Electrogenerated base-promoted synthesis and antimicrobial activity of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiolan-2-ylidene)-2-arylacetonitrile

Article abstract of DOI:10.1080/17415993.2015.1005620

The new preparation of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiol-2-ylidene)-2-arylacetonitrile is described. The electrogenerated cyanomethyl base/anion obtained from the electroreduction of acetonitrile promotes reactions between ar

Full text of DOI:10.1080/17415993.2015.1005620

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Electrogenerated base-promoted
synthesis and antimicrobial activity
of 2-(1,3-dithian-2-ylidene)-2-
arylacetonitrile and 2-(1,3-dithiolan-2-
ylidene)-2-arylacetonitrile
Kaouthar Hamrounia, Taieb Saiedab, Nariman El Abedc, Sami Ben
Hadj Ahmedc, Khaled Boujlela & Mohamed Lamine Ben Khouda
a Laboratoire de Chimie Analytique et Electrochimie, Faculté
des Sciences de Tunis, Université Tunis El-Manar, Campus
Universitaire, Tunis, Tunisie
b Département de Chimie et de Biologie Appliquées, Institut
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National des Sciences Appliquées et de Technologie, Tunis, Tunisie
c Laboratoire de protéines et molécules bioactives Ingénierie,
Institut National des Sciences Appliquées et de la Technologie
Centre Urbain Nord, Université de Carthage, Tunis, Tunisie
Published online: 03 Feb 2015.
To cite this article: Kaouthar Hamrouni, Taieb Saied, Nariman El Abed, Sami Ben Hadj Ahmed,
Khaled Boujlel & Mohamed Lamine Ben Khoud (2015) Electrogenerated base-promoted
synthesis and antimicrobial activity of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-
(1,3-dithiolan-2-ylidene)-2-arylacetonitrile, Journal of Sulfur Chemistry, 36:2, 196-206, DOI:
10.1080/17415993.2015.1005620
To link to this article: http://dx.doi.org/10.1080/17415993.2015.1005620
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Journal of Sulfur Chemistry, 2015
Vol. 36, No. 2, 196–206, http://dx.doi.org/10.1080/17415993.2015.1005620
Electrogenerated base-promoted synthesis and antimicrobial
activity of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and
2-(1,3-dithiolan-2-ylidene)-2-arylacetonitrile
Kaouthar Hamrounia, Taieb Saieda,b∗, Nariman El Abedc, Sami Ben Hadj Ahmedc, Khaled
Boujlela and Mohamed Lamine Ben Khouda
aLaboratoire de Chimie Analytique et Electrochimie, Faculté des Sciences de Tunis, Université Tunis El-
Manar, Campus Universitaire, Tunis, Tunisie; bDépartement de Chimie et de Biologie Appliquées, Institut
National des Sciences Appliquées et de Technologie, Tunis, Tunisie; cLaboratoire de protéines et molécules
bioactives Ingénierie, Institut National des Sciences Appliquées et de la Technologie Centre Urbain Nord,
Université de Carthage, Tunis, Tunisie
(Received 18 October 2014; accepted 5 January 2015)
The new preparation of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiol-2-ylidene)-2-
arylacetonitrile is described. The electrogenerated cyanomethyl base/anion obtained from the electrore-
duction of acetonitrile promotes reactions between arylacetonitrile, carbon disulfide and 1-bromo-3-
chloropropane or 1,2-dibromoethane. Obtained products have been identified according to their spec-
troscopic data (IR and 1H NMR and 13C NMR) and elemental analysis. The possible antibacterial
activities of some of these compounds were investigated. Promising results were found against few types
of bacteria.
N
C
R
Br-(CH2)2-Br
S
S
R
1) EGB
2) CS2
CH2
N
NC
C
R
S
Br-(CH2)3-Cl
S
Keywords: 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile; 2-(1,3-dithiol-2-ylidene)-2-arylacetonitrile; anion
EGBs; carbone disulfur; antimicrobial activity
1. Introduction
Ketene dithioacetals are well known as versatile intermediates in organic synthesis. Therefore,
functionalized ketene dithioacetals have revealed to be a push pull system in synthetic organic
*Corresponding author. Email: saied.taieb@gmail.com
c
ꢀ 2015 Taylor & Francis

Journal of Sulfur Chemistry 197
N
N
1) EGB
2) CS
Ar
CH
C
C
R
R
2
or
2
3)
r-
B
(CH2)3-Cl
Br-(CH2)2-Br
or
N
C
S
S
a-e
2
1
a-e
3
S
S
Scheme 1. Synthesis of 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiol-2-ylidene)-2-arylacetonitrile.
sulfur chemistry.[1] Thereby, many methods of synthesis of substituted ketene dithioacetals have
been developed.[2] Extensive research, since the last decade, has shown the importance of the
use of these molecules in several syntheses such as the synthesis of 4-functionalized quinoline
derivatives, 4-((1,3-dithian-2-ylidene)methyl)quinolines.[3] On the other hand, arylacetonitriles
are of great importance due to their use in the synthesis of several biologically active molecules
such as flavonoïd pigments,[4] antibiotics [5] and vitamin A.[6] Herein and as an extension to our
works,[7,8] we have combined two interesting functions ketene dithioacetal and arylacetonitrile
to obtain new sulfur heterocycles having five 2 and six atoms 3.
As a result of mild reaction conditions and elimination of the use of toxic and harmful chem-
icals, we synthesized these products by an electrochemical approach which is based on the use
of electrogenerated base (EGB). This entity is obtained by simple galvanostatic reduction of
acetonitrile in the presence of quaternary ammonium salts as supporting electrolyte.[9] One of
the most important advantages of the use of EGB is the excellent control of the base strength
depending on the choice of the solvent acidity, the current imposed density and the duration of
the electrolysis.[10,11]
In the last few years, numerous papers reported the use of EGB, particularly the electrogen-
erated acetonitrile anion.[9,12–16] The reactivity of this anion makes it an important reagent
in organic chemistry.[17] It is well established that the electrochemical reduction of acetonitrile
in the presence of quaternary ammonium salt as a supporting electrolyte produces the corre-
sponding cyanomethyl anion which is strong enough (pKa value of 31.3) to remove weak acidic
protons and is also able to act as a nucleophile.[18–20]
In previous works, we have successfully exploited electrochemical approach for the syn-
thesis of acyclic dithiocarbamates, N-benzylic rhodanines and thiazolidine-2-thiones.[21–23]
More recently, we reported on an EGB-promoted synthesis of a series of 3,3-bis(ethylthiol)-
2-arylacrylonitriles, of 3,3-bis(ethoxyacetatethiol)-2-arylacrylonitriles and 2-aryl-3,3-bis ((per-
fluoroalkyl)thio) acrylonitriles starting from arylacetonitrile.[7,8] In these works, we failed
to obtain expected sulfur heterocyclic compounds; this is probably due to the weak reactiv-
ity of esters regarding thiocarbamate anion. Herein, as an extension to the previous results,
1-bromo-3-chloropropane and 1,2-dibromoethane are used through the same methodology in
aim to synthesize 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiolan-2-ylidene)-
2-arylacetonitrile. As presumed, some of the heterocyclic prepared in this study have shown
significant antibacterial activity (Scheme 1).
2. Electrochemical synthesis
2.1. Experimental
The current–potential curves of all arylacetonitriles used in this work were recorded in a solu-
tion of acetonitrile and tetrabutylammonium tetrafluoroborate (0.1 mol·L−1) with a platinum

198 K. Hamrouni et al.
electrode and a reference electrode Ag/Ag+ and showed that arylacetonitriles are not reducible
under these conditions. Thus, arylacetonitriles can be introduced at the beginning of electrolysis
according to the method of Feroci et al.[24]
Electrolysis of arylacetonitriles (3 mmol) in the presence of tetrabutylammonium tetrafluorob-
orate (0.1 mol·L−1) as the supporting electrolyte and acetonitrile as solvent (100 mL) was carried
out under galvanostatic conditions (i = 80 mA). The solution was placed in an undivided elec-
trochemical cell cooled at −20 °C, with a magnesium rod as a sacrificial anode and a stainless
steel grid cathode, maintained under inert atmosphere of nitrogen.
The acetonitrile is reduced at the cathode leads to the formation in situ of the cyanomethyl
carbanions −CH2CN. This EGB was stabilized as (NC-CH2)2Mg by the magnesium cation gen-
erated from the anode oxidation. Then, it deprotoned the arylacetonitrile into the corresponding
anion.
The electrolysis is stopped when the desired quantity of EGB is produced, then, carbon
disulfide in small excess (5 mmol) is added immediately to the solution followed by 1-bromo-
3-chloropropane or 1,2-dibromoethane (5 mmol) 15 min later. The mixture is continually stirred
over night at ambient temperature.
After the removal of excess acetonitrile, the obtained residue was extracted with ether. The
solvent was removed and the residue was purified by column chromatography on silica gel 60.
A mixture of ethyl acetate/petroleum ether (2:8) was used as eluant. All the resulting products
(2a–2e) and (3a–3e) are reported in Table 1 and were identified on the basis of their spectroscopic
data.
For this reaction, we used 2 F per mole of arylacetonitrile. According to a formal study realized
within our research group, the best yield was obtained using 2–2.5 F per mole of substrate.[23]
As indicated in Scheme 2, the reduction of acetonitrile gave the corresponding EGB, which
attacked the arylacetonitrile to produce the appropriate anion. In the second step, arylacetonitrile
anion reacted with carbon disulfide to form a stabilized carbamodisulfide intermediate which is
probably stabilized by ion-pairing with the electrogenerated magnesium cations from the sacri-
ficial magnesium anode. Addition of 1.2- or 1.3-dihalogenated alkyl gave the corresponding five
or six rings heterocyclic compounds with good yields. We did not detect the presence of acyclic
intermediates resulting from a single attack of carbamodisulfide on the dihalogenated alkyl.
Obtained products have been identified according to their spectroscopic data (IR and 1H NMR
and 13C NMR) and elemental analysis.
3. Biological activity
3.1. Bacterial strains and growth conditions
Bacteria tested in this study were obtained from international culture collections ATCC and the
local culture collection of Pasteur Institute of Tunis. Test organisms included six Gram-negative
bacterial strains: Escherichia coli (ATCC 25922), Proteus mirabilis (ATCC 29906), Salmonella
typhimurium (ATCC 14028), Shigella flexneri (ATCC 29903), Enterobacter cloacae (ATCC
18147) and Pseudomonas aeruginosa (ATCC 27853); and three Gram-positive bacterial strains;
Staphylococcus aureus (ATCC 25923), Listeria monocytogenes (ATCC 19118) and Bacillus
cereus (ATCC 11778). All bacterial strains were cultivated in Luria Bertani (LB) Medium (Oxoid
Ltd, UK) at 37 °C except for Bacillus species, which were incubated at 30 °C. Working cultures
were prepared by inoculating a loopful of each test bacteria in 5 ml of LB Medium (Oxoid Ltd,
UK), and were incubated at 37 °C for 18 h.

Journal of Sulfur Chemistry 199
Table 1. Synthesized 2-(1,3-dithian-2-ylidene)-2-arylacetonitrile 2 and 2-(1,3-dithiolan-2-ylidene)-2-arylacetonitrile 3.
Entry
Starting arylacetonitrile
Electrophile
Product
Yielda (%)
N
S
S
1
N
A
69
2a
F
N
S
S
N
2
A
73
2b
F
N
S
S
N
3
A
77
H
3C
2c
O
N
S
S
N
N
4
A
75
H
3CO
2d
O
S
S
N
5
A
78
H
OC
e
2
3
(Continued)

200 K. Hamrouni et al.
Table 1. Continued
Entry
Starting arylacetonitrile
Electrophile
Product
Yielda (%)
N
S
S
6
N
B
67
3a
F
N
S
S
N
7
B
70
3b
F
N
S
S
N
8
B
75
H
3C
3c
O
N
S
S
N
N
9
B
80
H
3CO
3d
O
S
S
N
10
B
70
H
OC
3
3e
Notes: A, 1-bromo-3-chloropropane; B, 1,2-dibromoethane.
aThe yield was calculated in regard to the starting arylacetonitrile. Q = 2 Fmol−1
.

Journal of Sulfur Chemistry 201
H
r
A
-
2é
CN
r
A
+
3
-
N
A
H
-
NC C
H
C C
-
+
1 2 H
NC CH2
/
3
2
-
-
N
C
(EGB)
S
S
=
=
S C S
r
S
H
S
N
C
r
A
r
A
CN
S
CN
r
B
N
r
B
S
S
r
A
-
r
HB
r
B
H
S
H
S
-
r
r
A
S
S
r
A
CN
CN
CN
CN
Cl
S
N
r
A
H
S
H
S
r
B
Cl
-
H
Cl
r
O
A
S
S
r
A
Scheme 2. Proposed mechanism of the preparation of products (2 and 3) by EGB-promoted reaction.
3.2. In vitro antibacterial bioassay: agar well-diffusion method
The in vitro antibacterial activity of the synthesized compounds has been evaluated against var-
ious Gram-negative and Gram-positive bacteria by the agar well-diffusion method, as described
by Murthy et al.[25] Briefly, a suspension (0.1 mL of 106 CFU/mL) of each microorganism was
spread using a sterile cotton swab on the surface of solid LB media plates. Cylindrical plugs
were removed from the agar plates by a sterile cork borer (Pyrex, UK) to produce wells with
a diameter of approximately 6 mm. On the other hand, solutions of the test compounds were
prepared in ethanol and adjusted at a concentration of 20 mmol·L−1, and then a 50 µL of each
sample solution was added to the respective wells and allowed to diffuse at room temperature
for 2 h. Then, the plates were incubated for 18 h at 37 °C. Results were recorded by measuring
the diameter inhibitory zones in millimeter, including the well diameter. The diameters of the
zone of inhibition produced by the agent were compared with those produced by the commercial
control antibiotics, Streptomycin B (15 µg/mL).
3.3. Result and discussions
The results of the antibacterial activity of the newly synthesized heterocyclic compounds have
been presented in Table 2. It can be noted from these data that, in general, all the test compounds
possessed moderate-to-good antibacterial activity against Gram-positive and Gram-negative bac-
teria, except for L. monocytogenes where the size of their inhibition zones ranges from 8 to
15 mm. On the basis of the zone of inhibition against the test bacterium, compounds 2d, 2a
and 3e were found to be the most effective against E. coli (ATCC 25922), whereas compound
2b exhibited a high antibacterial activity against B. cereus (ATCC 11778) and P. mirabilis
(ATCC 29906). Compound 3b showed a moderate activity towards E. coli (ATCC 25922) and
E. cloacae (ATCC 18147). However, Compound 3d showed moderate activity against S. flexneri

202 K. Hamrouni et al.
Table 2. Antibacterial activity of selected compounds, using the agar well-diffusion method.
Agar well-diffusion method (DD)
Compounds
Antibiotic:
streptomycin
Strains
2d
2b
2a
3b
3d
3e
E. coli (ATCC 25922)
15
9
11
14
11
10
13
15
12
9
14
8
13
11
12
12
11
10
12
13
11
12
11
12
12
22
16
12
14
NT
15
23
15
S. aureus (ATCC 25923)
B. cereus (ATCC 11778)
P. aeruginosa (ATCC 27853)
E. cloacae (ATCC 18147)
P. mirabilis (ATCC 29906)
S. flexneri (ATCC 29903)
Inactive Inactive
Inactive
Inactive
Inactive Inactive Inactive Inactive
Inactive 12 13 10
11
13
Inactive
10
14
9
L. monocytogenes (ATCC 19118) Inactive Inactive Inactive Inactive Inactive Inactive
S. typhimurium (ATCC 14028)
9
8
8
9
8
8
Note: NT, not tested.
(ATCC 29903). Also, the results revealed that new compound 2a was weakly active against the
tested microorganisms compared to other test compounds.
On the other hand, our investigations presented in this study showed that the test 2-
(1,3-dithian-2-ylidene)-2-arylacetonitrile and 2-(1,3-dithiolan-2-ylidene)-2-arylacetonitrile com-
pounds express promising antibacterial properties in vitro comparable or even better than those
of the antibiotic streptomycin (positive control).
To the best of our knowledge, the mechanism of the antibacterial activity of the test compounds
has not been elucidated. In fact, it seems that the mechanism is not related to the synthesis of
the cell envelope, as Gram-positive and Gram-negative bacteria exhibit sensitivity. Thus, the
selectivity of the compounds was dependent on their molecular structure.[26]
From the structure–activity relationship viewpoint, we propose that the membrane disrupting
and antibacterial potential of the test synthesized compounds correlated with their chain lengths,
[27,28] an increase in the positive charge and hydrophobicity, which is apparently the more
important for membrane interaction.[29,30] In addition, these findings of our study indicated that
the test compounds have the potential to generate novel antibacterial proprieties by displaying
moderate to high affinities for most of the receptors.[31] This allows us to create a bank of
bioactive compounds for discovery and development of new, innovative therapeutic agents.[32]
4. Conclusion
The use of an EGB as a new electrochemical methodology that allows the preparation of
2-(1,3-dithian-2-ylidene)-2-arylacetonitrile (2) and 2-(1,3-dithiolan-2-ylidene)-2-arylacetonitrile
(3) from arylaceyonitrile, carbon disulfide and 1-bromo-3-chloropropane or 1,2-dibromoethane
in high yields, under mild conditions and avoiding the use of polluting or hazardous chemicals or
the addition of a base is reported. The mechanism of the reaction is investigated and the obtained
1
products have been identified according to their spectroscopic data (IR and H NMR and 13C
NMR) and elemental analysis.
Antibacterial activities of some of these compounds were tested for their antibiotic properties.
Some of the tested compounds showed an interesting antibiotic activity against bacteria E. coli,
S. aureus, B. cereus, P. aeruginosa, E. cloacae, P. mirabilis, S. flexneri, L. monocytogenes and
S. typhimurium.

Journal of Sulfur Chemistry 203
4.1. 2a-2-(1,3-dithian-2-ylidene)-2-phenylacetonitrile
1
Yield: 69%: IR (cm−1, CHCl3); ν: 2196 (CN); 1603 (C C). H NMR (300 MHz, CDCl3); δ:
2.10 (m, 2H, CH2); 2.83 (t, 2H, CH2); 3.01 (t, 2H, CH2); 7.20–7.40 (m, 5H, CHarom.). 13C
NMR (75.47 MHz, CDCl3); δ: 22.69; 29.28; 29.73; 106.12; 117.97; 128.48; 128.57; 128.89;
129.17; 129.32; 133.30; 158.29. Elemental analysis: %C = 61.06; %H = 4.92; %N = 5.95
(experimental). %C = 61.76; %H = 4.75; %N = 6.00 (calculated).
=
4.2. 2b-2-(1,3-dithian-2-ylidene)-2-(4-fluorophenyl)acetonitrile
1
Yield: 73%: IR (cm−1, CHCl3); ν: 2199 (CN); 1608 (C C). H NMR (300 MHz, CDCl3);
=
δ: 2.16 (m, 2H, CH2); 2.91 (t, 2H, CH2); 3.06 (t, 2H, CH2); 6.98–7.36 (m, 4H, CHarom.).
13C NMR (75.47 MHz, CDCl3); δ: 23.05; 29.24; 29.23; 106.19; 115.47; 115.78; 129.31;
129.36; 129.62; 129.73; 130.80; 130.91; 158.33. 19F NMR (282.37 MHz, CDCl3) δ: − 111.99
(s, 1F, CFarom.). Elemental analysis: %C = 58.95; %H = 4.86; %N = 5.33 (experimental).
%C = 57.34; %H = 4.01; %N = 5.57 (calculated).
4.3. 2c-2-(1,3-dithian-2-ylidene)-2-(p-tolyl)acetonitrile
1
Yield: 77%: IR (cm−1, CHCl3); ν: 2198 (CN); 1604 (C C). H NMR (300 MHz, CDCl3);
=
δ: 2.15 (m, 2H, CH2); 2.29 (s, 3H, CH3); 2.89 (t, 2H, CH2); 3.05 (t, 2H, CH2); 7.11–
7.26 (m, 4H, CHarom.). 13C NMR (75.47 MHz, CDCl3); δ: 21.32; 23.23; 29.21; 29.70;
106.69; 117.90; 127.81; 128.76; 129.21; 129.78; 130.45; 138.55; 156.80. Elemental analysis:
%C = 62.13; %H = 5.44; %N = 5.98 (experimental). %C = 63.12; %H = 5.30; %N = 5.66
(calculated).
4.4. 2d-2-(1,3-dithian-2-ylidene)-2-(4-methoxyphenyl)acetonitrile
1
Yield: 75%: IR (cm−1, CHCl3); ν: 2196 (CN); 1603 (C C). H NMR (300 MHz, CDCl3);
=
δ: 2.22 (m, 2H, CH2); 2.98 (t, 2H, CH2); 3.12 (t, 2H, CH2); 3.83 (s, 3H, CH3); 6.91–
7.38 (m, 4H, CHarom.). 13C NMR (75.47 MHz, CDCl3); δ: 23.15; 29.21; 29.24; 55.36;
106.32; 113.92; 117.99; 125.70; 128.53; 128.89; 130.25; 155.99; 159.54. Elemental analysis:
%C = 60.14; %H = 6.08; %N = 5.33 (experimental). %C = 59.28; %H = 4.98; %N = 5.32
(calculated).
4.5. 2e-2-(1,3-dithian-2-ylidene)-2-(2-methoxyphenyl)acetonitrile
1
Yield: 78%: IR (cm−1, CHCl3); ν: 2217 (CN); 1601 (C C). H NMR (300 MHz, CDCl3); δ:
=
2.11 (m, 2H, CH2); 2.81 (t, 2H, CH2); 3.02 (t, 2H, CH2); 3.78 (s, 3H, CH3); 6.84–7.27 (m, 4H,
CHarom.). 13C NMR (75.47 MHz, CDCl3); δ: 21.98; 27.93; 28.01; 54.63; 101.72; 110.40 116.32;
119.36; 120.84; 129.59; 130.16; 155.87; 157.61. Elemental analysis: %C = 59.92; %H = 6.11;
%N = 5.17 (experimental). %C = 59.28; %H = 4.98; %N = 5.32 (calculated).
4.6. 3a-2-(1,3-dithiolan-2-ylidene)-2-phenylacetonitrile
1
Yield: 67%: IR (cm−1, CHCl3); ν: 2199 (CN); 1602 (C C). H NMR (300 MHz, CDCl3); δ:
=
3.42 (s, 4H, 2 CH2 cyclic); 7.15–7.30 (m, 5H, CHarom.). 13C NMR (75.47 M Hz, CDCl3); δ:

204 K. Hamrouni et al.
38.03; 40.28; 97.85; 118.97; 127.49; 128.06; 128.78; 129.51; 134.81; 162.72; 167.55. Elemen-
tal analysis: %C = 59.15; %H = 4.07; %N = 6.67 (experimental). %C = 60.24; %H = 4.14;
%N = 6.39 (calculated).
4.7. 3b-2-(1,3-dithiolan-2-ylidene)-2-(4-fluorophenyl)acetonitrile
1
Yield: 70%: IR (cm−1, CHCl3); ν: 2200 (CN); 1603 (C C). H NMR (300 MHz, CDCl3);
=
δ: 3.51 (s, 4H, 2 CH2 cyclic); 7.00–7.41 (m, 4H, CHarom.). 13C NMR (75.47 M Hz,
CDCl3); δ: 38.08; 40.13; 96.99; 115.61; 115.90; 127.49; 129.46; 129.57; 129.84; 160.40;
162.47. 19F NMR (282.37 MHz, CDCl3); δ: −112.51(s, 1F, CFarom). Elemental analysis:
%C = 58.66; %H = 3.35; %N = 6.10 (experimental). %C = 55.67; %H = 3.40; %N = 5.90
(calculated).
4.8. 3c-2-(1,3-dithiolan-2-ylidene)-2-(p-tolyl)acetonitrile
1
Yield: 75%: IR (cm−1, CHCl3); ν: 2120 (CN); 1600 (C C). H NMR (300 MHz, CDCl3); δ:
=
2.26 (s, 3H, CH3); 3.45 (s, 4H, 2 CH2 cyclic); 7.09–7.33 (m, 4H, CHarom.). 13C NMR (75.47 M
Hz, CDCl3); δ: 21.26; 37.93; 40.12; 98.06; 118.92; 127.39; 127.39; 129.39; 129.39; 132.02;
138.04; 161.34. Elemental analysis: %C = 58.93; %H = 5.02; %N = 6.40 (experimental).
%C = 61.76; %H = 4.75; %N = 6.00 (calculated).
4.9. 3d-2-(1,3-dithiolan-2-ylidene)-2-(4-methoxyphenyl)acetonitrile
1
Yield: 80%: IR (cm−1, CHCl3); ν: 2206 (CN); 1603 (C C). H NMR (300 MHz, CDCl3); δ:
=
3.47 (s, 4H, 2 CH2 cyclic); 3.73 (s, 3H, CH3); 6.78–7.37 (m, 4H, CHarom.). 13C NMR (75.47 M
Hz, CDCl3); δ: 37.99; 40.00; 55.39; 97.76; 114.07; 114.96; 118.97; 127.36; 128.93; 129.06;
159.18; 160.44. Elemental analysis: %C = 56.20; %H = 5.07; %N = 5.80 (experimental).
%C = 57.80; %H = 4.45; %N = 5.62 (calculated).
4.10. 3e-2-(1,3-dithiolan-2-ylidene)-2-(2-methoxyphenyl)acetonitrile
1
Yield: 70%: IR (cm−1, CHCl3); ν: 2200 (CN); 1601 (C C). H NMR (300 MHz, CDCl3); δ:
=
3.30 (t, 2H, CH2); 3.40(t, 2H, CH2); 3.70 (s, 3H, CH3); 6.80–7.30 (m, 4H, CHarom.). 13C
NMR (75.47 M Hz, CDCl3); δ: 38.76; 39.53; 55.69; 94.18; 111.43; 118.42; 120.62; 123.72;
130.39; 130.53; 156.50; 164.36. Elemental analysis: %C = 56.18; %H = 4.62; %N = 6.02
(experimental). %C = 57.80; %H = 4.45; %N = 5.62 (calculated).
Acknowledgements
The authors gratefully acknowledge the Tunisian “Ministère de l’Enseignement Supérieur, de la Recherche et la
Technologie” for Financial support (Lab CH-02).
Disclosure statement
No potential conflict of interest was reported by the authors.
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