8930
N. L. Fur et al. / Tetrahedron 61 (2005) 8924–8931
JZ8.7 Hz, 1H); 8.10 (d, JZ8.7 Hz, 1H); 7.74 (dd, JZ7.5,
131.0 (CH); 130.2(CH); 60.0 (C); 29.5 (CH ); 27.7 (CH );
2 2
24.6 (CH ); 17.0 (CH ); 14.0 (CH ). IR (KBr) (cm ):
3 2 3
K1
7
8
2
.5 Hz, 1H); 7.56 (dd, JZ7.2, 7.9 Hz, 1H); 7.08 (d, JZ
.3 Hz, 2H); 6.86 (d, JZ6.8 Hz, 1H); 6.64 (d, JZ8.3 Hz,
2870–3425, 1627, 1466, 1041, 1012, 761. Anal. Calcd for
C H N OSSn: C, 55.08; H, 7.70; N, 5.35; S, 6.13. Found:
C, 55.66; H, 7.74; N, 5.53; S, 6.02%.
1
3
H); 6.30 (d, JZ7.2 Hz, 1H); 3.59 (s, 3H); 1.29 (s, 9H).
C
2
4 40 2
NMR (CDCl ): d 159.2 (C); 155.1 (C); 150.8 (C); 140.0 (C);
1
3
34.7 (C); 132.3 (CH); 132.1 (CH); 130.7 (CH); 127.9
CH); 126.1(CH); 125.2 (C); 114.1 (CH); 69.2 (CH); 60.9
C); 55.5 (CH ); 24.9 (CH ). Anal. Calcd for C H N O S:
(
(
3.2.9. 4-Deutero-3-p-tolylsulfinylcinnoline (15). Metala-
tion of 14 (0.15 g, 0.56 mmol) according to the general
procedure for direct lithiation with n-BuLi 1.6 M (0.73 ml,
3
3
20 22 2 3
C, 64.94; H, 5.99; N, 7.56. Found: C, 64.61; H, 6.15; N,
7
.72%.
1.17 mmol), DIPAH (0.16 ml, 1.17 mmol), t Z30 min,
1
TZK78 8C, followed by reaction with DCl in D O
2
3
.2.6. 2,2-Dimethyl-1-(3-tert-butylsulfinylcinnolin-4-yl)
(1 ml), t Z5 min, gave after purification by column
2
propan-1-ol (11). Metalation of 6 (0.15 g, 0.64 mmol)
was performed according to the general procedure for direct
lithiation modified as described below with n-BuLi 1.6 M
chromatography on silica gel (dichloromethane/petroleum
ether (2:1)) 0.12 g (81%) of 15.
(
1
0.84 ml, 1.34 mmol), TMPH (0.23 ml, 1.34 mmol), t Z
h, TZK78 8C, followed by reaction with pivaldehyde
3.2.10. (4-Methoxyphenyl)(3-p-tolylsulfinylcinnolin-4-yl)
methanol (16). Metalation of 14 (0.15 g, 0.56 mmol)
according to the general procedure for direct lithiation
with n-BuLi 1.6 M (0.73 ml, 1.17 mmol), DIPAH (0.16 ml,
1
(
ration of the solvent, the crude product was determined by
0.15 ml, 1.34 mmol), t Z1 h. After hydrolysis and evapo-
2
1
H NMR as a single diastereoisomer. The crude product was
washed with water and dichloromethane giving 0.144 g
1.17 mmol), t Z30 min, TZK78 8C, followed by reaction
1
with p-anisaldehyde (0.19 ml, 1.5 mmol), t Z1 h, gave
2
1
(
(
70%) of 11 as a pale yellow solid. Mp 238 8C. H NMR
DMSO-d ): d 9.08 (d, JZ9.0 Hz, 1H, H ); 8.59 (d, JZ
after purification by column chromatography on silica gel
(ethyl acetate/dichloromethane (1:1)) 0.180 g (82%) of 16
as a mixture of two diastereoisomers (ratio 63:37
6
8
8
.3 Hz, 1H, H ); 8.08 (dd, JZ7.5, 6.6 Hz, 1H, H ); 7.95
5
6
1
(
dd, JZ8.3, 7.1 Hz, 1H, H ); 6.44 (d, JZ4.9 Hz, 1H); 5.56
determined by H NMR) as a yellow solid.
7
1
3
(
(
d, JZ4.9 Hz, 1H); 1.23 (s, 9H); 1.00 (s, 9H). C NMR
DMSO-d ): d 154.7 (C, C ); 151.3 (C, C ); 137.1 (C, C );
1
6
3
9
4
Major diastereoisomer. H NMR (CDCl ): d 8.42 (d, JZ
3
1
C ); 124.9 (C, C ); 76.7 (CH, CHOH); 58.0 (C); 38.8 (C);
32.3 (CH, C ); 130.9 (CH, C ); 129.9 (CH, C ); 129.7 (CH,
8.3 Hz, 1H); 7.95 (d, JZ8.7 Hz, 1H); 7.77 (dd, JZ7.2,
7.9 Hz, 1H); 7.70 (m, 1H); 7.64 (d, JZ7.9 Hz, 2H); 7.13 (d,
JZ7.9 Hz, 2H); 6.97 (m, 2H); 6.87 (d, JZ7.9 Hz, 1H); 6.69
(d, JZ9.1 Hz, 2H); 6.13 (d, JZ8.7 Hz, 1H); 3.68 (s, 3H);
7
6
5
8
10
K1
2
1
7.5 (CH ); 23.4 (CH ). IR (KBr) (cm ): 3316, 2964,
3 3
479, 1099, 1044, 1018, 787. Anal. Calcd for
1
3
C H N O S: C, 63.72; H, 7.55; N, 8.74; S, 10.01.
2
2.24 (s, 3H). C NMR (CDCl ): d 159.8 (C); 159.4 (C);
150.6 (C); 142.2 (C); 139.8 (C); 138.8 (C); 134.2 (C); 132.6
1
7
24
2
3
Found: C, 63.43; H, 7.69; N, 8.35; S, 9.78%.
(CH); 132.1 (CH); 130.9 (CH); 130.4 (CH); 128.3 (CH);
3
.2.7. 3-tert-Butylsulfinyl-4-iodocinnoline (12). Metala-
126.0 (CH); 125.6 (C); 125.1 (CH); 114.2 (CH); 69.6 (CH);
55.6 (CH ); 21.8 (CH ).
tion of 6 (0.15 g, 0.64 mmol) according to the general
procedure for direct lithiation with n-BuLi 1.6 M (0.84 ml,
1
K78 8C, followed by reaction with iodine (0.34 g,
1
chromatography on silica gel (ethyl acetate/dichloro-
3
3
1
.34 mmol), TMPH (0.23 ml, 1.34 mmol), t Z1 h, TZ
Minor diastereoisomer. H NMR (CDCl ): d 8.23 (d, JZ
1
3
8.2 Hz, 1H); 8.16 (d, JZ8.7 Hz, 1H); 7.63 (m, 2H); 7.44 (d,
JZ7.9 Hz, 2H); 6.97 (m, 5H); 6.67 (m, 2H); 5.77 (d, JZ
.34 mmol), t Z1 h, gave after purification by column
2
1
3
5.7 Hz, 1H); 3.68 (s, 3H); 2.21 (s, 3H). C NMR (CDCl ): d
3
methane (1:1)) 0.196 g (85%) of 12 as a yellow solid. Mp
1
159.3 (C); 158.0 (C); 151.0 (C); 142.3 (C); 139.7 (C); 137.8
(C); 134.1 (C); 132.2 (CH); 131.9 (CH); 130.8 (CH); 130.2
(CH); 127.9 (CH); 126.5 (CH); 126.0 (CH); 125.1 (C);
114.2 (CH); 69.0 (CH); 55.6 (CH ); 21.8 (CH ). Anal. Calcd
1
34 8C. H NMR (CDCl ): d 8.49 (d, JZ8.4 Hz, 1H); 7.94
3
1
3
m, 3H); 1.40 (s, 9H). C NMR (CDCl ): d 158.8 (C); 150.2
(
3
(
1
C); 133.8 (CH); 133.1 (CH); 131.6 (CH); 130.5 (CH);
3
3
K1
29.1 (C); 110.5 (C); 60.7 (C); 23.9 (CH ). IR (KBr) (cm ):
for C H N O S: C, 68.30; H, 4.98; N, 6.93; S, 7.93.
23 20 2 3
3
2920–3060, 1460, 1377, 1041, 770. Anal. Calcd for
C H IN OS: C, 40.01; H, 3.64; N, 7.78; S, 8.90. Found:
C, 40.45; H, 3.99; N, 7.75; S, 8.66%.
Found: C, 68.58; H, 4.66; N, 6.73; S, 7.64%.
1
2
13
2
3.2.11. 5-Phenylsulfinyl-2-tert-butyl-6-trimethylsilylquin-
azoline (24) and 2-tert-butyl-6-trimethylsilyl-7-thia-1,3-
diaza-benzo[de]anthracene 7-oxide (25). Compound 22
(0.10 g, 0.32 mmol) dissolved in 5 ml of anhydrous
tetrahydrofuran and trimethylsilyl chloride (0.085 ml,
0.67 mmol) were simultaneously introduced at K78 8C
into the solution containing the metalating agent (LTMP)
prepared according to the general procedure for direct
lithiation with n-BuLi 1.6 M (0.42 ml, 0.67 mmol) and
TMPH (0.12 ml, 0.67 mmol). The mixture was then stirred
for 1 h 30 min at K78 8C. The following steps are similar to
general procedure for direct lithiation. A purification by
column chromatography on silica gel (dichloromethane/
3
.2.8. 3-tert-Butylsulfinyl-4-tri-n-butylstannylcinnoline
13). Metalation of 6 (0.15 g, 0.64 mmol) according to the
general procedure for direct lithiation with n-BuLi 1.6 M
0.84 ml, 1.34 mmol), TMPH (0.23 ml, 1.34 mmol), t Z
(
(
1
1
h, TZK78 8C, followed by reaction with tri-n-butyltin
chloride (0.37 ml, 1.34 mmol), t Z1 h, gave after purifi-
2
cation by column chromatography on silica gel (dichloro-
methane/ethyl acetate (7:3)) 0.225 g (67%) of 13 as a yellow
1
oil. H NMR (CDCl ): d 8.49 (d, JZ8.3 Hz, 1H); 8.10 (d,
3
JZ8.3 Hz, 1H); 7.83 (dd, JZ7.5, 7.5 Hz, 1H); 7.74 (dd, JZ
7
0
1
.2, 7.9 Hz, 1H); 1.44 (m, 6H); 1.23 (m, 12H); 1.20 (s, 9H);
1
3
.78 (t, JZ7.2 Hz, 9H). C NMR (CDCl ): d 164.6 (C);
ethyl acetate (9:1)) gave 25 (41 mg, 37%) in a first fraction
as a yellow solid. Mp 260 8C. H NMR (CDCl ): d 8.96
3
1
49.7 (C); 143.2 (C); 134.7 (C); 131.5 (CH); 131.3 (CH);
3