Synthesis of novel 1,2,3-thiadizoles and 1,2,3-selenadiazoles as new antimicrobial agents

Article abstract of DOI:10.1080/10426507.2019.1576676

A series of novel 1,2,3-thiadiazoles and 1,2,3-selenadiazoles having a long alkyl chain were synthesized by reacting semicarbazones with SOCl₂ and SeO₂, respectively. The structures of the target compounds 5–12 were confirmed by spec

Full text of DOI:10.1080/10426507.2019.1576676

Phosphorus, Sulfur, and Silicon and the Related Elements
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Synthesis of novel 1,2,3-thiadizoles and 1,2,3-
selenadiazoles as new antimicrobial agents
Hatice Başpınar Küçük, Zeynep Banu Salt, Emel Mataracı Kara, Aysema Sayık
Mehan & Ayşe Sergüzel Yusufoğlu
To cite this article: Hatice Başpınar Küçük, Zeynep Banu Salt, Emel Mataracı Kara, Aysema
Sayık Mehan & Ayşe Sergüzel Yusufoğlu (2019): Synthesis of novel 1,2,3-thiadizoles and 1,2,3-
selenadiazoles as new antimicrobial agents, Phosphorus, Sulfur, and Silicon and the Related
Elements, DOI: 10.1080/10426507.2019.1576676
To link to this article: https://doi.org/10.1080/10426507.2019.1576676
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2019.1576676
Synthesis of novel 1,2,3-thiadizoles and 1,2,3-selenadiazoles as new
antimicrobial agents
a
, Zeynep Banu Salta, Emel Mataracı Karab, Aysema Sayık Mehana, and
€ €
Hatice Bas¸pınar Kuc¸uk
a
€
ꢀ
Ays¸e Serguzel Yusufoglu
b
aDepartment of Chemistry, Organic Chemistry Division, Faculty of Engineering, Istanbul University-Cerrahpasa, Istanbul, Turkey; Department
of Pharmaceutical Microbiology Faculty of Pharmacy, Istanbul University, Istanbul, Turkey
ABSTRACT
ARTICLE HISTORY
Received 26 September 2018
Accepted 28 January 2019
A series of novel 1,2,3-thiadiazoles and 1,2,3-selenadiazoles having a long alkyl chain were synthe-
sized by reacting semicarbazones with SOCl2 and SeO21, respectively. The structures of the target
compounds 5–12 were confirmed by spectroscopy (IR, H NMR, 13C NMR, and MS) and elemental
analysis. Their antibacterial and antifungal activities were evaluated against six bacteria
(Pseudomonas aeruginosa, Escherichia coli, Klebsiella pneumoniae, Proteus mirabilis, Enterococcus fae-
calis, Staphylococcus epidermidis, Staphylococcus aureus) and three fungi (Candida albicans, Candida
parapsilosis, Candida tropicalis). The results of bioassays indicated that the compounds 5-Dodecyl-
4-(4-methoxy-phenyl)-[1-3]selenadiazole (7), 4-Methyl-5-tetradecyl-[1-3]selenadiazole (8) and 5-
Dodecyl-4-(4-methoxy-phenyl)-[1-3]thiadiazole (11) displayed moderate antibacterial activity
against S. Epidermidis. On the other hand, according to antifungal screening results, compounds 5-
Dodecyl-4-phenyl-[1-3]selenadiazole (5), 4-p-Tolyl-5-undecyl-[1-3]selenadiazole (6), and 5-Dodecyl-
4-(4-methoxy-phenyl)-[1-3]selenadiazole (7) exhibited significant antifungal activities studied
yeast strains.
KEYWORDS
1,2,3-Thiadiazole; 1,2,3-
selenadiazole; antibacterial
activity; antifungal activity
GRAPHICAL ABSTRACT
Introduction
Considering the above mentioned studies, in the present
work, we have synthesized substituted new 1,2,3-thiadiazole
and 1,2,3-selenadiazole compounds (Scheme 1). The synthe-
sized compounds were subjected to antibacterial and antifun-
gal activity testing, and the obtained results were evaluated.
According to the literature data, 1,2,3-thiadiazoles and
1,2,3-selenadiazoles have been prepared using aromatic, ali-
phatic and cyclic ketones with short alkyl chain
lengths.[10,11] However, these products with long alkyl chain
lengths are missing in the literature. Motivated by the afore-
mentioned findings, we have designed and synthesized new
1,2,3-thiadiazole and 1,2,3-selenadiazoles using aryl, mono-
substituted aryl, and aliphatic ketones with long alkyl chains.
Synthetic methods for the preparation of organosulfur and
organoselenium compounds annelated their importance for
medicinal[1] and synthetic chemistry.[2,3] 1,2,3-Thiadiazoles
and 1,2,3-selenadiazoles are well-known compounds, and
researchers are interested in the synthesis of their intermedi-
ates.[4–11] Many substituted 1,2,3-thia- and 1,2,3-selenadia-
zole derivatives were synthesized and most of them have
shown important antibacterial and antifungal activities.[12–16]
When the 1,2,3-thiadiazole group is added to a known bio-
logically active compound, the activity of the molecule
changes and in some cases, the biological activity
increases.[17,18]
€ €
CONTACT Hatice Bas¸pınar Kuc¸uk
baspinar@istanbul.edu.tr
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
Supplemental data for this article can be accessed on the publisher’s website.
ß 2019 Taylor & Francis Group, LLC

€ €
H. BAS¸PINAR KUC¸UK ET AL.
2
Se
R
N
N
n
SeO2/AcOH
60-70 °C
1,2,3-Selenadiazoles
R
n
-C6H5
12
11
12
14
5
6
7
8
O
NNHCONH2
n
4-CH3 C6H4
4-OCH3 C6H4
-CH3
NH2NHCONH2
R
R
n
C2H5OH / Reflux
R
R
n
n
-C6H5
-C6H5
S
N
N
12
SOCl2/CH2Cl2
0 °C - 10 °C
1
2
3
4
12
11
12
14
1a
n
4-CH3 C6H4
4-OCH3 C6H4
-CH3
4-CH3 C6H4
4-OCH3 C6H4
-CH3
11
12
14
2a
3a
4a
R
1,2,3-Thiadiazoles
R
n
-C6H5
4-CH3 C6H4
12
9
11
12
14
10
11
12
4-OCH3 C6H4
-CH3
Scheme 1. Synthesis of 1,2,3-thiadiazoles and 1,2,3-selenadiazoles.
We then investigated biological properties of these new exhibited a triplet signal for the methylene protons (belong-
compounds. Thus, we have examined the effect of the long
alkyl chain added to 1,2,3-thiadiazole and 1,2,3-selenadiazole
rings on their biological activities.
ing to the C6) being adjacent to 1,2,3-thiadiazole or 1,2,3-
selenadiazole rings around at 2.79–3.08 ppm. In the 1H
NMR spectra, the methylene protons (belonging to the C7)
showed a pentet signal at 1.52–1.55 ppm due to their pos-
ition adjacent to two methylene groups (C6 and C8). The
13C NMR spectra showed characteristic resonances for 1,2,3-
thiadiazole and 1,2,3-selenadiazole rings. The typical 13C
NMR shifts for C4 being adjacent to N were observed
around d 156–163 ppm. Also C5 (adjacent to Se or S)
showed a signal about d 151–160 ppm. Aromatic carbons
for the compounds 5,6,7,9,10, and 11 were observed at d
128-131 ppm. In 13C NMR spectra, peaks due to aliphatic
carbons were recorded between 12 ppm and 37 ppm. Mass
spectra (EI) of 1,2,3- selenadizole compounds showed a
molecular ion peak ([M–N2–Se]þ) in line with their molecu-
lar formula. 1,2,3-Thiadizole compounds gave a molecular
ion peak ([M–N2]þ). Mass spectra (EI) and mass fragmenta-
tions of the products 6 and 10 were given as examples in
supplemental materials. Also, the elemental analyses of the
compounds was in agreement with the proposed structures
of the compounds.
Results and discussion
Chemistry
The synthetic route to the target compounds 5–12 are
depicted in Scheme 1. Ketones with aryl, monosubstituted
aryl, and long alkyl chains 1–4 were synthesized and charac-
terized in our previous works.[19–22] Ketones were converted
into their semicarbazones by reacting 1–4 with semicarba-
zide hydrochloride.[23] The physical properties of semicarba-
zones 1a–4a are given in Table S1 (Supplementary
materials). On treatment with SeO2/AcOH (Lalezari
Method)[24,25] the semicarbazones gave the corresponding 1,
2,3-selenadiazoles 5–8. On the other hand, when the semi-
carbazones were subjected to the Hurd-Mori reaction
process[26] with excess thionylchloride at ꢀ10 C for 3 h, 1,
ꢁ
2,3-thiadiazoles 9–12 were obtained in a one pot reaction
(Scheme 1).
All reactions were monitored by TLC (petroleum ether:
ethyl acetate: acetic acid, 2:0.6:0.1). The synthesized com-
pounds were purified by column chromatography and char-
Antimicrobial activity
1
acterized by FTIR, H NMR, 13C NMR, elemental analyses
In vitro antibacterial activities of compounds against
Pseudomonas aeruginosa ATCC 27853, Escherichia coli
ATCC 25922, Klebsiella pneumoniae ATCC 4352, Proteus
mirabilis ATCC 14153, Enterococcus faecalis ATCC 29212,
Staphylococcus epidermidis ATCC 12228, Staphylococcus aur-
eus ATCC 29213, and antifungal activities against Candida
albicans ATCC 10231, Candida parapsilosis ATCC 22019,
Candida tropicalis ATCC 750 were investigated. Minimum
inhibitory concentrations (MICs) of compounds were deter-
mined by microbroth dilution technique as described by the
Clinical and Laboratory Standards Institute[27,28] Serial two
fold dilutions ranging from 5000 to 1.22 mg/L were pre-
and mass spectrometry. The detailed spectral description of
compounds 5–12 are given below. The FTIR spectra of the
products 5-12 exhibited bands between 1463–1468 cmꢀ1
,
indicating the presence of N = N. The 1259-1282 cmꢀ1 was
assigned to be C–N stretching absorption bands. The
absorption bands observed in the region of 801–889 cmꢀ1
1
were assigned to C–S for 9–12. H NMR spectra of the syn-
thesized compounds showed some characteristic peaks. All
protons due to aromatic groups were found to be in their
expected region. Aromatic protons in the spectra of the
compounds 5,6,7,9,10, and 11 were observed at 7.25–7.78
ppm. The 1H NMR spectra of the compounds 5–12 pared in Mueller-Hinton broth (MHB) for bacteria and

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
RPMI-1640 medium for yeast. Each well was inoculated
with 50 lL of a 4–6 h broth culture that gave a final con-
centration of 5 ꢂ 105 cfu/mL for bacteria and 5 ꢂ 103 cfu/
mL for yeast in the test tray. The trays were covered and
placed in plastic bags to prevent evaporation. The trays con-
taining MHB were incubated at 35 ꢁC for 18–20 h, those
ꢁ
containing RPMI-1640 medium at 35 C for 46–50 h. The
MIC was defined as the lowest concentration of compound
producing complete inhibition of visible growth. Amikacin
and fluconazole were used as reference antibiotics for bac-
teria and yeast, respectively. The MIC values of the amikacin
and fluconazole were within the accuracy range in CLSI
throughout the study.[29] The MIC values of the compounds
are given in Table 1.
All the compounds were investigated for their in vitro
antibacterial activities against three Gram-positive
(Staphylococcus aureus ATCC 29213, Staphylococcus epider-
midis ATCC 12228, Enterococcus faecalis ATCC 29212) and
four Gram-negative bacteria (Pseudomonas aeruginosa
ATCC 27853, Escherichia coli ATCC 25922, Klebsiella pneu-
moniae ATCC 4352, Proteus mirabilis ATCC 14153). The
antifungal activities were also tested against three yeasts,
namely Candida albicans ATCC 10231, Candida parapsilosis
ATCC 22019, Candida tropicalis ATCC 750. All the bio-
logical results of the tested compounds are given in Table 1.
As seen in Table 1, all the studied compounds, have no anti-
microbial activity against four Gram negative bacteria (E.
coli, K. Pneumoniae, P. Mirabilis, and E. faecalis). However,
in our study it is shown that compound 11 has a weak
activity against P. aeruginosa (MIC = 625 mg/L). The pre-
sent study showed that compounds 7, 8 and 11 showed
moderate antibacterial activity against S. epidermidis (MIC =
156.2 mg/L). Moreover, compounds 5, 6 and 7 exhibited
significant antifungal activity against studied yeast strains.
However, compounds 9 and 12 were not shown to have any
antimicrobial activity against the studied microorganisms.
Experimental
Materials and physical measurements
All reagents were obtained from commercial suppliers unless
otherwise stated. Organic solvents were routinely dried and/
or distilled prior to use and stored over molecular sieves
under argon. Solvents for chromatography were of technical
grade and distilled prior to use. Thin layer chromatography
(TLC) was carried out on Merck aluminum support plates
Silica gel 60 F254. Visualization was achieved under a UV
mineral light. Column chromatography was performed using
silica gel Merck 60 (particle size 0.2–0.063 mm). NMR spec-
1
tra were recorded at 500 MHz for H and at 125 MHz for
13C using Me4Si as the internal standard in CDCl3 with a
Varian UNITY INOVA 500 MHz NMR spectrometer. GC-
MS were recorded on Shimadzu/QP2010 Plus. IR spectra
were recorded on a Mattson 1000 FT-IR spectrometer.
Melting points were determined with Bu€chi melting point
B-540. Chemical yields refer to pure isolated substances. The
1
Supplementary materials contains sample H and 13C NMR
spectra for the products 5–12 (Figures S1–S18).

€ €
H. BAS¸PINAR KUC¸UK ET AL.
4
General procedure for the synthesis of
5 -Dodecyl-4-(4-methoxy-phenyl)-[1–3]selenadiazole (7)
Yield, 69%, yellow slurry, m.p., 45-46 ꢁC; FTIR (neat; t,
cmꢀ1): 3031 (aromatic CH), 2915 (aliphatic CH), 2850, 1468
[23]
semicarbazones
1a–4a
Semicarbazide hydrochloride (67 g, 0.6 mol), along with
sodium acetate (67 g, 0.8 mol) in ethanol (500 mL) were
heated at reflux. The precipated sodium chloride was filtered
from the hot solution, and the ketone (0.5 mol) was added.
The mixture was heated at reflux for a further 2 h. Then
water was added to the hot solution until precipitation
started. After cooling, the crystals of the semicarbazone were
collected, washed with water and air-dried. The product is
sufficiently pure for further reactions.
1
(N = N), 1371, 1278 (C–N), 1181, 968, 806, 718. H NMR
(CDCl3; d, ppm): 7.78(d, J = 10.0 Hz, 2H); 7.17(d, J = 10.0
Hz, 2H); 2.85(t, J = 7.5 Hz, 2H); 2.33(s, 3H); 1.68–1.62
(multiplet, 2H); 1.29–1.18 (m, 18H); 0.81(t, J = 7.5 Hz, 3H).
13C NMR (CDCl3; d, ppm): 161.3 (C4), 158.3 (C5), 142.5,
133.7, 128.4, 128.2, 127.2, 127.1, 37.6, 28.7, 28.5, 28.4, 28.3,
28.2, 23.6, 21.7, 13.1. Anal. Calcd. for C21H32N2OSe (M =
407.45), %: C, 61.90; H, 7.92; N, 6.88; Found, %: C, 62.01;
H, 7.89; N, 6.93. MS (m/z) = 239, 253, 270, 281,
299 ([M–N2–Se]þ).
General procedure for the synthesis of
[30]
4 -Methyl-5-tetradecyl-[1–3]selenadiazole (8)
compounds
5–8
Yield, 81%, yellow oil; FTIR (neat; t, cmꢀ1): 2915 (aliphatic
The semicarbazone (0.05 mol) wasꢁdissolved in glacial acetic
acid (15 mL) and warmed to 60 C with stirring. To this,
selenium dioxide (0.55 g, 0.05 mol) was added portionwise
over a period of 30 min and the stirring was continued at
60 ꢁC for 2–3 h until the evolution of gas ceased. After
completion of the reaction, it was filtered to remove the
deposited elemental selenium. The filtrate was poured over
crushed ice and the solid obtained was filtered, and washed
thoroughly with cold water and sodium carbonate and again
with water. The crude product was purified by column chro-
matography (petroleum ether: ethyl acetate: acetic acid,
2:0.6:0.1) to yield substituted 1,2,3-selenadiazoles 5-8.
1
CH), 2850, 1465 (N = N), 1266 (C–N), 1167, 718. H NMR
(CDCl3; d, ppm): 2.33(t, J = 7.5 Hz, 2H); 2.05(s, 3H);
1.52–1.45(m, 2H); 1.24–1.19(m, 22H); 0.81(t, J = 5.0 Hz,
3H). 13C NMR (CDCl3; d, ppm): 160.9 (C4), 155.3 (C5),
33.6, 32.1, 30.0, 29.9, 29.8, 29.7, 29.6, 29.4, 22.9, 14.3, 13.2.
Anal. Calcd. for C17H32N2Se (M = 343.41), %: C, 59.46; H,
9.39; N, 8.16; Found, %: C, 59.37; H, 9.47; N, 8.11. MS (m/
z)= 152, 180, 194, 211, 236 ([M–N2–Se]þ).
General procedure for the synthesis of
[30]
compounds
9–12
The dried semicarbazone (10 mmol) was added portionwise
to an excess of freshly distilled thionyl chloride (3 mL) at 0
ꢁC with an ice/salt bath. The reaction mixture was allowed
to stand at room temperature until the disappearance of
semicarbazone (monitored by TLC). At the end of the reac-
tion, methylene chloride (15 mL) was added and the result-
ing mixture was decomposed with saturated sodium
carbonate. The organic layer was washed with water and
dried on sodium sulfate. Products 9–12 were purified by col-
umn chromatography (petroleum ether: ethyl acetate: acetic
acid, 2:0.6:0.1).
5-Dodecyl-4-phenyl-[1–3]selenadiazole (5)
Yield, 79%, orange slurry, m.p., 33–34 ꢁC; IR (neat; t,
cmꢀ1): 3082 (aromatic CH), 2915 (aliphatic CH), 2846, 1468
1
(N = N), 1282 (C–N), 889, 769, 686. H NMR (CDCl3; d,
ppm): 7.61–7,58(m, 2H); 7.45-7.42(m, 2H); 7.38–7.36(m,
1H); 3.00(t, J = 7.5 Hz, 2H); 1.69–1.63(pentet, J = 5.0 Hz,
2H); 1.18–1.17(m, 18H); 0.80(t, J = 7.5 Hz, 3H). 13C NMR
(CDCl3; d, ppm): 163.9 (C4), 160.4 (C5); 133.3, 130.5, 129.6,
128.9, 35.2, 32.3, 30.0, 29.9, 29.8, 29.7, 29.6, 29.5, 23.0, 14.4.
Anal. Calcd. for C20H30N2Se (M = 377.43), %: C, 63.65; H,
8.01; N, 7.42; Found, %: C, 63.78; H, 8.11; N, 7.36. MS (m/
z)= 213, 227, 241, 255, 270 ([M–N2–Se]þ).
5 -Dodecyl-4-phenyl-[1–3]thiadiazole (9)
Yield, 75%, brown oil; FTIR (neat; t, cmꢀ1): 3073 (aromatic
CH), 2920 (aliphatic CH), 2850, 1463 (N = N), 1259 (C–N),
820 (C-S), 723, 686. 1H NMR (CDCl3; d, ppm):
7.73–7.71(m, 2H); 7.55–7.46(m, 3H); 3.08(t, J = 7.5 Hz, 2H);
1.75(pentet, J = 7.5 Hz, 2H); 1.42–1.36(m, 2H); 1.31–1.26(m,
16H); 0.90(t, J = 7.5 Hz, 3H). 13C NMR (CDCl3; d, ppm):
159.1 (C4), 153.3 (C5), 131.5, 128.9, 128.8, 128.7, 32.1, 31.9,
29.6, 29.5, 29.4, 29.3, 29.1, 25.9, 22.7, 14.1. Anal. Calcd. for
C20H30N2S (M = 330.53), %: C, 72.68; H, 9.15; N, 8.48;
Found, %: C, 72.80; H, 9.01; N, 8.67. MS (m/z)= 203, 217,
270, 287, 302 ([M-N2]þ).
4 -p-Tolyl-5-undecyl-[1–3]selenadiazole (6)
Yield, 75%, dark orange oil; FTIR (neat; t, cmꢀ1): 3073 (aro-
matic CH), 2920 (aliphatic CH), 2850, 1463 (N = N), 1259
1
(C–N), 820, 723, 686. H NMR (CDCl3; d, ppm): 7.50(d, J =
10.0 Hz, 2H); 7.25(d, J = 10.0 Hz, 2H); 3.00(t, J = 7.5 Hz,
2H); 2.37(s, 3H); 1.69–1.62(pentet, J = 6.0 Hz, 2H);
1.31–1.27(m, 2H); 1.21–1.17(m, 14H); 0.81(t, J = 7.5 Hz,
3H). 13C NMR (CDCl3; d, ppm): 161.3 (C4), 158.3 (C5),
137.3, 128.4, 128.3, 127.2, 33.7, 30.9, 28.6, 28.5, 28.4, 28.3,
28.2, 28.1, 21.7, 20.3, 13.1. Anal. Calcd. for C20H30N2Se (M
= 377.43), %: C, 63.65; H, 8.01; N, 7.42; Found, %: C, 63.71; 4 -p-Tolyl-5-undecyl-[1–3]thiadiazole (10)
H, 8.06; N, 7.39. MS (m/z)= 213, 227, 241, 255,
Yield, 84%, brown oil; FTIR (neat; t, cmꢀ1): 3077 (aromatic
CH), 2915 (aliphatic CH), 2850, 1463 (N = N), 1268 (C–N),
270 ([M–N2–Se]þ).

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
1
968, 801 (C–S), 723. H NMR (CDCl3; d, ppm): 7.53(d, J =
ORCID
10.0 Hz, 2H); 7.25(d, J = 10.0 Hz, 2H); 2.97(t, J = 7.5 Hz,
2H); 2.36(s, 3H); 1.68–1.62(pentet, J = 6.0 Hz, 2H);
1.32–1.27(m, 2H); 1.22–1.17(m, 14H); 0.80(t, J = 7.5 Hz,
3H). 13C NMR (CDCl3; d, ppm): 159.0 (C4), 152.6 (C5),
138.4, 129.1, 128.4, 128.3, 31.2, 31.0, 28.7, 28.6, 28.5, 28.4,
28.2, 25.0, 21.8, 13.1. Anal. Calcd. for C20H30N2S (M =
330.53), %: C, 72.68; H, 9.15; N, 8.48; Found, %: C, 72.82;
H, 9.03; N, 8.65. MS (m/z)= 203, 217, 270, 287,
302 ([M–N2]þ).
Hatice Ba¸spınar Ku€c¸u€k
http://orcid.org/0000-0002-1735-6260
References
[1] Morzherin, Y. Y.; Glukhareva, T. V.; Bakulev, V. A.
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[6] Krantz, V.; Laureni, J. Matrix Photolysis of 1,2,3-thiadiazole.
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5 -Dodecyl-4-(4-methoxy-phenyl)-[1–3]thiadiazole (11)
Yield, 72%, dark brown oil; FTIR (neat; t, cmꢀ1): 3031 (aro-
matic CH), 2915 (aliphatic CH), 2850, 1468 (N = N), 1371,
1
1278 (C–N), 1181, 968, 868 (C–S), 714. H NMR (CDCl3; d,
ppm): 7.78 (d, J = 5.0 Hz, 2H); 7.16(d, J = 10.0 Hz, 2H);
2.84(t, J = 7.5 Hz, 2H); 2.32(s, 3H); 1.67–1.61 (pentet, J =
5.0 Hz, 2H); 1.31–1.26(m, 2H); 1.22–1.18 (m, 16H); 0.80 (t,
J = 7.5 Hz, 3H). 13C NMR (CDCl3; d, ppm): 158.1 (C4),
151.7 (C5), 142.5, 137.7, 133.7, 127.2, 37.5, 30.9, 28.6, 28.5,
28.4, 28.3, 28.2, 24.9, 21.7, 13.1. Anal. Calcd. for
C21H32N2OS (M = 360.56), %: C, 69.95; H, 8.95; N, 7.77;
Found, %: C, 69.99; H, 9.07; N, 7.61. MS (m/z)= 259, 273,
287, 302, 331 ([M-N2]þ).
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4 -Methyl-5-tetradecyl-[1–3]thiadiazole (12)
Yield, 83%, orange oil; FTIR (neat; t, cm1): 2915 (aliphatic
CH), 2846, 1465 (N = N), 1265 (C–N), 992, 855 (C–S), 723.
1H NMR (CDCl3; d, ppm): 2.79(t, J = 7.5 Hz, 2H); 2.55(s,
3H); 1.63–1.57(m, 2H); 1.22–1.18(m, 22H); 0.80(t, J = 7.5
Hz, 3H). 13C NMR (CDCl3; d, ppm): 156.1 (C4), 152.1 (C5);
32.1, 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 25.3, 22.9, 14.3, 12.5.
Anal. Calcd. for C17H32N2S (M = 296.51), %: C, 68.86; H,
10.88; N, 9.45; Found, %: C, 69.04; H, 11.09; N, 9.51. MS
(m/z)= 183, 207, 235, 253,268 ([M–N2]þ).
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Funding
This work was supported by Scientific Research Projects Coordination [16] Xu, Y. F.; Zhao, Z. J.; Qian, X. H.; Qian, Z. G.; Tian, W. H.;
Unit of Istanbul University, Grant/Award Number: BYP-2018-30546. Zhong, J. J. Novel, unnatural Benzo-1,2,3-thiadiazole-7-

€
€
6
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