Synthesis and characterization of multihalogen substituted salamo-type bisoximes

Article abstract of DOI:10.14233/ajchem.2014.15925

Four tetrahalogen substituted Salamo-type bisoximes H2L1-H2L4 have been synthesized from 3-bromo-5-chloro-2-hydroxybenzaldehyde and 1,3-bis(aminooxy) propane, 1,4-bis(aminooxy)butane, 1,5-bis(aminooxy)pentane or 1,6-bis(aminooxy)hexane in ethanol solution

Full text of DOI:10.14233/ajchem.2014.15925

Asian Journal of Chemistry; Vol. 26, No. 1 (2014), 285-288
http://dx.doi.org/10.14233/ajchem.2014.15925
Synthesis and Characterization of Multihalogen Substituted Salamo-Type Bisoximes
*
YU-HUA YANG, XIU-YAN DONG , YU-JIE ZHANG, GANG LI and MENG-MENG ZHAO
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R. China
*
Corresponding author: E-mail: dxy568@163.com
Received: 17 June 2013;
Accepted: 23 July 2013;
Published online: 26 December 2013;
AJC-14525
1
4
2 2
Four tetrahalogen substituted Salamo-type bisoximes H L -H L have been synthesized from 3-bromo-5-chloro-2-hydroxybenzaldehyde
and 1,3-bis(aminooxy)propane, 1,4-bis(aminooxy)butane, 1,5-bis(aminooxy)pentane or 1,6-bis(aminooxy)hexane in ethanol solution,
1
respectively and characterized by elemental analyses as well as IR, UV-visible and H NMR spectroscopy.
Keywords: Salamo-type bisoxime, Synthesis, Characterization.
recorded on aVERTEX70 FT-IR spectrophotometer using KBr
pellets. UV/Visible absorption spectra were recorded on a
INTRODUCTION
Recently, the design and synthesis of multimetallic comp-
lexes has been actively investigated because of not only their
unique and attractive structures but also their diverse appli-
1
Shimadzu UV-2550 spectrometer. H NMR spectra were
recorded on a Mercury-400BB spectrometer. Melting points
were measured by the use of a microscopic melting point
apparatus made in Beijing Taike Instrument Limited Company
and the thermometer was uncorrected.
1
cations such as optical materials , magnetic materials ,
2,3
4,5
6,7
catalysts for organic reactions and multimetalloreceptors .
Among the various metal clusters, Salen (N,N'-bis(salicylidene)-
General procedure: 1,3-Bis(aminooxy)propane, 1,4-
bis(aminooxy)butane, 1,5-bis(aminooxy)pentane and 1,6-
bis(aminooxy)hexane were synthesized according to an analo-
1
,2-ethylenediamine) and its analogues have been utilized as
ligands to form multimetallic complexes because they are
multidentate ligands having an O coordination site besides
site . Comparing the ligand properties of Salen and
2
13,17
gous method reported earlier . Synthetic route to Salamo-
4
8
-12
an N
O
2 2
1
type bisoxime compounds H
2 2
L –H L is shown in Scheme-I.
its oxime-based analogue Salamo, the Salamo derivatives are
4
at least 10 times more stable than Salen derivatives and the
4
,4'-Dichloro-6,6'-dibromo-2,2'-[(propylene-1,3-
1
2
diyldioxy)bis(nitrilomethylidyne)]diphenol (H L ): To an
large electronegativity of oxygen atoms is expected to affect
ethanolic solution (8 ml) of 3-bromo-5-chloro-2-hydroxy-
benzaldehyde (235.5 mg, 1 mmol) was added an ethanolic
solution (5 mL) of 1,3-bis(aminooxy)propane (53.0 mg, 0.50
mmol). After the solution had been stirred at 55 °C for 2 h,
When cooled to room temperature, the pale-yellow precipitate
was filtered and washed successively with ethanol/hexane (1:4)
2 2
strongly the electronic properties of N O coordination sphere,
which can lead to different and novel properties and structures
1
3-16
of the resulted complexes . Thus, we have recently studied
some novel Salamo-type chelating compounds on the basis of
O-alkyloxime moiety (-CH=N-O-(CH
2 n
) -O-N=CH-) instead
17
2 n
of the imine (-CH=N-(CH ) -N=CH-) group . Here we report
and hexane, respectively. The product was dried under reduced
1
L ).
the synthesis and characterization of a series of tetrahalogen
substituted Salamo-type compounds.
pressure and obtained white crystalline compound (H
2
4
,4'-Dichloro-6,6'-dibromo-2,2'-[(butylene-1,4-
2
2
diyldioxy)bis(nitrilomethylidyne)]diphenol (H L ): To an
EXPERIMENTAL
ethanolic solution (6 mL) of 3-bromo-5-chloro-2-hydroxy-
benzaldehyde (242 mg, 1.03 mmol) was added an ethanolic
solution (4 mL) of 1,4-bis(aminooxy)butane (61 mg, 0.51
mmol).After the solution had been stirred at 55 °C for 3 h, the
formed precipitate was separated by filtration and washed
successively with ethanol/hexane (1:4) and hexane, respectively.
3
-Bromo-5-chloro-2-hydroxybenzaldehyde (≥ 99 %), 1,3-
dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane and
,6-dibromohexane were purchased fromAlfaAesar and used
1
without further purification. The other reagents and solvents
were analytical grade reagents from Tianjin Chemical Reagent
Factory. C, H and N analyses were carried out with a GmbH
VariuoELV3.00 automatic elemental analyzer. IR spectra were
The product was dried under reduced pressure to obtain white
2
L ).
crystalline compound (H
2

286 Yang et al.
Asian J. Chem.
O
O
C
O
C
C
n
Br
NH NH ·H O
2
n
n
N O O N
2
2
Br
2
H N O
2
O NH2
N OH
C
O
C
O
C
O
n
O
O
N
N
CHO
n
Ethanol
Cl
OH
HO
Br
H N O
2
O NH2
Cl
OH
Cl
+
Br
Br
1
H L : n=2; H L : n=3; H L : n=4; H L : n=5.
2
3
4
2
2
2
2
1
4
2 2
Scheme-I: Synthetic route to salamo-type bisoximes H L -H L .
4
diyldioxy)bis(nitrilome-thylidyne)]diphenol (H
,4'-Dichloro-6,6'-dibromo-2,2'-[(propane-1,5-
3
L ): To an
and soluble in DMF and DMSO, insoluble in methanol,
1
2
2
ethanol, n-hexane, ether and water. In addition, H
2 2
L and H L
ethanolic solution (5 mL) of 3-bromo-5-chloro-2-hydroxy-
benzaldehyde (176.6 mg, 0.75 mmol) was added an ethanolic
solution (3 mL) of 1,5-bis(aminooxy)pentane (49.0 mg, 0.37
mmol).After the solution had been stirred at 55 °C for 5 h, the
mixture was filtered, washed successively with ethanol/
hexane and hexane, respectively. The product was dried under
are soluble in hot acetone, acetonitrile, chloroform, dichloro-
3
4
2 2
methane and tetrahydrofuran, but H L and H L are insoluble
in hot acetone, acetonitrile, chloroform, dichloromethane and
tetrahydrofuran.
1
L -H
4
L are given in Figs. 1-4, respectively.
IR spectra of H
2
2
1
L -H
4
L , the bands due to characteristic
In the IR spectra of H
2
2
-1
reduced pressure and obtained white crystalline compound
(
C=N stretching absorption bands appear at 1606-1604 cm ,
18
respectively . The Ar-O stretching frequencies appear within
3
L ).
H
2
-1
19
4
,4'-Dichloro-6,6'-dibromo-2,2'-[(hexane-1,6-diyldioxy)-
1272-1251 cm as reported for similar bisoxime compounds .
These provide evidence for the formation of the present
compounds. The O-H stretching frequency of the bisoxime
4
bis(nitrilomethylidyne)]diphenol (H
solution (6 mL) of 3-bromo-5-chloro-2-hydroxybenzaldehyde
158 mg, 0.67 mmol) was added an ethanolic solution (2 mL)
2
L ): To an ethanolic
-1
(
compounds is expected in the 3800-3300 cm region, but this
-1
of 1,6-bis(aminooxy)hexane (49 mg, 0.33 mmol). After the
solution had been stirred at 55 °C for 4 h, the mixture was
filtered, washed successively with ethanol/hexane (1:4) and
frequency is generally displaced to 3424 cm because of the
17
internal hydrogen bond OH···N=C . Here a strong band at
1
-
1
4
2 2
3429 cm was observed in H L -H L and assigned to phenolic
hexane, respectively. The product was dried under reduced
4
L ).
alcohol stretching absorption bands. In addition, in the 1481-
-1
1433 cm region, the observed bands were attributed to aromatic
pressure and obtained white crystalline compound (H
2
C=C vibrations.
RESULTS AND DISCUSSION
1
L -H
4
The UV-visible spectra of the compounds H
-5
× 10 DMF solution are presented in Table-2. UV-visible spectra
2
2
L in 5
1
L -H
4
A series of Salamo-type bisoxime compounds H
2
2
L
1
4
have been synthesized with good yields and the composition
are confirmed by elemental analyses, IR, UV-Visible spectra
1
and H NMR data.
2 2
of the compounds H L -H L exhibit two intense peaks at
around 278 and 321 nm. The former absorption peak at about
*
278 nm can be assigned to the π-π transition of the benzene
*
The colour, yields, melting points and elemental analytical
1
L -H
rings, while the latter can be attributed to the intra-ligand π-π
20
transition of the C=N bonds . There was no absorption around
4
L are presented
results of the synthesized compounds H
2
2
in Table-1. Their compositions agree with the formulae. All
the compounds are white microcrystalline solid, stable in air
400 nm, which is seen in the corresponding Salen derivatives.
2
1,22
The absorption is ascribed to the quinoid form of H Salen
2
.
TABLE-1
COLOUR, YIELDS, MELTING POINTS AND ANALYTICAL DATA OF SYNTHESIZED SALAMO-TYPE COMPOUNDS H L -H L
1
4
2
2
Elemental analysis (%): Found (calcd.)
Comp.
Colour
m.p. (°C)
Yield (%)
m.f. (m.w.)
C
H
N
1
H2L
White
White
White
White
232-234
210-212
215-216
220-221
72.6
70.8
68.2
75.4
C H Br Cl N O (541.0)
2
37.92 (37.74)
39.71 (39.95)
40.04 (40.10)
41.35 (41.20)
2.69 (2.61)
2.97 (2.91)
3.22 (3.19)
3.21 (3.46)
5.21 (5.18)
5.06 (5.05)
4.93 (4.92)
4.88 (4.80)
17
14
2
2
4
2
H2L
C H Br Cl N O (555.0)
18 16 2 2 2 4
3
H2L
C H Br Cl N O (569.1)
19 18 2 2 2 4
4
H2L
C H Br Cl N O (583.1)
20 20 2 2 2 4

Vol. 26, No. 1 (2014)
Synthesis and Characterization of Multihalogen Substituted Salamo-Type Bisoximes 287
3000
2500
2000
1500
1000
500
4
000
3500
3000
2500
2000
1500
1000
500
–
1
–1
Wavenumber (cm )
Wavenumber (cm )
4
2
Fig. 4. IR spectrum of H L
1
2
Fig. 1. IR spectrum of H L
TABLE-2
H NMR DATA FOR THE SALAMO-TYPE BISOXIMES H L -H L
1
1
4
2
2
1
Comp. π-π*(nm)
H NMR (400 MHz, DMSO-d , δ/ppm)
6
2.38 (d, J = 8.8 Hz, 2H), 4.48 (s, 4H), 7.56 (d,
J = 2.4 Hz, 2H), 7.74 (d, J = 2.4 Hz, 2H),
1
H L
2
278, 321
278, 321
279, 323
279, 325
8.26 (s, 2H), 10.39 (s, 2H).
2.36 (d, J = 8.6 Hz, 4H), 4.46 (s, 4H), 7.55 (d,
J = 2.2 Hz, 2H), 7.72 (d, J = 2.2 Hz, 2H),
2
H L
2
8.25 (s, 2H), 10.20 (s, 2H).
2.33 (s, 2H), 2.36 (d, J = 8.7 Hz, 4H), 4.45 (s,
4H), 7.54 (d, J = 2.0 Hz, 2H), 7.71 (d, J = 2.2
Hz, 2H), 8.24 (s, 2H), 10.12 (s, 2H).
3
H L
2
2.32 (s, 4H), 2.35 (d, J = 8.0 Hz, 4H), 4.44 (s,
4H), 7.54 (d, J = 2.0 Hz, 2H), 7.70 (d, J = 2.2
Hz, 2H), 8.24 (s, 2H), 10.02 (s, 2H).
4
H L
2
1
1
4
The H NMR spectra of the compounds H
2
L -H
are shown in Table-2. The H NMR spectra showed
a singlet at about 8.24-8.26 ppm indicating the existence of
2
L in
1
DMSO-d
6
4
000
3500
3000
2500
2000
1500
1000
500
15
–
1
oxime bonds .
Wavenumber (cm )
Conclusion
2
2
Fig. 2. IR spectrum of H L
1
4
2 2
Four new Salamo-type compounds H L -H L that have
two oxime bonds instead of imine bonds have been designed
and synthesized by the reaction of 2 equivalents of 3-bromo-
5
-chloro-2-hydroxybenzaldehyde with 1,3-bis(aminooxy)
propane, 1,4-bis(aminooxy)butane, 1,5-bis(aminooxy)pentane
or 1,6-bis(aminooxy)hexane under mild conditions, respec-
tively. The synthesized Salamo-type compounds may be prom-
ising units for the construction of supramolecular complexes.
REFERENCES
1
.
V. Balzani and S. Campagna, Photochemistry and Photophysics of
Coordination Compounds II, Springer: Berlin (2007).
2
3
4
.
.
.
R. Bagai and G. Christou, Chem. Soc. Rev., 38, 1011 (2009).
D. Gatteschi and R. Sessoli, Angew. Chem. Int. Ed., 42, 268 (2003).
M. Shibasaki and Y. Yamamoto, Multimetallic Catalysts in Organic
Synthesis, Wiley-VCH: Weinheim, Germany (2004).
5
.
E.N. Jacobsen, in ed.: I. Ojima, In Catalytic Asymmetric Synthesis;
VCH: New York (1993).
6
7
.
.
A. Robertson and S. Shinkai, Coord. Chem. Rev. 205, 157 (2000).
P.D. Beer and E.J. Hayes, Coord. Chem. Rev. 240, 167 (2003).
4
000
3500
3000
2500
2000
1500
1000
500
8. S.J. Wezenberg andA.W. Kleij, Angew. Chem. Int. Ed., 47, 2354 (2008).
9. A.W. Kleij, Chem.-Eur. J., 14, 10520 (2008).
–1
Wavenumber (cm )
1
0. H.L.C. Feltham and S. Brooker, Coord. Chem. Rev. 253, 1458 (2009).
3
Fig. 3. IR spectrum of H
2
L
11. A.W. Kleij, Dalton Trans., 4635 (2009).

288 Yang et al.
Asian J. Chem.
1
1
2. S. Akine and T. Nabeshima, Dalton Trans., 10395 (2009).
3. S. Akine, T. Taniguchi and T. Nabeshima, Angew. Chem. Int. Ed., 41,
and J.C. Wu, Spectrochim. Acta A, 76, 476 (2010); (g) W.K. Dong, L.
Wang, Y.X. Sun, J.F. Tong and J.C. Wu, Chinese J. Inorg. Chem., 27,
372 (2011); (h) W.K. Dong, Y.X. Sun, S.J. Xing, Y. Wang and X.H.
Gao, Z. Naturforsch. 67b, 197 (2012); (i) W.K. Dong, Y.X. Sun, G.H.
Liu, L. Li, X.Y. Dong and X.H. Gao, Z. Anorg. Allg. Chem., 638, 1370
(2012); (j) W.K. Dong, S.J. Xing, Y.X. Sun, L. Zhao, L.Q. Chai and
X.H. Gao, J. Coord. Chem., 65, 1212 (2012); (k) W.K. Dong and Y.J.
Ding, Cryst. Res. Technol. 43, 321 (2008).
4
670 (2002).
1
1
4. S. Akine, W.K. Dong and T. Nabeshima, Inorg. Chem., 45, 4677 (2006).
5. S. Akine, T. Tadokoro and T. Nabeshima, Inorg. Chem., 51, 11478
(
2012).
6. S. Akine, S. Hotate and T. Nabeshima, J. Am. Chem. Soc., 133, 13868
2011).
7. (a) W.K. Dong,Y.X. Sun, C.Y. Zhao, X.Y. Dong and L. Xu, Polyhedron,
9, 2087 (2010); (b) W.K. Dong, Y.X. Sun, Y.P. Zhang, L. Li, X.N. He
1
1
(
18. S. Akine, T. Taniguchi, W.K. Dong and T. Nabeshima, J. Org. Chem.,
70, 1704 (2005).
2
and X.L. Tang, Inorg. Chim. Acta, 362, 117 (2009); (c) W.K. Dong,
X.N. He, H.B. Yan, Z.W. Lv, X. Chen, C.Y. Zhao and X.L. Tang, Poly-
hedron, 28, 1419 (2009); (d) W.K. Dong, Y.X. Sun, Y.P. Zhang, L. Li,
X.N. He and X.L. Tang, Inorg. Chim. Acta, 362, 117 (2009); (e) W.K.
Dong, C.Y. Zhao, Y.X. Sun, X.L. Tang and X.N. He, Inorg. Chem.
Commun., 12, 234 (2009); (f) W.K. Dong,Y.X. Sun, X.N. He, J.F. Tong
19. J.A. Faniran, K.S. Patel and J.C. Bailar Jr., J. Inorg. Nucl. Chem., 36,
1547 (1974).
20. T. Ghosh, B. Mondal, T. Ghosh, M. Sutradhar, G. Mukherjee and M.
Drew, Inorg. Chim. Acta, 360, 1753 (2007).
21. H.E. Smith, Chem. Rev., 83, 359 (1983).
22. S. Akine, T. Taniguchi and T. Nabeshima, Chem. Lett., 30, 682 (2001).