
intermediates of carcinogenesis of PAHs” at KSU by the NCI
of NIH (2R15-CA078235-02A1) is gratefully acknowledged.This
work was also supported in part by a grant to S.K. (#R826192)
by the US-EPA, Washington, D.C.
3
) δ
1
1
1
45.1 (C), 139.8 (C), 134.9 (C), 130.9 (C), 129.3 (CH), 127.4 (CH),
27.0 (CH), 126.7, 126.6 (CH), 124.7 (2CH), 124.4 (C), 124.2 (CH),
22.0 (C), 64.0 (CH ); IR (KBr) 2925, 1522, 1260, 1092, 805 cm ;
3
-1
+
ES-MS (ESI+) m/z 416.1/418.0 (M + Ag) .
8392 J. Org. Chem., Vol. 72, No. 22, 2007