Bis(dialkylamino)benzochalcogenadiazole
J . Org. Chem., Vol. 66, No. 26, 2001 8959
Calcd for C10H12N4S‚(1/4)H2O: C, 53.43; H, 5.61; N, 24.92; S,
14.26. Found: C, 53.30; H, 5.27; N, 24.61; S, 14.26.
Calcd for C10H14N4O‚(C12H2N6S)2‚H2O: C, 54.54; H, 2.69; N,
29.93. Found: C, 54.62; H, 2.74; N, 29.56.
Other CT complexes were also obtained by a similar direct
method in CH2Cl2 or MeCN.
P r ep a r a tion of 4,7-Bis(d im eth yla m in o)ben zo[c][1,2,5]-
selen a d ia zole (3a ) via 1,2-Dia m in o-3,6-bis(d im eth yla m i-
n o)ben zen e (5a ). To a solution of 2a (500 mg, 2.25 mmol) in
THF (1 mL) was added dropwise a suspension of LiAlH4 (1.3
g, 34 mmol) in dry THF (8 mL) at 0 °C under N2. After stirring
for 1 h at 0 °C, water-saturated ether (150 mL, degassed) and
then 60 mL of degassed water were added. The mixture was
extracted with ether under N2. To the combined extracts
containing tetramine (5a ) was added a solution of SeO2 (440
mg, 3.37 mmol) in degassed water (20 mL), and the mixture
was stirred for 20 h at room temperature under N2. The
mixture was poured into water and extracted with ether. The
combined extracts were washed with brine and dried over Na2-
SO4. Chromatographic separation on Al2O3 (CH2Cl2) followed
by recrystallization from n-hexane gave 3a (350 mg) as violet
rods in 59% yield.
Data for 1a -BTDA (2:3). Dark green powder, mp 170-200
°C (dec.). Anal. Calcd for (C10H14N4O)2‚(C12N8S2)3‚0.5H2O: C,
48.65; H, 2.11; N, 32.42. Found: C, 48.50; H, 2.07; N, 32.57.
Data for 2a -MTDA (1:1). Dark violet powder, mp 133-135
°C (dec.). Anal. Calcd for C10H14N4S‚C12H2N6S: C, 54.53; H,
3.33; N, 28.91; S. 13.23. Found: C, 53.92; H, 3.32; N, 28.59; S,
13.89.
Data for 2a -BTDA (1:1). Dark green powder, mp 183-186
°C (dec). Anal. Calcd for C10H14N4S‚C12N8S2: C, 48.70; H, 2.60;
N, 30.98; S. 17.73. Found: C, 48.00; H, 2.73; N, 30.56; S, 17.87.
Data for 3a -BTDA (1:1). Dark gray powder, mp 170-185
°C (dec.). Anal. Calcd. for C10H14N4Se‚C12N8S2‚0.5H2O: C,
44.15; H, 2.53; N, 28.08. Found: C, 44.09; H, 2.55; N, 29.56.
Some of the analytical values deviate more than 0.4% from
the corresponding calculated value, yet they still support the
donor-to-acceptor molar ratios indicated above.
Data for 3a . Violet cubes (Al2O3 chromatography, CH2Cl2);
1
mp 94-94.5 °C; H NMR (200 MHz, CDCl3) δ/ppm 6.52 (2H,
s), 3.03 (12H, s); IR (KBr) 2920, 2810, 2770, 1480 cm-1; UV-
vis (MeCN) λmax 258 (log ꢀ 4.18), 324 (3.86), 330 (3.86), 512
(3.38) nm; EI-MS m/z 270 (M+). Anal. Calcd for C10H14N4Se:
C, 44.62; H, 5.24; N, 20.81. Found: C, 44.53; H, 5.12; N, 20.64.
Data for 5a . Colorless plates (sublimation), mp 77-80 °C;
1H NMR (90 MHz, CDCl3) δ/ppm 6.57 (2H, s), 3.83 (4H, broad
Powder conductivities (σ) were measured in compacted
samples by a two-probe method at room temperature. Under
the present conditions, σ ) 2.7 S cm-1 for a TTF-TCNQ
complex, a representative molecular metal.
Red ox P oten tia l Mea su r em en ts. Redox potentials (Eox
and Ered.) were measured by cyclic voltammetry in dry MeCN
containing 0.1 mol dm-3 Et4NClO4 as a supporting electrolyte.
Ferrocene undergoes 1e-oxidation at +0.38 V under the same
conditions. All of the values shown in the text are in E/V vs
SCE. In the case of irreversible waves, half-wave potentials
s), 2.65 (12H, s); IR (KBr) 3330, 2920, 2800, 2760, 1495 cm-1
;
EI-MS m/z (relative intensity) 194 (M+, 100), 179 (30), 164 (70),
149 (35). Anal. Calcd for C10H18N4: C, 61.82; H, 9.34; N, 28.83.
Found: C, 61.47; H, 9.22; N, 28.64.
were estimated from the anodic peak potentials (Epa) as Eox
)
P r ep a r a tion of 4,7-Bis(1-p yr r olid in yl)ben zo[c][1,2,5]-
selen a d ia zole (3b) via 1,2-Dia m in o-3,6-bis(1-p yr r olid i-
n yl)ben zen e (5b). This compound was prepared from thia-
diazole derivative 2b in 34% yield by a procedure similar to
that for 3a via tetramine 5b.
Epa - 0.03 V or the cathodic peak potentials (Epc) as Ered ) Epc
+ 0.03 V. Although Ered of 1e,27 2e,28 and 3e29 have been
reported previously,3 the values shown in Table 1 were
measured under the present conditions for direct comparisons
with other compounds.
Data for 3b. Violet plates (Al2O3 chromatography, CH2Cl2),
1
X-r a y An a lyses. Crystal data for 2a . C10H14N4S, M 222.31,
thin red plate, 0.5 × 0.2 × 0.01 mm (EtOH), orthorhombic
P212121, a ) 5.5824(3) Å, b ) 19.046(1) Å, c ) 10.0343(7) Å, V
) 1066.9(1) Å3, F (Z ) 4) ) 1.384 g cm-1. A total of 1382 unique
data (2θmax ) 54.2°) were measured at T ) 123 K by a Rigaku
Mercury CCD apparatus (Mo KR radiation, λ ) 0.710 69 Å).
Absorption correction was applied (µ ) 2.75 cm-1). The
structure was solved by the direct method (SIR92) and refined
by the full-matrix least-squares method on F with anisotropic
temperature factors for non-hydrogen atoms. Hydrogen atoms
were located at the calculated positions. The final R and Rw
values are 0.041 and 0.058 for 1185 reflections with I > 3σΙ
and 136 parameters. Estimated standard deviations are
0.003-0.005 Å for bond lengths and 0.1-0.3° for bond angles.
Crystal data for 2b. C14H18N4S, M 274.38, violet plate, 0.4
× 0.15 × 0.05 mm (CHCl3/n-hexane), monoclinic C2/c, a )
26.69(2) Å, b ) 4.841(4) Å, c ) 22.35(2) Å, â ) 114.15(1)°, V )
2635(3) Å3, F (Z ) 8) ) 1.383 g cm-1. A total of 2995 unique
data (2θmax ) 54.9°) were measured at T ) 123 K by a Rigaku
Mercury CCD apparatus (Mo KR radiation, λ ) 0.710 69 Å).
Absorption correction was applied (µ ) 2.38 cm-1). The
structure was solved by the direct method (SIR92) and refined
by the full-matrix least-squares method on F with anisotropic
temperature factors for non-hydrogen atoms. Hydrogen atoms
were located at the calculated positions. The final R and Rw
values are 0.079 and 0.097 for 1123 reflections with I > 3σΙ
and 173 parameters. Estimated standard deviations are
0.007-0.01 Å for bond lengths and 0.4-0.7° for bond angles.
Crystal data for 2e. C6H4N2S, M 136.17, colorless cube, 0.4
× 0.4 × 0.4 mm (sublimation), orthorhombic Pna21, a )
12.572(8) Å, b ) 12.132(8) Å, c ) 3.803(2) Å, V ) 580.1(6) Å3,
mp 101-102 °C; H NMR (90 MHz, CDCl3) δ/ppm 6.23 (2H,
broad s), 3.57 (8H, broad), 2.03 (8H, m); IR (KBr) 2950, 2800,
1580, 1460, 1390, 1300 cm-1; UV-vis (MeCN) λmax 270 (log ꢀ
4.30), 322 (3.82), 580 (3.40) nm; EI-MS m/z (relative intensity)
321 (M+, 33), 242 (100). Anal. Calcd for C14H18N4Se: C, 52.34;
H, 5.65; N, 17.44. Found: C, 52.08; H, 5.55; N, 17.23.
Data for 5b. Colorless plates (sublimation), mp 92-94 °C;
1H NMR (90 MHz, CDCl3) δ/ppm 6.45 (2H, s), 2.89 (8H, m),
2.82 (4H, broad s), 1.80 (8H, m); IR (KBr) 3400, 2950, 2810
cm-1; EI-MS m/z 246 (M+). Anal. Calcd for C14H22N4: C, 68.26;
H, 9.00. Found: C, 68.76; H, 9.09 (correct analytical values
could not be obtained due to its instability).
P r ep a r a tion of 4-(1-P yr r olid in yl)ben zo[c][1,2,5]th ia -
d ia zole (4b). This compound was prepared from trifluoroa-
mide 4d in 75% yield by a procedure similar to that for 2b:
orange crystals (Al2O3 chromatography, CH2Cl2); mp 84-84
1
°C; H NMR (200 MHz, CDCl3) δ/ppm 7.41 (1H, dd, J ) 7.5,
8.5 Hz), 7.20 (1H, d, J ) 8.5 Hz), 6.23 (1H, d, J ) 7.5 Hz),
3.03 (4H, m), 2.06 (4H, m); IR (KBr) 2950, 2820, 1520, 732
cm-1; UV-vis (MeCN) λmax 262 (log ꢀ 4.42), 302 (3.53), 314
(3.47), 458 (3.63) nm; EI-MS m/z 205 (M+). Anal. Calcd for
C
10H11N3S: C, 58.51; H, 5.40; N, 20.47. Found: C, 58.60; H,
5.49; N, 20.35.
P r ep a r a tion of 4-Tr iflu or oa cetyla m in oben zo[c][1,2,5]-
th ia d ia zole (4d ). This compound was prepared from amine
4c26 in 78% yield by a procedure similar to that for 1d : faintly
orange plates (recrystallization from petroleum ether); mp 85-
88 °C; 1H NMR (90 MHz, CDCl3) δ/ppm 9.13 (1H, broad s),
8.47 (1H, d, J ) 8 Hz), 7.80 (1H, dd, J ) 8, 8 Hz), 7.61 (1H, d,
J ) 8 Hz); IR (KBr) 3380, 1725, 1619, 1563, 1144 cm-1; EI-
MS m/z 247 (M+). Anal. Calcd for C8H4N3SOF3: C, 38.87; H,
1.63; N, 17.00. Found: C, 39.12; H, 1.36; N, 16.93.
P r ep a r a tion of Cr ysta llin e CT Com p lexes. To a solution
of 1a (50 mg, 0.24 mmol) in CH2Cl2 (1 mL) was added a filtered
solution of MTDA18a (50 mg, 0.19 mmol) in CH2Cl2 (10 mL),
and the mixture was allowed to stand overnight. Dark green
fine needles of the 1a -MTDA (1:2) complex (57 mg, y. 80%)
were filtered and dried in vacuo: mp 150-152 °C (dec.). Anal.
F (Z ) 4) ) 1.559 g cm-1. A total of 743 unique data (2θmax
)
55.0°) were measured at T ) 123 K by a Rigaku Mercury CCD
(27) Zincke, T.; Schwarz, P. Liebigs Ann. Chem. 1899, 307, 28.
(28) Khaletskii, A. M.; Pesin, V. G. Z. Obs. Khim. 1950, 20, 1914
[cf. Chem. Abstr. 1952, 46, 106f].
(29) Bird, C. W.; Cheeseman, G. W. H.; Sarsfield, A. A. J . Chem.
Soc. 1963, 4767.