[1,2,5]Thiadiazolo[3,4-f][1,10]phenanthroline as a building block for organic materials

Article abstract of DOI:10.1055/s-2006-950323

[1,2,5]Thiadiazolo[3,4-f][1,10]phenanthroline was prepared using a straightforward and efficient methodology, in four steps, starting from phenanthroline. This compound was fully characterized by mass spectrometry, IR, UV, ¹H and ¹³C NMR spectroscopy, and its structure was determined by X-ray crystallography. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2006-950323

SHORT PAPER
3945
[
1,2,5]Thiadiazolo[3,4-f][1,10]phenanthroline as a Building Block for Organic
Materials
P
G
reparationof
[
1,2
i
,5]Thia
l
diazol
m
o[3,4-f][1,10]phena
a
nthroline r Conte, Adailton J. Bortoluzzi, Hugo Gallardo*
Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC - 88040-900, Brazil
Fax +55(48)33319711; E-mail: hugo@qmc.ufsc.br
Received 10 May 2006
[
1,2,5]Thiadiazolo[3,4-f][1,10]phenanthroline was pre-
Abstract: [1,2,5]Thiadiazolo[3,4-f][1,10]phenanthroline was pre-
pared using a straightforward and efficient methodology, in four
steps, starting from phenanthroline. This compound was fully char-
pared using a straightforward and efficient methodology,
in four steps, from phenanthroline (Scheme 1). Phenan-
1
13
acterized by mass spectrometry, IR, UV, H and C NMR spectros- throline (1) was easily oxidized to 1,10-phenanthroline-
copy, and its structure was determined by X-ray crystallography.
5,6-dione (2) following the method used by Yamada et
1
3
al, and this was then condensed with hydroxylamine in
methanol and BaCO to give dioxime 3 as a yellow solid.
Key words: heterocyclic, 1,10-phenanthrolines, X-ray crystal
structure
3
The dioxime was not purified; TLC indicated the presence
of a mixture of syn and anti isomers. This crude product
was converted into the corresponding diamine by Pd/C-
catalyzed reduction in ethanol with hydrated hydrazine, to
furnish 4 as a dark yellow solid. Finally, the diamine was
treated with freshly distilled thionyl chloride, in the pres-
ence of triethylamine in dichloromethane, affording
Heteroaromatic molecules are important constituents in
both pharmaceutical and natural products. However, in
1
recent years the parent compounds have also attracted
considerable attention for the design, synthesis, and inves-
tigation of new molecular materials, especially conduct-
ing, superconducting, and magnetic materials. Currently,
research into these types of compounds is enjoying great
[
1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (5) in 65%
yield. This procedure was very simple, clean and repro-
ducible.
2
,3
scientific and technological progress. In particular,
,10-phenanthroline and its derivatives play an important
role as molecular scaffolds for supramolecular assem-
1
O
O
blies, molecular switches, and artificial nucleases6
4
5
H2SO4, HNO3
KBr
MeOH, BaCO3
(
DNA cleavers). Our attention is focused on the design
2
H NOH⋅HCl
and synthesis of functional molecular materials, and a
new core for liquid crystals with special electrical and/or
optical properties. In this context, we have already pre-
N
N
N
N
1
2
7
8
9
HON
NOH
H2N
NH2
pared a wide variety of triazole, isoxazole, thiophene,
1
0
11
12
oxadiazole, benzothiazole and benzothiadiazole de-
rivatives. In this communication, the synthesis of a new
phenanthroline derivative is reported. To our knowledge,
the synthesis and crystalline structure of [1,2,5]thiadiazo-
lo[3,4-f][1,10] phenanthroline (5) has not been previously
described.
MeOH, N2H4
Pd/C 10%
SOCl2
CH2Cl2, Et3N
N
N
N
N
N
4
3
S
N
compound
yield
mp °C
The title compound, 5, is a heteroaromatic, planar, cyclic
molecule of C2n symmetry containing an 18p-electron
system. As such, it has several desirable characteristics:
2
3
4
5
85%
90%
81%
80%
255.3–258.2
233.1–234 (dec)
> 290
N
N
(
a) it affords well-ordered crystal structures, (b) it con-
230.8–231.9
5
tains the 1,2,5-thiadiazole group, which is a planar aro-
matic ring system with molecular parameters similar to
thiophene, (c) it is characterized by the presence of differ-
Scheme 1
ent coordination sites, forming metal complexes of an N2-
Besides spectroscopic analysis, we used single-crystal X-
ray diffraction to conclusively identify compound 5.
Figure 1 shows an ORTEP representation of the crystal
structure. The structure of the chloroform adduct of 5
showed that all the 12 carbon atoms, 4 nitrogen atoms and
the sulfur atom are coplanar, being similar to the core of
phenanthroline derivatives, which is also flat. From the
analysis of the bond lengths, it was concluded that the
molecule must be extensively conjugated. This compound
type ligand, (d) the p-conjugated derivatives are generally
efficient fluorophores, (e) it can be used as an attractive
building block for constructing polynuclear systems, and
(
f) it can be intercalated in DNA.
SYNTHESIS 2006, No. 23, pp 3945–3947
x
x.
x
x
.
2
0
0
6
Advanced online publication: 12.10.2006
DOI: 10.1055/s-2006-950323; Art ID: M03406SS
Georg Thieme Verlag Stuttgart · New York
©

3
946
G. Conte et al.
SHORT PAPER
has a tendency to form strong H-bonded adducts with The transparent crystals showed fissures as soon as they were ex-
tracted from the crystallization solution and, without protection,
they become opaque in a few minutes. The crystal data were mea-
sured with an Enraf-Nonius CAD4 diffractometer, at r.t., with
chloroform or methanol, similar to other phenanthroline
1
4
derivatives. Table 1 shows the hydrogen bond distances
and angles between chloroform and [1,2,5]thiadiazo-
lo[3,4-f][1,10] phenanthroline.
graphite-monochromated MoK radiation (l = 0.71073 Å) using
a
the w – 2q scan technique.
X-ray crystal data for 4b; Empirical formula C H C N S; Formula
1
3
7
l3
4
Table 1 Hydrogen Bond Lengths and Angles between [1,2,5]Thia-
diazolo[3,4-f][1,10]phenanthroline and Chloroform
weight 357.64; Crystal size 0.50 × 0.40 × 0.30 mm; ; Crystal sys-
tem = monoclinic; Space group P2 /m; Unit cell dimensions
1
a = 9.8252(5) Å, b = 6.7474(12) Å, c = 11.4344(5) Å;
Bond length (Å)
Bond angle (°)
C–H–N
3
3
V = 743.07(14) Å ; Z = 2; D (calculated) = 1.598 Mg/m ; Absorp-
C–H
0.98
0.98
H–N
2.40
2.29
C–N
–1
tion coefficient = 0.753mm ; F(000)-360; Theta range for data col-
lection 1.82° to 26.98°; Reflected collections 1850; Independent
Cl C–H…N8
3.178(4) 135.5
3.196(5) 153.9
3
reflections 1765 [R(int) = 0.0555]; 1356 reflections with [I > 2s(I)];
2
Refinement method full-matrix least-squares method on F using
Cl C–H…N11
3
1
6
17
SHELXS97 and SHELXL97 respectively; Final R indices [I > 2
1
8
sigma (I)] R1= 0.0473, wR2 (all data) = 0.1326. The ORTEP3
program was used to represent the molecular structure.
Selected bond lengths (Å): S1–N17: 1.621(3), S1–N2: 1.622(3),
N2–C3: 1.334(4), C3–C16: 1.426(5), C3–C4: 1.447(4), C4–C5:
1
.406(5), C4–C9: 1.408(4), C5–C6: 1.369(5), C6–C7: 1.392(5),
C7–N8: 1.325(5), N8–C9: 1.354(4), C9–C10: 1.480(4), C10–N11:
1
1
1
.352(4), C10–C15: 1.408(4), N11–C12: 1.336(5), C12–C13:
.395(6), C13–C14: 1.365(6), C14–C15: 1.407(5), C15–C16:
.444(5), C16–N17: 1.341(4).
Selected bond angles (°): N17–S1–N2: 100.27(16), C3–N2–S1:
06.5(3), N2–C3–C16: 113.5(3), N2–C3–C4: 125.6(3), C16–C3–
1
C4: 120.9(3), C5–C4–C9: 118.5(3), C5–C4–C3: 123.2(3), C9–C4–
C3: 118.3(3), C6–C5–C4: 118.6(3), C5–C6–C7: 119.0(3), N8–C7–
C6: 124.2(3), C7–N8–C9: 117.6(3), N8–C9–C4: 122.1(3), N8–C9–
C10: 117.0(3), C4–C9–C10: 120.9(3), N11–C10–C15: 122.5(3),
N11–C10–C9: 117.1(3), C15–C10–C9: 120.3(3), C12–N11–C10:
1
17.4(3), N11–C12–C13: 123.8(4), C14–C13–C12: 119.0(4), C13–
C14–C15: 119.1(3), C14–C15–C10: 118.1(3), C14–C15–C16:
23.3(3), C10–C15–C16: 118.6(3), N17–C16–C3: 113.3(3), N17–
C16–C15: 125.6(3), C3–C16–C15: 121.1(3), C16–N17–S1:
06.4(3).
Figure 1 ORTEP representation of the molecular structure of
1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (5) with labeling
scheme. Ellipsoids are shown at 40% probability level.
1
[
1
In summary, an efficient procedure has been developed 1,10-Phenanthroline-5,6-dione (2)
1
9
for the synthesis of [1,2,5]thiadiazolo[3,4-f][1,10]phenan- Yield: 85%; mp 255–258.2 °C (Lit. 258–259 °C).
throline, which can be used as a building block for organic
materials. The target molecule contains a planar, rigid pol- 1007, 921, 810, 736 cm .
IR (KBr): 3058, 1682, 1568, 1457, 1411, 1312, 1289, 1202, 1114,
–
1
yaromatic core that can be used as molecular switches, or
alternatively to intercalate in DNA. With this aim in mind,
1
H NMR (400 MHz, DMSO-d ): d = 7.61 (dd, J = 8.4 Hz, 4.4 Hz,
6
2
H), 8.48 (dd, J = 8.4 Hz, 1.6 Hz, 2 H), 8.78 (dd, J = 4.4 Hz, 1.6
a
new methodology for synthesizing 5,10-dibro- Hz, 2 H).
mo[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline is cur-
rently in progress.
1
,10-Phenanthroline-5,6-dioxime (3)
2
0
Yield: 90%; mp 233–234 °C (dec) [Lit. 230 °C (dec)].
IR (KBr): 3374, 3005, 2840, 1666, 1564, 1468, 1401, 1299, 1133,
1H and 13C NMR spectra were recorded at 400 MHz and 100 MHz,
respectively. Infrared spectra were recorded with a Perkin Elmer
FTIR 2000 instrument, in KBr pellets. Elemental analyses were per-
formed with a Carlo Erba instrument, model E-1110. Low resolu-
tion mass spectra were recorded on a triple quadrupole mass
spectrometer, GCMS-QP5050A, Shimadzu. TLC was performed
using commercially prepared 60-mesh silica gel plates, and visual-
ization was effected with UV light (254 nm). All melting points are
uncorrected.
–1
9
80, 856, 808, 738 cm .
5
,6-Diamine-1,10-phenanthroline (4)
20
Yield: 81%; mp >350 °C (Lit. >350 °C).
IR (KBr): 3367, 3199, 1653, 1610, 1480, 1295, 1116, 1002, 797,
–
1
7
28 cm .
1
H NMR (400 Hz, DMSO-d ): d = 3.37 (s, 4 H), 7.67 (dd, J = 7.6
6
Hz, 4.0 Hz, 2 H), 8.39 (d, J = 7.6 Hz, 2 H), 8.98 (d, J = 4.0 Hz, 2 H).
All reagents were used directly as obtained from commercial sour-
ces, unless otherwise noted.
[
5
1,2,5]Thiadiazolo[3,4-f][1,10]phenanthroline (5)
,6-Diamine-1,10-phenanthroline (4; 1.0 g, 4.76 mmol), CH Cl
2
2
X-ray Crystallographic Analysis15
(30 mL) and Et N (1.92 g, 19.04 mmol) were combined and the so-
3
lution was stirred for 15 min, until the diamine went into solution.
Thionyl chloride (1.13 g, 9.5 mmol) was added slowly dropwise and
the mixture was refluxed for 4 h. The solvent was removed in a ro-
Colorless crystals of compound 5 were grown from CHCl . These
3
crystals were very sensitive to solvent loss and thus were handled in
protective oil. The selected crystal was isolated in a glass capillary.
Synthesis 2006, No. 23, 3945–3947 © Thieme Stuttgart · New York

SHORT PAPER
Preparation of [1,2,5]Thiadiazolo[3,4-f][1,10]phenanthroline
3947
tatory evaporator and H O (70 mL) was added. Concentrated HCl
(5) (a) Wilson, J. N.; Josowicz, M.; Wang, Y. Q.; Bunz, U. H. F.
2
was added to a final pH of 2, then the mixture was extracted into
Chem. Commun. 2003, 2962. (b) Wilson, J. N.; Bunz, U. H.
F. J. Am. Chem. Soc. 2005, 127, 4124.
(6) (a) Kalyanasundaram, K. Coord. Chem. Rev. 1982, 46, 159.
(b) Sigman, D. S.; Perrin, D. M. Chem. Rev. 1993, 93, 2295.
(c) Yamagishi, A. J. Chem. Soc., Chem. Commun. 1983,
CH Cl (3 × 70 ml), washed with H O (2 × 50 mL), dried over
2
2
2
Na SO and filtered. The solvent was removed, and the residue pu-
2
4
rified on a chromatographic column (silica gel; EtOAc–CHCl , 8:2)
3
to give 5.
5
72. (d) Erkkila, K. E.; Odom, D. T.; Barton, J. K. Chem.
Yield: 0.906 g (80%); mp 230.8–231.9 °C.
Rev. 1999, 99, 2777. (e) Sigman, D. S.; Graham, D. R.;
D’Aurora, V.; Stern, A. M. J. Biol. Chem. 1979, 254, 12269.
7) (a) Conte, G.; Cristiano, R.; Ely, F.; Gallardo, H. Synth.
Commun. 2006, 36, 951. (b) Conte, G.; Ely, F.; Gallardo, H.
Liq. Cryst. 2005, 32, 1213.
8) Bartulín, J.; Martinez, R.; Gallardo, H.; Muller, J.; Taylor, T.
R. Mol. Cryst. Liq. Cryst. 1993, 225, 175.
(9) Gallardo, H.; Favarin, I. Liq. Cryst. 1993, 13, 115.
1
H NMR (400 MHz, CDCl ): d = 7.75 (dd, J = 8.0 Hz, 4.4 Hz, 2 H),
3
9
.0 (dd, J = 8.0 Hz, 1.6 Hz, 2 H), 9.24 (dd, J = 4.4 Hz, 1.6 Hz, 2 H).
(
(
1
3
C NMR (100 MHz, CDCl ): d = 123.4, 124.4, 133.6, 147.8, 152.0,
3
1
52.3.
IR (KBr): 3401, 1635, 1561, 1480, 1396, 1079, 842, 809, 735 cm–1.
+
MS (EI, 70 eV): m/z (%) = 237 (47.5) [M – 1], 238 (100) [M ], 239
(16.5) [M + 1], 240 (4.9) [M + 2].
(10) (a) Cristiano, R.; Ely, F.; Gallardo, H. Liq. Cryst. 2005, 32,
1
. (b) Cristiano, R.; Santos, D. M. P. D.; Gallardo, H. Liq.
UV/Vis (CH CN): l (log e) = 236 nm (4.5).
3
max
Cryst. 2005, 32, 7.
Anal. Calcd for C H N S: C, 60.49; H, 2.54; N, 23.51; S, 13.46.
1
2
6
4
(11) Meyer, E.; Zucco, C.; Gallardo, H. J. Mater. Chem. 1998, 8,
Found: C, 60.56; H, 2.68; N, 22.71; S, 13.36.
1351.
(
12) DaSilveira Neto, B. A.; Sant’Ana Lopes, A.; Ebeling, G.;
Gonçalves, R. S.; Costa, V. E. U.; Quina, F. H.; Dupont, J.
Tetrahedron 2005, 61, 10975.
Acknowledgment
(
13) Yamada, M.; Tanaka, Y.; Yoshimoto, Y.; Kuroda, S.;
Shimao, I. Bull. Chem. Soc. Jpn. 1992, 65, 1006.
14) Castellano, E. E.; Piro, O. E.; Caram, J. A.; Murífico, M. V.;
Aimone, S. L.; Vasinic, E. J.; Lucero, A. M.; Mitnik, D. G.
J. Mol. Struct. 2001, 562, 157.
This work was supported by grants from CNPq, FAPESC, FINEP
and PRONEX (Brazil).
(
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15) Further details of the structure determination of compound 5,
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Synthesis 2006, No. 23, 3945–3947 © Thieme Stuttgart · New York