Comptes Rendus Chimie

Marius Andruh

In
For
are
nan
info
cin
try,
ord
con
wit
em
 m
ca
m
 m
sy
m
 m
 m
 m
C. R. Chimie 15 (2012) 837
163
httporganic molecular materials
eword
Molecular inorganic materials represent an important
a of research in materials science, with applications in
otechnology, optoelectronics and photonics, quantum
rmation processing and data storage, catalysis, medi-
e, etc. Coordination chemistry, supramolecular chemis-
 and crystal engineering join their tools and efforts in
er to obtain materials with desired structures and,
sequently, technologically useful properties.
In the last two decades, new families of compounds
h exciting properties and promising applications
erged, such as:
etal-organic frameworks (MOFs) that can be used as
talysts or hosts for various organic or inorganic
olecules;
olecule-based magnets, especially low-dimensional
stems (molecular nanomagnets: single molecule
agnets and single chain magnets);
olecular conductors and supraconductors;
etal-based nonlinear optical materials;
etallomesogens.
Most of these topics are illustrated by the articles
collected in this special issue of the Comptes Rendus de
l’Académie des sciences (Chimie): Janiak and his co-workers,
as well as Ruiz-Perez et al. report on new MOFs and their
properties; novel magnetic compounds, including multi-
functional nanomagnets, are presented by Costes, Sutter,
Martins, Cangussu, Lloret, Julve, Plass, Verdaguer, Gouzerh,
Colacio, Brechin and their co-workers; Fourmigue, Decur-
tins, and Avarvari present their recent results in the
chemistry of dithiolene and tetrathiafulvalene complexes;
new luminescent organo-metallic complexes are reported
by Silvestru et al.
I would like to thank all the contributors for their
beautiful papers and stimulating results, and I hope that
the readers will enjoy this collection of papers devoted to
inorganic molecular materials.
Marius Andruh
Inorganic Chemistry Laboratory, Faculty of Chemistry,
University of Bucharest, Street Dumbrava Rosie nr. 23,
020464 Bucharest, Romania
E-mail address: marius.andruh@dnt.ro
Contents lists available at SciVerse ScienceDirect
Comptes Rendus Chimie
ww w.s c ien c edi r ec t . c om1-0748/$ – see front matter  2012 Published by Elsevier Masson SAS on behalf of Académie des sciences.
://dx.doi.org/10.1016/j.crci.2012.10.001


Inorganic molecular materials

José Martínez-Lillo

Lise-Marie Chamoreau

Anna Proust

Michel Verdaguer

Pierre Gouzerh

Hexanuclear manganese(III) single-molecule magnets from derivatized salicylamidoximes

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COMPTES RENDUS
CHIMIE 


Editorial Board

Frédéric Lefebvre

Sergio Rojo

ROMP of norbornene catalyzed by polyoxometalates

Daniel Maynau

Hélène Bolvin

Willem Van den Heuvel

Marc Bénard

Marie-Madeleine Rohmer

Nadia Ben Amor

Ferromagnetic coupling induced by spin-orbit coupling in dipyridylamide linear trinuclear Cu-Pd-Cu and Cu-Pt-Cu complexes

Samir Meskaldji

Abdelmalik Belkhiri

Lotfi Belkhiri

Abdou Boucekkine

Michel Ephritikhine

Magnetic exchange coupling in imido bimetallic uranium(V) complexes. A relativistic DFT study

Fan Yang

Mauro Boero

Pierre Rabu

Carlo Massobrio

First principles investigation of the atomic structure and magnetic properties of copper hydroxide acetate

Ebrahim Soleimani

Mohammad Mehdi Khodaei

Afsaneh Taheri Kal Koshvandi

Pre
On
b-
Eb
Dep
1. I
mu
mo
solv
can
syn
tag
form
mo
syn
inte
aqu
the
com
eco
disc
C. R. Chimie 15 (2012) 273–277
A R
Artic
Rece
Acce
Avai
Keyw
Alky
Mul
Wat
b-C
Sodi
Mel
* 
163
doi:liminary communication/Communication
e-pot three-component reaction: Synthesis of substituted
cyanocarbonyls in aqueous media
rahim Soleimani *, Mohammad Mehdi Khodaei, Afsaneh Taheri Kal Koshvandi
artment of Chemistry, Razi University, Kermanshah 67149-67346, Iran
ntroduction
Organic reactions in aqueous media have attracted
ch attention recently not only because water is the
st abundant, environmentally benign, and cheapest
ent but also because unique selectivity and reactivity
 be expected from this solvent [1].
Multicomponent reactions (MCR) are very efficient
thetic methods. The strategy offers significant advan-
es over classical stepwise approaches allowing the
ation of several bonds and the construction of complex
lecular architectures from simple precursors in a single
thetic operation without the need for isolation of
rmediates [2]. MCRs, particularly those performed in
eous media, have become increasingly useful tools for
 synthesis of chemically and biologically important
pounds because of their environmentally friendly atom
nomy and green characteristics [3]. Furthermore, the
overy of novel MCRs can be considered an interesting
topic for academic research that also satisfies the practical
interest of applied science [2,3].
The organic nitriles are of much importance in organic
synthesis as these are versatile intermediates in the
synthesis of amines, carboxylic acids, esters and ketones
which are useful raw materials for pharmaceuticals,
agrochemicals and dyes [4]. The cyano moiety is also
present in numerous bioactive molecules [5]. The classical
method for the synthesis of alkyl cyanide involves
nucleophilic substitution of an alkyl halide with metal
cyanides [4a].
Furthermore, the introduction of nitrile into organic
compounds can be achieved using different routes
including: the direct conversion of aldehydes [6], oxime
ethers [7], thioamides [8], carboxylic acid and their esters
[9], dehydration of aldoximes [10] and amides [11] with
various reagents, oxidation of amines [12], and reduction
of primary aliphatic nitro compounds [13], enzymatic
methods [14] and application of organoborane/diazoace-
tonitrile [15]. Unfortunately, most of the reported methods
suffer from serious drawbacks such as the difficulty of
available reagents, low yields, drastic reaction conditions
and tedious work-up procedures. Thus, the development of
a convenient and efficient methodology for the synthesis of
 T I C L E I N F O
le history:
ived 25 August 2011
pted after revision 6 January 2012
lable online 10 February 2012
ords:
l nitrile
ti-component reactions
er
yanocarbonyls
um cyanide
drum’s acid
A B S T R A C T
An environmentally friendly and simple method for the synthesis of alkyl nitriles or
b-cyanocarbonyls via a one-pot three-component reaction of Meldrum’s acid, aldehydes
and sodium cyanide in water, without using any catalyst or activation at room
temperature is reported.
 2012 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Corresponding author.
E-mail address: e_soleimanirazi@yahoo.com (E. Soleimani).
Contents lists available at SciVerse ScienceDirect
Comptes Rendus Chimie
ww w.s c ien c edi r ec t . c om1-0748/$ – see front matter  2012 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.
10.1016/j.crci.2012.01.004
E. Soleimani et al. / C. R. Chimie 15 (2012) 273–277274b-cyanocarbonyl compounds is an interesting target for
investigation.
One of the best methods for the introduction of a
cyanide group involves the Michael addition of cyanide
anion to an a,b-unsaturated carbonyl derivatives in the
presence of strong bases or Lewis acid catalysts [16]. As
part of our ongoing research aimed at developing synthesis
of alkyl nitriles [17], herein we report a one-pot, three-
component reaction of Meldrum’s acid 1, an aldehyde 2
and sodium cyanide 3, for the preparation of alkyl nitrile or
b-cyanocarbonyl 4 without using any catalyst at room
temperature in water (Scheme 1).
2. Results and discussion
We compared the reaction rate in different solvents by
measuring the isolated yield using identical amounts of
reactants for a fixed reaction time of 6 h at room
temperature. The desired product was obtained in protic
solvents such as water, ethanol, and methanol but water
can afford the product in good yield even better than
ethanol and methanol. The desired product was scarcely
obtained in dichloromethane, benzene, and toluene. We
also studied the reaction at different temperatures. The
reaction rate decreased as the reaction temperature was
raised. Because at high temperature reaction aldol-Michael
two equivalents of Meldrum’s acid with aldehyde is a
competing reaction; the product of this reaction was
separated as a by-product in high temperature [18].
With the optimal conditions in hand, the range of the
substrates was checked. The Knoevenagel condensation
and Michael addition reaction were carried out using a
series of different aldehydes with Meldrum’s acid and
sodium cyanide. The results are summarized in Table 1.
The structures of the products were established by
different spectroscopic methods (for details see Experi-
mental section). In all cases, excellent yields were
obtained, whatever the nature of the substituent present
on the aldehyde (electron-donating or electron-withdraw-
ing). This confirms the reliability of the synthetic method.
For the scope and limitation of the method, we
investigated the reaction of 2-naphthyl carbaldehyde with
Meldrum’s acid and sodium cyanide under the above
conditions led to the formation of the corresponding alkyl
nitriles in 99% yields (Scheme 2).
Mechanistically, it is conceivable that the reaction
involves the initial formation of activated alkene or a,b-
unsaturated carbonyl 5 through a Knoevenagel conden-
sation reaction of Meldrum’s acid and aldehyde. After-
wards the intermediate 5 undergoes Michael addition
reaction with cyanide to afford b-cyanocarbonyls 4
(mechanism A). Another mechanism possible for this
reaction involves the initial formation of cyanohydrin 6
through a cyanohydrin formation of sodium cyanide with
aldehyde. Afterwards nucleophilic substitution of the
cyanohdrin 6 with sodium cyanide affords to b-cyano-
carbonyls 4 (mechanism B) (Scheme 3). To clarify the
proposed mechanisms, first, the Michael acceptor 5 was
synthesized from condensation of Meldrum’s acid and
benzaldehyde, subsequently reaction of 5 with sodium
cyanide afforded corresponding b-cyanocarbonyl 4. Also
for further clarification, cyanohdrin 6 was synthesized
from reaction aldehyde with sodium cyanide in water;
subsequently cyanohdrin 6 did not undergo reaction with
Meldrum’s acid under the reaction conditions. Therefore
mechanism A is reasonable.
O O
+ NaCN
1 2 3
O ONa
CN
O O
O OMeMe
Me Me
CHO
R +
4
H2O
R
r.t
Scheme 1. Synthesis of b-cyanocarbonyls.
Table 1
Reaction of Meldrum’s acid and aldehyde with sodium cyanide in water at
room temperature.
Entry R1 Product Yield (%)a
1 H 4a 99
2 4-Cl 4b 98
3 4-OH 4c 98
4 4-NO2 4d 99
5 4-OMe 4e 99
6 4-Me 4f 99
7 3-OH 4g 98
8 3-NO2 4h 98
a Isolated yield.
O O
+ NaCN
O O
MeMe
+
H2O
r.t
CHO
CN
O
O
Me
Me
O
ONa
4iScheme 2. Synthesis of alkyl nitrile derivative.
3. C
wa
thr
aro
des
aro
don
ing
var
tha
syn
4. E
4.1.
app
a Sh
we
200
DM
the
Ald
4.2.
dim
phe
deh
1 m
E. Soleimani et al. / C. R. Chimie 15 (2012) 273–277 275onclusion
In conclusion, the efficient synthesis of alkyl nitrile in
ter, without employing catalyst has been described. The
ee-component reaction involving Meldrum’s acid, an
matic aldehyde and sodium cyanide afforded the
ired products with excellent yields. A wide range of
matic aldehydes were tested, bearing either electron-
ating or electron-withdrawing substituent’s, suggest-
 that this method can be used to synthesize a large
iety of compounds. It has therefore been demonstrated
t using water as the solvent is ideally suited for the
thesis of alkyl nitriles.
xperimental
 Materials and techniques
Melting points were taken on an Electrothermal 9100
aratus and left uncorrected. IR spectra were obtained on
imadzu IR-470 spectrometer. 1H and 13C NMR spectra
re recorded on a Bruker DRX-200 Avance spectrometer at
 and 50 MHz. NMR spectra were obtained on solutions in
SO using tetramethylsilane as internal standard. All of
 chemicals were purchased from Fluka, Merck and
rich and used without purification.
 Typical procedure: preparation of 2-(sodium 2,2-
ethyl-4-oxo-4H-1,3-dioxin-5-yl-6-oxide)-2-
nylacetonitrile (4a)
A solution of Meldrum’s acid (0.14 g, 1 mmol), benzal-
yde (0.11 g, 1 mmol) and sodium cyanide (0.05 g,
mol) in H2O (10 mL) was stirred for 6 h at room
temperature. After completion of the reaction as indicated
by TLC, the solvent was evaporated, and the residue was
washed with ether and recrystallized in ether/n-hexane
(50/50) to give the pure product 4a. White powder (0.28 g,
yield 99%). Mp 218 8C. IR (KBr) (nmax /cm
1): 3183, 2272,
1720. MS, (m/z): 232 (M+-NaCN). 1H NMR (200 MHz,
DMSO-d6): dH (ppm) 1.44 (6H, s, CH3-C-CH3), 5.09 (1H, s,
CH-CN), 7.16–7.35 (5H, m, H-Ar). 13C NMR (50 MHz,
DMSO-d6): dC (ppm) 26.2 (CH3-C-CH3), 32.4 (CH-CN), 71.7
(C=CC-ONa), 100.4 (CH3-C-CH3), 121.7, 126.8, 127.2, 128.4,
139.2 (C-Ar and CN), 164.6 (C=CO). Anal. Calcd for
C14H12NNaO4: C, 59.79; H, 4.30; N, 4.98. Found: C,
59.83; H, 4.27; N, 5.11.
4.3. 2-(4-chlorophenyl)-2-(sodium-2,2-dimethyl-4-oxo-4H-
1,3-dioxin-5-yl-6-oxide) acetonitrile (4b)
Yellow powder (0.29 g, yield 98%). Mp 197 8C. IR (KBr)
(nmax /cm
1): 3182, 2271, 1725. MS, (m/z): 266 (M+-NaCN).
1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.42 (6H, s, CH3-C-
CH3), 5.07 (1H, s, CH-CN), 7.30–7.32 (4H, m, H-Ar).
13C
NMR (50 MHz, DMSO-d6): dC (ppm) 26.1 (CH3-C-CH3), 31.9
(CH-CN), 71.8 (C=C-ONa), 100.7 (CH3-C-CH3), 121.3, 128.4,
129.1, 131.5, 138.2 (C-Ar and CN), 164.7 (C=O). Anal. Calcd
for C14H12ClNO4: C, 57.25; H, 4.12; Cl, 12.07; N. Found: C,
57.33; H, 4.17; N, 12.11.
4.4. 2-(sodium-2,2-dimethyl-4-oxo-4H-1,3-dioxin-5-yl-6-
oxide)-2-(4-hydroxyphenyl) acetonitrile (4c)
Red powder (0.29 g, yield 98%). Mp 193 8C. IR (KBr)
(nmax /cm
1): 3184, 2273, 1727. MS, (m/z): 248 (M+-NaCN).
1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.49 (6H, s, CH3-C-
CH3), 3.47 (OH exchanged with water of DMSO-d6), 5.02
(1H, s, CH-CN), 6.70 (2H, d, 3JHH = 8.4 Hz, H-Ar), 7.20 (2H, d,
O O
+ NaCN
1 2 3
O O
MeMe
CHO
+
CN
OH
NaCN
O O
O O
MeMe
5
6
SN Reaction Michael addition
O O
O O
MeMe
O ON a
CN
O O
Me Me
4
Kno evenagel condensationCyano hydrin formatio n
Mechanism AMechan ism B
Scheme 3. Proposal mechanisms.
E. Soleimani et al. / C. R. Chimie 15 (2012) 273–2772763JHH = 8.4 Hz, H-Ar).
13C NMR (50 MHz, DMSO-d6): dC
(ppm) 26.3 (CH3-C-CH3), 31.6 (CH-CN), 71.7 (C=C-ONa),
100.1 (CH3-C-CH3), 115.1, 122.1, 128.3, 129.7, 156.2 (C-Ar
and CN), 164.4 (C=O). Anal. Calcd for C14H12NNaO5: C,
56.57; H, 4.07; N, 4.71. Found: C, 56.62; H, 4.17; N, 4.79.
4.5. 2-(sodium-2,2-dimethyl-4-oxo-4H-1,3-dioxin-5-yl-6-
oxide)-2-(4-nitrophenyl) acetonitrile (4d)
Brown powder (0.32 g, yield 99%). Mp 178 8C. IR (KBr)
(nmax /cm
1): 3187, 2270, 1726. MS, (m/z): 248 (M+-
NaCN). 1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.48 (6H,
s, CH3-C-CH3), 5.29 (1H, s, CH-CN), 7.63 (2H, d,
3JHH = 8.5 Hz, H-Ar), 8.22 (2H, d,
3JHH = 8.5 Hz, H-Ar).
13C
NMR (50 MHz, DMSO-d6): dC (ppm) 26.2 (CH3-C-CH3),
31.8 (CH-CN), 71.10 (C=C-ONa), 100.1 (CH3-C-CH3), 123.0,
123.7, 128.4, 130.4, 147.5 (C-Ar and CN), 164.4 (C=O).
Anal. Calcd for C14H11N2NaO6: C, 51.54; H, 3.40; N, 8.59.
Found: C, 51.60; H, 3.38; N, 8.60.
4.6. 2-(sodium-2,2-dimethyl-4-oxo-4H-1,3-dioxin-5-yl-6-
oxide)-2-(4-methoxyphenyl) acetonitrile (4e)
Cream powder (0.31 g, yield 99%). Mp 195 8C. IR (KBr)
(nmax /cm
1): 3183, 2277, 1730. MS, (m/z): 262 (M+-NaCN).
1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.40 (6H, s, CH3-C-
CH3), 3.67 (3H, s, OCH3), 5.10 (1H, s, CH-CN), 7.80 (2H, d,
3JHH = 8.0 Hz, H-Ar), 7.22 (2H, d,
3JHH = 8.0 Hz, H-Ar).
13C
NMR (50 MHz, DMSO-d6): dC (ppm) 26.3 (CH3-C-CH3), 31.6
(CH-CN), 55.5 (OCH3), 71.7 (C=C-ONa), 100.2 (CH3-C-CH3),
113.8, 122.0, 128.4, 131.4, 158.2 (C-Ar and CN), 164.4
(C=CO). Anal. Calcd for C15H14NNaO5: C, 57.88; H, 4.53; N,
4.50. Found: C, 57.78; H, 4.59; N, 4.42.
4.7. 2-(sodium-2,2-dimethyl-4-oxo-4H-1,3-dioxin-5-yl-6-
oxide)-2-p-tolylacetonitrile (4f)
White powder (0.29 g, yield 99%). Mp 160 8C. IR (KBr)
(nmax /cm
1): 3182, 2271, 1731. MS, (m/z): 268 (M+-NaCN).
1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.65 (6H, s, CH3-C-
CH3), 2.30 (3H, s, CH3), 5.15 (1H, s, CH-CN), 7.19 (2H, d,
3JHH = 8.1 Hz, H-Ar), 7.33 (2H, d,
3JHH = 8.1 Hz, H-Ar).
13C
NMR (50 MHz, DMSO-d6): dC (ppm) 21.0 (CH3), 26.3 (CH3-
C-CH3), 32.1 (CH-CN), 71.6 (C=CC-ONa), 100.2 (CH3-C-
CH3), 121.8, 127.2, 128.9, 135.7, 136.5 (C-Ar and CN), 164.4
(C=CO). Anal. Calcd for C15H14NNaO4: C, 61.02; H, 4.78; N,
4.74. Found: C, 61.12; H, 4.83; N, 4.64.
4.8. 2-(sodium-2,2-dimethyl-4-oxo-4H-1,3-dioxin-5-yl-6-
oxide)-2-(3-hydroxyphenyl) acetonitrile (4g)
Cream powder (0.29 g, yield 98%). Mp 192 8C. IR (KBr)
(nmax /cm
1): 3183, 2271, 1726. MS, (m/z): 248 (M+-NaCN).
1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.36 (6H, s, CH3-C-
CH3), 3.67 (OH exchanged with water of DMSO-d6), 4.91
(1H, s, CH-CN), 6.48–7.01 (4H, m, H-Ar). 13C NMR (50 MHz,
DMSO-d6): dC (ppm) 26.4 (CH3-C-CH3), 32.3 (CH-CN), 71.3
(C=CC-ONa), 100.1 (CH3-C-CH3), 113.7, 114.3, 117.9, 121.7,
129.2, 140.8, 157.5 (C-Ar and CN), 164.4 (C=CO). Anal.
Calcd for C14H12NNaO5: C, 56.57; H, 4.07; N, 4.71. Found: C,
4.9. 2-(sodium-2,2-dimethyl-4-oxo-4H-1,3-dioxin-5-yl-6-
oxide)-2-(3-nitrophenyl) acetonitrile (4h)
Cream powder (0.32 g, yield 98%). Mp 185 8C. IR (KBr)
(nmax /cm
1): 3183, 2271, 1729. MS, (m/z): 248 (M+-NaCN).
1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.43 (6H, s, CH3-C-
CH3), 5.23 (1H, s, CH-CN), 7.50–8.13 (4H, m, H-Ar).
13C
NMR (50 MHz, DMSO-d6): dC (ppm) 26.1 (CH3-C-CH3), 32.4
(CH-CN), 71.50 (C=CC-ONa), 100.8 (CH3-C-CH3), 120.8,
121.7, 122.1, 130.1, 134.0, 141.5, 147.5 (C-Ar and CN),
164.7 (C=CO). Anal. Calcd for C14H11N2NaO6: C, 51.54; H,
3.40; N, 8.59. Found: C, 51.44; H, 3.38; N, 8.51.
4.10. 2-(sodium-2,2-dimethyl-4-oxo-4H-1,3-dioxin-5-yl-6-
oxide)-2-(naphthalen-3-yl) acetonitrile (4i)
Cream powder (0.33 g, yield 98%). Mp 188 8C. IR (KBr)
(nmax /cm
1): 3184, 2270, 1726. MS, (m/z): 304 (M+-NaCN).
1H NMR (200 MHz, DMSO-d6): dH (ppm) 1.50 (6H, s, CH3-C-
CH3), 5.32 (1H, s, CH-CN), 7.50–7.91 (7H, m, H-Ar).
13C
NMR (50 MHz, DMSO-d6): dC (ppm) 26.2 (CH3-C-CH3), 32.6
(CH-CN), 71.80 (C=CC-ONa), 100.5 (CH3-C-CH3), 120.6,
125.1, 126.0, 126.1, 126.6, 127.8, 128.0, 128.1, 132.2, 133.0,
136.9 (C-Ar and CN), 164.6 (C=CO). Anal. Calcd for
C18H14NNaO4: C, 65.26; H, 4.26; N, 4.23. Found: C,
65.34; H, 4.22; N, 4.32.
Acknowledgements
We gratefully acknowledge financial support from the
Research Council of Razi University.
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