Transformations of (ferrocenylmethylidene)malononitrile under the action of molecular sulfur and NaHS

Article abstract of DOI:10.1016/j.mencom.2021.07.038

Reaction of (ferrocenylmethylidene)malononitrile with molecular sulfur and NaHS in PriOH/H2O medium gives (di)ferrocenyl-substituted 3-imino-, 3-oxo- and 3-thioxo-1,2-dithioles, ferrocenyl-substituted aminoisophthalonitrile and pyridine derivatives as wel

Full text of DOI:10.1016/j.mencom.2021.07.038

Mendeleev
Communications
Mendeleev Commun., 2021, 31, 550–551
Transformations of (ferrocenylmethylidene)malononitrile
under the action of molecular sulfur and NaHS
Jessica J. Sánchez García, Gustavo Huerta Vargas, Marcos Flores-Alamo and Elena I. Klimova*
Facultad de Química, Universidad Nacional Autónoma de México, Cd. Universitaria Coyoacán, C. P. 0410,
CDMX, México. E-mail: eiklimova@yahoo.com.mx
DOI: 10.1016/j.mencom.2021.07.038
Me
X
Reaction of (ferrocenylmethylidene)malononitrile with
molecular sulfur and NaHS in PriOH/H2O medium gives
(di)ferrocenyl-substituted 3-imino-, 3-oxo- and 3-thioxo-1,2-
dithioles, ferrocenyl-substituted aminoisophthalonitrile and
pyridine derivatives as well as products of fragmentation of
the starting reactant. The posible mechanism for their
formation is discussed.
CN
R
Fc
CN
CN
S8/NaHS
PriOH/H2O
80 °C
S
+
S
Fe
NH2
Fc
Fc
CN
NC
R = CN, Fc
X = NH, O, S
CN
Fc
Fc
CO2Pri
+
+
H2N
N
OPri
Keywords: ferrocene derivatives, acrylonitriles, malononitriles, sulfur, sulfuration, 1,2-dithioles, cycloaddition, pyridine-3,5-dicarbo-
nitrile derivatives, isophthalonitrile derivatives.
The reactions of molecular sulfur with organic compounds
have been a subject of extensive investigation1 owing to some
of its properties and the special character of sulfur bonds.
Elemental sulfur shows an extremely high tendency for self-
coupling and forming S–S bonds to give cyclic or linear
molecules of Sn (n = 6, 8, 12 or more) type.2 The physical and
chemical properties of sulfur are strongly environment-
dependent. The problems of activating molecular sulfur with
acids, bases, transition metals, and salts such as InX3, CuBr,
Cu(OAc)2 and KF in the reactions with C–H, C–Cl, C–N and
C–O bonds are documented.3–8 Many of the mechanistic
features of these reactions are yet to be clarified. For example,
in reactions of sulfur with unsaturated compounds it is not
certain whether the reaction proceeds through the heterolytic or
the homolytic pathway, whether the reaction is initiated by the
abstraction of hydrogen or by the addition of sulfur to the
double bond.9 The electrophilic and nucleophilic displacement
at a sulfur atom is of particular interest, a typical example being
the three-component reaction for the synthesis of 2-aryl-
thiophenes from arylacetaldehydes, 1,3-dicarbonyl compounds
and molecular sulfur.4,10,11
All experiments were carried out under reflux conditions
(Scheme 1). The following competitive processes did occur.
Ferrocenylcarboxaldehyde 2 (5%), malononitrile 3 (traces), and
ferrocenylacetonitrile 4 (5%) were formed. Other products arose
from fragmentation reactions of initial 1 (see Scheme 1), namely,
4-cyano-5-ferrocenyl-1,2-dithiol-3-imine 5 (14%, [3+2]-cyclo-
addition of 1 with two sulfur atoms), isopropyl cis/trans-2,3-di-
ferrocenylacrilates 8 (16%, products of the condensation of
FcCHO with FcCH2CN and the alcoholysis of 2,3-diferro-
cenylacrylonitrile), 4,5-diferrocenyl-1,2-dithiol-3-one 6 (12%)
and analogous thione 7 (10%, [3+2]-cycloaddition of 8 with two
sulfur atoms), 3-amino-5-ferrocenyl-1-methylisophthalonitrile 9
(20%, cyclocondensation of 1 with 3,3-dimethylacrylonitrile),
2-amino-4-ferrocenyl-6-isopropoxypyridine-3,5-dicarbonitrile
10 (10%, cyclocondensation of 1 with malononitrile12(c)).
The reaction mixtures were separated by chromatography
methods, the structure of the products was determined based on
their IR, NMR and mass spectra and elemental analysis (for
details, see Online Supplementary Materials). The physico-
chemical characteristics of compounds 2, 4,13 6,14 cis-815 and
1012(c) corroborate completely with their structures.
During the last years, the application of molecular sulfur has
increased in many fields to obtain various valuable materials.10,11
A wide range of electrophilic compounds were reacted with
molecular sulfur to produce sulfur-containing functionalized
aromatic compounds, aldehydes, ketones, heterocycles, 1,3-di-
carbonyl compounds and 1,2-enones.10,11
The synthesis of sulfur-containing ferrocene derivatives has
not been extensively reported. The interest in these compounds
may stem from the peculiar chemical behaviors of both ferrocene
and heterocyclic moieties. On the other hand, compounds with
β-dicarbonyl and acrylonitrile systems were used as
1,3-bielectrophiles in cycloaddition, fragmentation or
condensation reactions with N–N, S–S, N–C–S, N–C–N building
blocks.12 Therefore, in this work we have investigated the
transformation of the (ferrocenylmethylidene)malononitrile 1 in
the presence of elemental sulfur S8 and NaHS in a PriOH/H2O
medium.
Fc
CN
CN
S8/NaHS
i
FcCH2CN
+
FcCHO
CH2(CN)2
+
S
1
2
3
4
O
NH
S
S
NC
Fc
Fc
Fc
+
+
+
S
S
S
S
Fc
Fc
5
6
7
Me
Fc
N
Fc
Fc
CN
NC
CN
+
+
+
O
Fc
PriO
NH2
H2N
OPri
CN
cis,trans-8
9
10
Scheme 1 Reagents and conditions: i, PriOH, H2O, reflux, 6–8 h.
© 2021 Mendeleev Communications. Published by ELSEVIER B.V.
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
– 550 –

Mendeleev Commun., 2021, 31, 550–551
N
C
Fc
O
O
S
S
H
Fc
H2C
Me
CN
CN
S
OPri
H
–
Fc
Fc
C
O
S
S
S
+ S8
Fc
CN
Fc
NH
CN
H
Fc
H
Fc
S
H+
H+
7
– PriOH
+
S
NH
S
S
+
C
N
Fc
+
1
H
cis,trans-8
11
6
H
Me
S
S
S
S
S
S
S
13
14
S
Me
CN
CN
12
Scheme 2 Reagents and conditions: PriOH, H2O, reflux, 6–8 h.
NH2
CN
Fc
[S]
9
– H+
– H2S
The most feasible mechanism for the formation of compounds
6 and 7 involves the initial nucleophilic attack of one sulfur atom
of octamer S8 on the C3 atoms of 2,3-diferrocenylacrylates 8 (the
Michael reaction) resulting in unstable intermediate species 11.
Intramolecular cyclization of 11 afforded the final oxo and
thioxo 4,5-diferrocenyl-1,2-dithioles 6, 7 (Scheme 2).
Me
15
Scheme 3 Reagents and conditions: PriOH, H2O, reflux, 6–8 h.
The structure of isophthalonitrile derivative 9 was verified by
single crystal X-ray diffraction (Figure 1)† and was in accordance
with the 1H and 13C NMR spectroscopic data. The main
geometrical parameters are given in Tables S1 and S2 (see Online
Supplementary Materials).16–20
A tentative mechanism for the formation of compound 9 is
outlined in Scheme 3. The reaction may begin with the initial
addition of 3,3-dimethylacrylonitrile 12 at the triple nitrile bond
of (ferrocenylmethylidene)malononitrile 1 (the anti-Michael
addition) resulting in the intermediate species 13. Subsequent
intramolecular cyclization of intermediate 13 is accompanied by
the aromatization of intermediate 14 and finally leads to
product 9. 3,3-Dimethylacrylonitrile 12 could be formed through
a condensation of acetone (oxidation product of isopropyl
alcohol) with acetonitrile (product of the fragmentation of the
initial compound 1).
realization of different chemical processes between the
fragmentation products and initial compound 1. The formation
of diferrocenyl-substituted 1,2-dithiol-3-one and 1,2-dithiole-3-
thione is noteworthy. This new type of transformation of
compound 1 leading to a wide variety of products should be of
interest to synthetic, theoretical and practical organic chemists.
The work was supported by DGAPA-UNAM (Mexico, grant
IN 217421) and CONACyT (Mexico, grant CB-2015/251437).
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2021.07.038.
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Figure 1 Molecular structure of compound 9 according to XRD data.
Crystal data for 9. C19H15FeN3 (M = 341.19), orthorhombic, space
†
group Pbca at 130(2) K: a = 10.9523(10), b = 12.5542(12) and
c = 22.231(2) Å, a = b = g = 90°, Z = 8,
dcalc = 1.483 g cm–3,
m(MoKa) = 1.374 mm–1, F(000) = 1408. A total of 21447 reflections
were collected (3878 independent reflections, Rint = 0.3216), Goodness-
of-fift on F2 1.243, final R indices [I > 2s(I)] R1 = 0.1754 and wR2 =
= 0.3558, R indices (all data) R1 = 0.2740 and wR2 = 0.3839, 3878 refined
parameters. Data were collected on an Oxford Diffraction Gemini ‘A’
diffractometer with a CCD area detector with l(CuKa) = 1.54184 Å at
130 K. Structure solution and refinement were carried out using the
programs SHELXS-201416 and SHELXL-2014,16 respectively, WinGX
v2018.317 and Mercury CSD 4.1.018 were used to prepare the material for
publication. Full-matrix least-squares refinement was carried out by
minimizing (Fo2–Fc2).2 All nonhydrogen atoms were refined
anisotropically. Hydrogen atoms attached to carbon atoms were placed in
geometrically idealized positions and refined as riding on their parent
atoms, with C–H = 0.95–1.00 Å with Uiso(H) = 1.2Ueq(C) for aromatic
and methyne groups, and Uiso(H) = 1.5Ueq(C) for methyl group.
CCDC 2065188 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via http://www.ccdc.cam.ac.uk.
Received: 3rd March 2021; Com. 21/6476
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