anhyd Et
2
O (3 mL) was added, and then the reaction mixture
3
DMF (56.4 mL), and 2 equiv of Et N (1.26 mL) was added. The
was filtered. The filtrate was concentrated to afford 221 mg
mixture was heated to 100 °C for 1 h and cooled to room
temperature, and the solvent was removed under reduced
pressure. The solid obtained was purified by flash chromatog-
1
(
100%) of ppz 1 as a beige solid: mp 284-285 °C; H NMR
(CDCl
3
) δ 7.78 (dd, 2H, J ) 8.2, 4.4 Hz), 8.89 (dd, 2H, J ) 1.6,
8
.2 Hz), 9.21 (s, 2H), 9.23 (dd, 2H, J ) 1.6, 4.4 Hz); 13C NMR
2 2 f
raphy (2 M ammonia in MeOH/CH Cl 4.8: 0.4, R 0.47) to give
1
(CDCl
3
) δ 124.3, 125.8, 131.1, 142.9, 145.2, 146.0, 151.3; HRMS
103.1 mg (80%) of 13: mp > 360 °C; H NMR (DMSO) δ 8.10
+
(
MH ) calcd for m/ z C14
,3-Dip h en yl-1,4,5,12-tetr a a za tr ip h en ylen e (7). Diamine
(250 mg, 1.19 mmol) was stirred in anhyd EtOH (15 mL) at
8 4
H N 233.0827, found 233.1818.
(dd, 2H, J ) 8.4, 4.4 Hz), 9.27 (dd, 2H, J ) 4.4, 1.2 Hz), 9.42
2
(dd, 2H, J ) 8.4, 1.2 Hz); 13C NMR (DMSO) δ 114.6, 126.5, 128.0,
+
6
132.5, 132.7, 142.2, 142.5, 151.9; HRMS (MH ) calcd for C16
H
6
N
6
room temperature and degassed with argon for 15 min. 1,2-
Diphenylethane-1,2-dione (benzil) (270 mg, 1.31 mmol) was
injected and refluxed for 3 h under argon. After being cooled to
room temperature, the product was filtered and washed with
m/ z 283.0732, found 283.0736. This procedure results in a
significant higher yield than reported previously.1
8
1,4,5,12-Tetr aazatr iph en ylen e-2,3-dicar boxylic Acid (14).
A solution of dicarbonitrile 13 (200 mg, 0.709 mmol) in 50% H
SO (14 mL) was heated under reflux for 3 h. The mixture was
cooled, H O added (4 mL), and NaHCO used for neutralization.
2
-
anhyd EtOH and Et
2
O to afford 333 mg (73%) of 7 as a beige
4
1
solid: mp 300-301 °C dec; H NMR (CDCl
3
) δ 7.37 (m, 6H), 7.73
dd, 4H, J ) 6.6, 2.0 Hz), 7.79 (dd, 2H, J ) 8.4, 4.4 Hz), 8.95
dd, 2H, J ) 8.4, 1.4 Hz), 9.27 (dd, 2H, J ) 4.4, 1.4 Hz); 13
) δ 123.8, 125.9, 128.3, 128.9, 130.3, 131.0, 138.8,
2
3
(
(
Precipitation was then initiated by adding concentrated HCl (4
mL). After the mixture was stirred for 20 min, additional HCl
was added until there was no more precipitation. The light
C
NMR (CDCl
3
+
1
3
40.5, 145.4, 151.4, 154.4; HRMS (MH ) calcd for C26
H
16
N
4
m/ z
yellow suspension was filtered, washed with cold H
acetone, and Et O, and dried in a vacuum at 100 °C to afford
197.5 mg (87%) of 14 as a light yellow solid: mp > 360 °C; IR
2
O, cold
85.1453, found 385.1456. Anal. Calcd for C26 : C, 81.23;
H
16
N
4
2
H, 4.20; N, 14.57. Found: C, 81.45; H, 3.98; N, 14.5. Compounds
-10 were synthesized following the procedures described above.
,3-Dim eth yl-1,4,5,12-tetr a a za tr ip h en ylen e (8). This com-
pound was purified by flash chromatography (2 M ammonia in
MeOH/CH Cl 4.8: 0.4, R 0.45) to afford 83% of 8 as a white
solid: mp 241-243 °C; H NMR (CDCl ) δ 2.99 (s, 6H), 7.76 (dd,
H, J ) 8.3, 4.4 Hz), 8.93 (dd, 2H, J ) 8.3, 1.6 Hz), 9.26 (dd,
H, J ) 4.4, 1.6 Hz); 13C NMR (CDCl
) δ 123.5, 125.2, 131.0,
-
1 1
8
1658, 3470 cm ; H NMR (DMSO) δ 8.01 (dd, 2H, J ) 8.2, 4.4
Hz), 9.21 (dd, 2H, J ) 4.4, 1.4 Hz), 9.38 (dd, 2H, J ) 8.4, 1.4
Hz); 13C NMR (DMSO) δ 125.3, 126.9, 132.4, 141.6, 143.6, 145.3,
2
2
2
f
151.2, 166.2; Anal. Calcd for C16
2.85; N, 16.83, found C, 57.62; H, 2.77; N, 17.19; HRMS (MH )
calcd for C16 m/ z 321.0624, found 321.0620.
8 4 4 2
H N O 0.7H O: C, 57.73; H,
1
+
3
2
2
1
2
8 4 4
H N O
3
+
1,4, 5,12-Tetr a a za tr ip h en ylen e-2,3-d ica r boxylic Acid Di-
a m id e (15). A solution of dicarbonitrile 13 (200 mg, 0.709 mmol)
40.3, 145.4, 151.2, 155.2; HRMS (MH ) calcd for C16
H
12
N
4
m/ z
61.1140, found 261.1131. Anal. Calcd for C16 : C, 73.83;
H
12
N
4
in concd H
and diluted by dropwise addition to vigorously stirred ice-H
(20 mL). The mixture was neutralized with solid NaHCO until
no more precipitation occurred. The suspension was filtered,
washed with cold H O, acetone, and Et O, and dried in a vacuum
at 100 °C to afford 178.2 mg (79%) of 15 as a beige solid: mp
2 4
SO (5 mL) was stirred at room temperature for 3 d
H, 4.65; N, 21.52. Found: C, 73.63; H, 4.50; N, 21.06.
,3-Dip yr id in -2-yl-1,4,5,12-tetr a a za tr ip h en ylen e (9). This
compound was purified by flash chromatography (2 M ammonia
in MeOH/CH Cl 4.8: 0.4, R 0.67) to afford 70% of 9 as a white
solid: mp > 360 °C; H NMR (CDCl ) δ 7.26 (dd, 2H, J ) 7.6,
.8 Hz), 7.81 (dd, 2H, J ) 8.4, 4.4 Hz), 7.88 (dd, 2H, J ) 7.6, 7.6
Hz), 8.27 (d, 2H, J ) 7.6 Hz), 8.38 (d, 2H, J ) 4.8 Hz), 8.96 (dd,
2
O
2
3
2
2
f
2
2
1
3
-
1 1
4
260-261 °C dec; IR (Nujol) 1684, 3275 cm ; H NMR (DMSO)
δ 7.9 (s, 2H), 8.0 (dd, 2H, J ) 8.1, 4.4 Hz), 8.22 (s, 2H), 9.22 (dd,
H, J ) 8.4, 1.6 Hz), 9.29 (dd, 2H, J ) 4.4, 1.6 Hz); 13C NMR
CDCl ) δ 123.1, 124.0, 125.2, 126.1, 131.1, 136.8, 140.9, 145.2,
2H, J ) 4.4, 1.4 Hz), 9.39 (dd, 2H, J ) 8.1, 1.4 Hz); HRMS (MH )
+
2
(
1
3
7
3
10 6 2
calcd for C16H N O m/ z 319.0943, found 319.0939.
+
48.4, 151.5, 153.6, 157.2; HRMS (MH ) calcd for C24
87.1358, found 387.1360. Anal. Calcd for C24 ‚0.4H
3.06; H, 3.65; N, 21.10. Found: C, 73.28; H, 3.71; N, 21.37.
,8,9,10,17,18-Hexa a za p h en a n th r o[9,10-b]tr ip h en ylen e
H
14
N
6
m/z
1,4,5,12-Tetr a a za tr ip h en ylen e-2,3-d ica r boxylic Acid Di-
m eth yl Ester (16). To an argon-flushed solution of diamide 15
(200 mg, 0.629 mmol) in concd H SO (4 mL) was injected anhyd
2 4
MeOH (15 mL) at room temperature. The reaction mixture was
refluxed for 12 h until the full consumption of the diamide 15
2 2 f
was observed (TLC, 2 M ammonia in MeOH/CH Cl 2.8:1.2, R
0.65). The brown mixture was cooled, water was added (25 mL),
and then the solution was filtered. The filtrate was neutralized
H
14
N
6
2
O: C,
1
1
(
10). The isolated yield was 81%: mp > 360 °C; H NMR (CD
3
-
OD/D O 10:1) δ 7.62 (dd, 4H, J ) 8.0, 4.4 Hz), 8.32 (br, 4H),
2
+
8
.77 (d, 4H, J ) 8.0); HRMS (MH ) calcd for C24
85.1202, found 385.1190.
,4,5,12-Tetr a a za tr ip h en ylen e-2,3-d iol (11). To a vigor-
ously stirred mixture of diamine 6 (100 mg, 0.476 mmol) in 100
H
12
N
6
m/ z
3
1
with solid NaHCO
the combined organic layers were washed with brine, dried
(MgSO ), and concentrated. The residue was dissolved in CHCl
(5 mL) and filtered and the filtrate concentrated to afford 151
3 2 2
. The product was extracted with CH Cl , and
2
7
mL of THF and 5 equiv of anhyd pyridine (0.2 mL, 2.3 mmol)
under an argon atmosphere at -78 °C was added oxalyl chloride
4
3
-
1 1
(
66.48 mg, 0.524 mmol) dropwise. After the red mixture was
mg (69%) of ester 16: IR 1737 cm ; H NMR (DMSO) δ 4.14 (s,
6H), 7.86 (dd, 2H, J ) 8.4, 4.4 Hz), 8.96 (dd, 2H, J ) 8.4, 1.2
Hz), 9.31 (dd, 2H, J ) 4.4, 1.2 Hz); 13C NMR (DMSO) δ 52.6,
stirred at -78 °C for 4 h under argon, the temperature was
gradually raised to room temperature, stirred for 3 h, and
refluxed for 2 h. The orange mixture was filtered and the filtrate
124.1, 126.0, 130.2, 141.4, 143.0, 144.0, 150.9, 163.9; HRMS
+
concentrated, after which 5 mL of H
Na CO were added and the residue filtered and recrystallized
from CH Cl to afford 69.1 mg (55%) of 11 as a light brown
solid: mp 331-332 °C dec; IR (Nujol) 1695, 3236-3612 (br) cm
2
O and 0.5 mL of saturated
(MH ) calcd for C18
H
12
N
4
O
4
m/ z 349.0937, found 349.0934.
2
3
2
2
Ack n ow led gm en t. We thank Dr. David Locke at
Queens College CUNY for IR analyses and Dr. Cliff Soll
at Hunter College CUNY for mass spectral analyses.
-1
;
1
H NMR (DMSO) δ 7.83 (dd, 2H, J ) 8.0, 4.0 Hz), 9.07 (br, 2H),
+
9
.37 (dd, 2H, J ) 8.0, 1.0 Hz), 11.86 (s, 2H); HRMS (MH ) calcd
for C14 m/ z 265.0712, found 265.0717.
,4,5,12-Tetr a a za tr iph en ylen e-2,3-dica r bon itr ile (13). Di-
8 4 2
H N O
Su p p or tin g In for m a tion Ava ila ble: NMR spectra for
compounds 1, 6-11, and 13-17. This material is available free
of charge via the Internet at http://pubs.acs.org.
1
one 2 (960 mg, 4.57 mmol) was dissolved in THF (117 mL) at
room temperature under argon, and with stirring 12 (544 mg,
5
.03 mmol) was added and refluxed for 2 h. The solvent was
evaporated, the light brown residue was redissolved in anhyd
J O0495283
7
744 J . Org. Chem., Vol. 69, No. 22, 2004