Synthesis of Novel N,N′,N″-Tris[aryl(hetaryl)-methylideneamino]guanidine Derivatives as Efficient and Selective Colorimetric Sensors for Fluoride Ion

Article abstract of DOI:10.1134/S1070428019090215

A series of N,N′,N″-tris[aryl(hetaryl)methylideneamino]guanidines have been synthesized in good yields by condensation of N,N′,N″-triaminoguanidine hydrochloride with aromatic and heteroaromatic aldehydes. All compounds have been characterized by ¹H and ¹³C NMR and FT-IR spectra, and the molecular structure of one compound has been determined by single crystal X-ray diffraction. Study of the optical properties of the title compounds in the presence of fluoride ions has shown selective color change from colorless to yellow and purple due to red shift in their UV-Vis absorption spectra.

Full text of DOI:10.1134/S1070428019090215

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 9, pp. 1399–1406. © Pleiades Publishing, Ltd., 2019.
Synthesis of Novel N,N′,N′′-Tris[aryl(hetaryl)-
methylideneamino]guanidine Derivatives as Efficient
and Selective Colorimetric Sensors for Fluoride Ion
J. Jia, X. Chena, P.-Z. Zhanga,* A.-Q. Jiaa, and Q.-F. Zhanga**
a Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma’anshan, Anhui, China
e-mail:*pzzhang@ahut.edu.cn; **zhangqf@ahut.edu.cn
Received February 23, 2019; revised March 16, 2019; accepted July 2, 2019
Abstract—A series of N,N′,N′′-tris[aryl(hetaryl)methylideneamino]guanidines have been synthesized in good
yields by condensation of N,N′,N′′-triaminoguanidine hydrochloride with aromatic and heteroaromatic
aldehydes. All compounds have been characterized by 1H and 13C NMR and FT-IR spectra, and the molecular
structure of one compound has been determined by single crystal X-ray diffraction. Study of the optical
properties of the title compounds in the presence of fluoride ions has shown selective color change from
colorless to yellow and purple due to red shift in their UV-Vis absorption spectra.
Keywords: N,N′,N′′-Triaminoguanidinium chloride, Schiff bases, selective chemosensor, X-ray analysis.
DOI: 10.1134/S1070428019090215
Being nitrogen-rich compounds, N,N′,N′′-tri-
aminoguanidine derivatives have broad ranges of
physical, chemical, and biological properties and found
wide applications in fuels, enzyme inhibitors, medi-
cines, and chemical engineering fields [1, 2]. In partic-
ular, Schiff bases derived from triaminoguanidine are
widely used as multidentate organic ligands to prepare
various polynuclear transition metal complexes [3–9].
In most studies reported so far, triaminoguanidine
easily reacted with typical carbonyl compounds; for
example, reactions of triaminoguanidinium salts with
aldehydes, ketones, 1,3-diketones, acyl chlorides, car-
boxylic acids, sodium nitrite, and cyanogen bromide
have been described [10–18]. Among products of these
reactions, N,N′,N′′-tris(arylmethylideneamino)- and
N,N′,N′′-tris(alkylideneamino)guanidinium salts
possess an attractive C3-symmetrical molecular plat-
form, which could act as triangular ligand to form
transition metal complexes with novel architectures
[3–9]. It is well known that guanidinium moieties are
widely used as anion binding sites in colorimetric
molecular probes selective for fluoride ion [19–22].
We previously reported a series of diaminoguanidi-
nium chloride derivatives as efficient and selective
colorimetric sensors for fluoride ion [23]. Herein, we
describe the synthesis of a series of new tris[aryl-
(hetaryl)methylideneamino]guanidinium chlorides as
efficient and selective colorimetric sensors for fluoride
ion via naked eye detection. In addition, their ultra-
violet spectra in the presence of fluoride ions are also
reported.
The desired N,N′,N′′-tris[aryl(hetaryl)methyli-
deneamino]guanidinium chlorides 3a–3u were easily
prepared in moderate to good yields by condensation
of N,N′,N′′-triaminoguanidine hydrochloride (1) with
the corresponding aromatic and heteroaromatic alde-
hydes 2a–2u (Scheme 1). The 1H NMR spectra of 3a–
3u showed a broadened singlet in the region δ 11.13–
12.54 ppm due to the NH proton, and the signal at
δ 8.31–9.22 ppm was assigned to the azomethine
proton (CH=N). In the 13C NMR spectra of 3a–3u, the
signal around δC 160 ppm was attributed to the CH=N
carbon, which agreed well with the data for tris(pro-
pan-2-ylideneamino)guanidine [12]. The IR spectra of
3a–3u contained a broadened absorption band in the
region 3400–3200 cm–1 due to N–H stretching vibra-
tions, and in the region 1700–1600 cm–1 due to C=N
stretchings, which is consistent with the data for struc-
turally related triaminoguanidine derivatives [12].
The structure of 3u·H2O was established by single-
crystal X-ray diffraction. Figure 1 shows the molecular
structure of 3u·H2O and its crystal packing. All carbon
and nitrogen atoms in the cationic moiety of 3u have
sp2 hybridization, and the bonds between the central
1399

JI et al.
1400
Scheme 1.
R
NH2
Cl–
EtOH–H2O (5:1, v/v)
reflux, 6 h
N
Cl–
N
HN
HN
+
RCHO
H2N
NH2
N
R
R
N
N
H
N
N
H
H
H
1
2a–2u
3a–3u
R = 2-HOC6H4 (a), 2-HO-5-ClC6H3 (b), 2-HO-5-O2NC6H3 (c), 2-HO-3,5-Br2C6H2 (d), 2-HO-4-Et2NC6H4 (e), 2-HO-
3,5-(t-Bu)2C6H2 (f), 4-i-PrC6H4 (g), 2-O2NC6H4 (h), 3-HOC6H4 (i), 3-HO-4-MeOC6H3 (j), 4-MeSO2C6H4 (k), 4-Me2NC6H4 (l),
4-MeOC6H4 (m), 4-BrC6H4 (n), Ph (o), (E)-PhCH=CH (p), naphthalen-1-yl (q), pyridin-3-yl (r), thiophen-2-yl (s), thiophen-3-yl (t),
5-bromothiophen-2-yl (u).
carbon and nitrogen atoms have a partial double-bond
character. The average C=N bond length is
1.266(10) Å, which is significantly shorter than the
average C–N bond length [1.330(9) Å]. This is in good
agreement with the data for tris(5-bromo-2-hydroxy-
benzylideneamino)guanidinium chloride (C=N
1.279(5) Å, C–N 1.327(7) Å) [7, 24]. The planar struc-
ture of the N2CN entity follows from the sum of the
angles subtended at the central carbon atom, which
equals 359.9(7)°. As expected, N–H···Cl, C–H···Cl,
and O–H···Cl hydrogen bonding interactions exist in
the crystal structure of 3u·H2O, as shown in Fig. 1b.
fluoride ion selectively. Then, colorimetric changes of
3b–3u in the presence of fluoride ion were examined
(Fig. 2), and distinct color changes for most of these
compounds were observed in the presence of fluoride
ions. Exceptions were compounds 3g, 3i, 3l, and 3m
which bear electron-donating substituents. Fluoride
ions caused drastic color changes from colorless to
yellow and even to red, reddish orange, and purple.
Compounds 3b–3d, 3h, 3k, 3n, and 3u containing
electron-withdrawing groups like nitro, bromo, chloro,
or methanesulfonyl on the phenyl ring or heterocycle,
showed remarkable color changes, presumably due to
the presence of a positive charge on the central nitro-
gen atom of the trisaminoguanidinium moiety, which
favored selective electrostatic interaction with spheri-
cal and basic fluoride ions [23]. If there are electron-
withdrawing groups in the Schiff base moieties, the
positive charge on the central nitrogen is higher, so that
the interaction with fluoride ion is enhanced.
The colorimetric changes and absorption and emis-
sion spectra of compounds 3a–3u were recorded from
1.0×10–4 M solutions in acetonitrile. Initially, color-
imetric changes of 3a in the presence of different
halide ions (F–, Cl–, Br–) were tested. Only in the
presence of fluoride ions, solutions of 3a changed from
colorless to yellow, indicating that 3a could detect
Br3
(a)
(b)
C15
C16
S3
C14
C13
C12
N6
N5
Cl1
N1
N2
C2
O1w
N4
C1
N3
C3
C4
C5
S2
Br2
C8
C9
C7
S1
C6
Br1
C11
C10
Fig. 1. (a) Structure of the molecule of N,N′,N′′-tris[(5-bromothiophen-2-yl)methylideneamino]guanidine hydrochloride (3u) hydrate
according to the X-ray diffraction data with arbitrary atom numbering. Non-hydrogen atoms are shown as thermal displacement
ellipsoids with a probability of 40%; (b) packing of molecules 3u·H2O in a unit cell viewed along the crystallographic ac plane;
hydrogen bonds are shown as dashed lines.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 9 2019

SYNTHESIS OF NOVEL N,N′,N′′-TRIS[ARYL(HETARYL)METHYLIDENE...
1401
3a/F–
3b/F–
3c/F–
3d/F–
3e/F–
3f/F–
3g/F–
3h/F–
3a
3b
3c
3d
3e
3f
3g
3h
3i/F–
3j/F–
3k/F–
3l/F–
3m/F–
3n/F–
3o/F–
3p/F–
3i
3j
3k
3l
3m
3n
3o
3p
3q/F–
3r/F–
3s/F–
3t/F–
3u/F–
3q
3r
3s
3t
3u
Fig. 2. Color change of compounds 3a–3u in acetonitrile in the presence of fluoride anion.
The UV-Vis spectral properties of 3a–3u were
studied in the presence of tetrabutylammonium
fluoride (TBAF), and the corresponding changes in the
optical spectra are shown in Fig. 3. The UV-Vis ab-
sorption peak at λ 359 nm of 3a was mainly due to the
Ar–CH=N–NH conjugated bond system [25]. In the
presence of fluoride anion, the intensity of that peak
decreases, and a new absorption band appears in the
region λ 400–600 nm (Fig. 3). For compounds 3g, 3l,
and 3m bearing electron-donating groups like iso-
propyl, dimethylamino, and methoxy, the position of
the UV-Vis absorption maximum almost did not
change, but the absorbance decreased. By contrast, for
compounds 3a–3f, 3i–3k, and 3n–3u bearing electron-
withdrawing or auxochromic moieties like hydroxy,
chloro, bromo, nitro, or methanesulfonyl, the UV-Vis
absorption maximum shifted red in the presence of
fluoride ions (Fig. 3), which might enhance the inter-
action of trisaminoguanidinium moiety with fluoride
ion. These findings were consistent with the results of
colorimetric change testing, according to which com-
pounds 3b–3d, 3f, 3k, 3n, and 3u showed more appre-
ciable color changes than 3g, 3i, 3l, and 3m (Fig. 2).
nium chlorides with electron-withdrawing groups
exhibited selective color changes in the presence of
fluoride ions and appreciable red shift in their UV-Vis
absorption spectra.
EXPERIMENTAL
N,N′,N′′-Triaminoguanidine hydrochloride was
supplied from Ma’anshan Huanyu Chemical Co. Tetra-
butylammonium fluoride/bromide/chloride and aro-
matic and heteroaromatic aldehydes were purchased
from Alfa Aesar, Sigma-Aldrich, J&K®, Aladdin®,
Energy Chemical, and Sinopharm Chemical Reagent
Co. All solvents were purified by routine procedures
and distilled under dry nitrogen before use. Unless
otherwise specified, all analytical reagents (>99.5%
purity) were purchased from Adamas-beta® and were
used as received without further purification. Melting
points were determined in capillaries using an X4
digital melting point apparatus and are uncorrected.
The IR spectra were recorded on a Nicolet 6700 spec-
trophotometer from pressed KBr discs. The UV ab-
sorption spectra were recorded on a Shimadzu UV-
1
2501 PC spectrophotometer. The H and 13C NMR
In summary, we have synthesized a series of new
triaminoguanidinium chloride derivatives functional-
ized with three Schiff base moieties. Single crystal
X-ray crystallography on one typical compound has
confirmed its ionic form. The colorimetric and UV-Vis
spectral studies in acetonitrile solution revealed that
N,N′,N′′-tris[aryl(hetaryl)methylideneamino]guanidi-
spectra were recorded on a Bruker Avance AV 400
spectrometer at 400 and 100 MHz, respectively, in
DMSO-d6 or CDCl3 with tetramethylsilane as internal
standard.
Typical procedure for the preparation of
N,N′,N′′-tris[aryl(hetaryl)methylideneamino]guani-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 9 2019

JI et al.
1402
D
D
3e
3a
3e/F–
3a/F–
0.4
3f
3b
3f/F–
3b/F–
0.2
3g
3c
3g/F–
3c/F–
0.3
0.2
0.1
0.0
3h
3d
3h/F–
3d/F–
0.1
0.0
300
350
400
450
500 λ, nm
300 350 400 450 500 550 600 650 λ, nm
3m
D
D
1.0
3i
3m/F–
3i/F–
3n
3j
3n/F–
1.0
3j/F–
3o
3k
0.8
0.6
0.4
0.2
0.0
3o/F–
3k/F–
0.8
0.6
0.4
0.2
0.0
3p
3l
3p/F–
3l/F–
300
350
400
450
500
550 λ, nm
300
350
400
450
500
550 λ, nm
D
3q
3q/F–
0.8
0.6
0.4
0.2
0.0
3r
3r/F–
3s
3s/F–
3t
3t/F–
3u
3u/F–
300
350
400
450
500
λ, nm
Fig. 3. Changes in the UV-Vis absorption spectra of compounds 3a–3u in the presence of fluoride ions.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 9 2019

SYNTHESIS OF NOVEL N,N′,N′′-TRIS[ARYL(HETARYL)METHYLIDENE...
1403
Table 1. Crystallographic data and experimental details for
compound 3u·H2O
dinium chlorides 3a–3u. A solution of 7.5 mmol of
aldehyde 2a–2u in 10 mL of ethanol was added drop-
wise to a mixture of N,N′,N′′-triaminoguanidine hydro-
chloride (0.351 g, 2.5 mmol) and 48 mL of ethanol–
water (5:1 by volume). The mixture was refluxed with
stirring for 6 h and cooled to room temperature, and
the white or yellow precipitate was filtered off, washed
with water, ethanol, and diethyl ether and dried under
reduced pressure.
Parameter
Value
Formula
C16H14N6OS3ClBr3
677.69
Molecular weight
Crystal system
Space group
a, Å
Monoclinic
P21/c
0008.5480(15)
12.510(2)
22.164(4)
98.259(3)
2345.7(7)
4
N,N′,N′′-Tris(2-hydroxybenzylideneamino)gua-
nidine hydrochloride (3a). Yield 0.91 g (80%), white
powder, mp 210‒213°C. IR spectrum, ν, cm–1: 3240
b, Å
c, Å
β, deg
V, Å3
1
(NH), 1623 (C=N). H NMR spectrum (DMSO-d6), δ,
ppm: 11.13 br.s (3H, NH), 9.00 s (3H, OH), 8.75 s
(3H, CH=N), 7.69 d (3H, Harom, J = 8.1 Hz), 7.45–
7.35 m (3H, Harom), 7.27 t (3H, Harom, J = 7.7 Hz),
6.95 d (3H, Harom, J = 8.9 Hz). 13C NMR spectrum
(DMSO-d6), δC, ppm: 163.17 (CH=N), 159.10
(CH=N), 157.43 (Carom), 133.69 (Carom), 131.22 (Carom),
120.19 (Carom), 120.06 (Carom), 116.63 (Carom).
Z
d
calc, g/cm3
1.919
Temperature, K
296(2)
F(000)
1320
μ(Mo Kα), mm–1
Total number of reflections
Number of independent reflections
Rint
5.562
6715
N,N′,N′′-Tris(5-chloro-2-hydroxybenzylidene-
amino)guanidine hydrochloride (3b). Yield 1.01 g
(73%), yellow powder, mp 241‒242°C. IR spectrum, ν,
3709
0.0955
Number of variables
277
1
cm–1: 3287 (NH), 1652 (C=N). H NMR spectrum
a
b
R1 /wR2 [I > 2s(I)]
0.0699/0.1588
0.1182/0.1769
0.848
(DMSO-d6), δ, ppm: 12.02 br.s (3H, NH), 10.76 s (3H,
OH), 8.91 s (3H, CH=N), 8.19 s (3H, Harom), 7.34 d
(3H, Harom, J = 6.8 Hz), 7.00 d (3H, Harom, J = 8.8 Hz).
13C NMR spectrum (DMSO-d6), δC, ppm: 155.42
(CH=N), 149.72 (CH=N), 146.02 (Carom), 133.14
(Carom), 126.05 (Carom), 123.97 (Carom), 122.86 (Carom),
118.24 (Carom).
a
b
R1 /wR2 (all data)
Goodness of fit Sc
Δρfin (max/min), e Å–3
+0.993/–1.633
a
R1 = Σ||Fo| – |Fc||/Σ|Fo|.
b
2
2 2 1/2
2
wR2 = [Sw(Fo – Fc22)2/Sw(Fo ) ] , w = [σ2(Fo ) + (AP)2 + BP]–1,
where P = (Max(Fo , 0) + 2Fc2)/3.
c
S = [Sw(Fo2 – Fc2)2/(nobs – nparam)]1/2.
N,N′,N′′-Tris(2-hydroxy-5-nitrobenzylidene-
amino)guanidine hydrochloride (3c). Yield 0.64 g
(43%), yellow powder, mp 276‒279°C. IR spectrum, ν,
(CH=N), 140.50 (Carom), 135.91 (Carom), 132.70 (Carom),
120.15 (Carom), 114.59 (Carom), 113.37 (Carom).
1
cm–1: 3404 (OH), 3267 (NH), 1655 (C=N). H NMR
spectrum (DMSO-d6), δ, ppm: 11.28 br (3H, NH),
9.30 s (3H, OH), 8.92 s (3H, CH=N), 8.42 d (3H,
N,N′,N′′-Tris[4-(diethylamino)-2-hydroxyben-
zylideneamino]guanidine hydrochloride (3e). Yield
0.88 g (53%), yellow powder, mp 174‒176°C. IR spec-
trum, ν, cm-1: 3461 (NH), 1627 (C=N). 1H NMR spec-
trum (DMSO-d6), δ, ppm: 11.28 br.s (3H, NH), 9.90 s
(3H, OH), 8.64 s (3H, CH=N), 7.75 d (3H, Harom, J =
14.9 Hz), 7.40 d (3H, Harom, J = 2.9 Hz), 6.34–6.21 m
(3H, Harom), 3.60–3.49 m (6H, NCH2), 1.18 t (9H,
CH2CH3, J = 12.6 Hz). 13C NMR spectrum
(DMSO-d6), δC, ppm: 159.37 (CH=N), 152.36
(CH=N), 144.53 (Carom), 142.78 (Carom), 130.01 (Carom),
109.28 (Carom), 105.12 (Carom), 98.38 (Carom), 45.09
(NCH2), 12.89 (CH3).
H
arom, J = 3.1 Hz), 8.17 d (3H, Harom, J = 9.8 Hz),
7.12 d (3H, Harom, J = 14.8 Hz). 13C NMR spectrum
(DMSO-d6), δC, ppm: 159.57 (CH=N), 144.29
(CH=N), 141.14 (Carom), 139.04 (Carom), 128.70 (Carom),
124.17 (Carom), 120.56 (Carom), 115.84 (Carom).
N,N′,N′′-Tris(3,5-dibromo-2-hydroxybenzyli-
deneamino)guanidine hydrochloride (3d). Yield
1.17 g (50%), yellow powder, mp 268‒271°C. IR spec-
trum, ν, cm–1: 3339 (NH), 1621 (C=N). 1H NMR spec-
trum (DMSO-d6), δ, ppm: 11.78 br.s (3H, NH), 8.74 s
(3H, OH), 8.51 s (3H, CH=N), 7.84 d (3H, Harom, J =
3.9 Hz), 7.68 d (3H, Harom, J = 3.9 Hz). 13C NMR spec-
trum (DMSO-d6), δC, ppm: 156.36 (CH=N), 146.54
N,N′,N′′-Tris(3,5-di-tert-butyl-2-hydroxybenzyli-
deneamino)guanidine hydrochloride (3f). Yield
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JI et al.
1404
1.18 g (60%), white powder, mp 244–247°C. IR spec-
trum, ν, cm–1: 3450 (NH), 1619 (C=N). 1H NMR spec-
trum (DMSO-d6), δ, ppm: 11.76 br.s (3H, NH), 10.51 s
(3H, OH), 8.67 s (3H, CH=N), 7.72 d (3H, Harom, J =
14.0 Hz), 7.25–7.19 m (3H, Harom), 1.33 s (27H, t-Bu),
1.27 s (27H, t-Bu). 13C NMR spectrum (DMSO-d6),
δC, ppm: 155.38 (CH=N), 142.86 (CH=N), 142.53
(Carom), 140.50 (Carom), 139.71 (Carom), 125.60 (Carom),
123.43 (Carom), 120.89 (Carom), 35.51 [C(CH3)3], 34.76
[C(CH3)3], 12.80 (CH3).
123.76 (Carom), 115.85 (Carom), 111.09 (Carom), 46.12
(OCH3).
N,N′,N′′-Tris[4-(methanesulfonyl)benzylidene-
amino)guanidine hydrochloride (3k). Yield 0.96 g
(60%), white powder, mp 213–215°C. IR spectrum, ν,
1
cm–1: 3410 (OH), 3021 (NH), 1638 (C=N). H NMR
spectrum (DMSO-d6), δ, ppm: 11.43 br (3H, NH),
8.77 s (3H, CH=N), 8.20–7.98 m (6H, Harom), 7.85–
13
7.80 m (6H, Harom), 3.28 s (9H, CH3). C NMR spec-
trum (DMSO-d6), δC, ppm: 150.54 (CH=N), 149.23
(CH=N), 144.92 (Carom), 142.51 (Carom), 142.48
(Carom), 138.53 (Carom), 129.10 (Carom), 127.83 (Carom),
43.85 (CH3).
N,N′,N′′-Tris[4-(propan-2-yl)benzylidene-
amino]guanidine hydrochloride (3g). Yield 1.05 g
(79%), white powder, mp 208–211°C. IR spectrum, ν,
1
cm–1: 3033 (NH), 1634 (C=N). H NMR spectrum
N,N′,N′′-Tris[4-(dimethylamino)benzylidene-
amino]guanidine hydrochloride (3l). Yield 0.88 g
(66%), white powder, mp 213–216°C. IR spectrum, ν,
(DMSO-d6), δ, ppm: 11.99 br.s (3H, NH), 8.69 s (3H,
CH=N), 7.90–7.76 m (6H, Harom), 7.48–7.35 m (6H,
H
arom), 3.02–2.90 m [3H, (CH3)2CH], 1.24 d (18H,
1
cm–1: 3322 (NH), 1642 (C=N). H NMR spectrum
13
CH3, J = 6.9 Hz). C NMR spectrum (DMSO-d6), δC,
ppm: 152.28 (CH=N), 151.52 (CH=N), 149.38 (Carom),
144.92 (Carom), 144.28 (Carom), 131.35 (Carom), 128.80
(Carom), 127.23 (Carom), 33.95 (CH), 24.11 (CH3).
(DMSO-d6), δ, ppm: 11.59 br.s (3H, NH), 8.54 s (3H,
CH=N), 7.76–7.59 m (6H, Harom), 7.09–6.82 m (6H,
H
arom), 3.01 s (18H, NCH3). 13C NMR spectrum
(DMSO-d6), δC, ppm: 152.44 (CH=N), 151.46 (CH=N),
148.30 (Carom), 144.28 (Carom), 142.13 (Carom), 130.07
(Carom), 120.88 (Carom), 111.99 (Carom), 36.47 (NCH3).
N,N′,N′′-Tris(2-nitrobenzylideneamino)guani-
dine hydrochloride (3h). Yield 1.01 g (75%), yellow
powder, mp 212–214°C. IR spectrum, ν, cm–1: 3299
1
N,N′,N′′-Tris(4-methoxybenzylideneamino)gua-
nidine hydrochloride (3m). Yield 0.91 g (74%), white
powder, mp 187–189°C. IR spectrum, ν, cm–1: 3396
(NH), 1635 (C=N). H NMR spectrum (DMSO-d6), δ,
ppm: 11.89 br.s (3H, NH), 8.99 s (3H, CH=N), 7.89–
7.74 m (6H, Harom), 7.42–7.12 m (6H, Harom). 13C NMR
spectrum (DMSO-d6), δC, ppm: 151.19 (CH=N),
148.83 (CH=N), 145.46 (Carom), 134.12 (Carom), 131.61
(Carom), 129.33 (Carom), 128.53 (Carom), 125.12 (Carom).
1
(OH), 3074 (NH), 1642 (C=N). H NMR spectrum
(DMSO-d6), δ, ppm: 11.92 br.s (3H, NH), 8.65 s (3H,
CH=N), 7.93–7.79 m (6H, Harom), 7.18–6.99 m (6H,
H
arom), 3.84 s (9H, OCH3). 13C NMR spectrum
N,N′,N′′-Tris(3-hydroxybenzylideneamino)gua-
nidine hydrochloride (3i). Yield 0.71 g (63%), white
powder, mp 245–248°C. IR spectrum, ν, cm–1: 3266
(DMSO-d6), δC, ppm: 162.07 (CH=N), 151.13 (CH=N),
148.52 (Carom), 144.08 (Carom), 142.28 (Carom), 130.41
(Carom), 126.14 (Carom), 114.78 (Carom), 55.91 (OCH3).
1
(NH), 1646 (C=N). H NMR spectrum (DMSO-d6), δ,
N,N′,N′′-Tris(4-bromobenzylideneamino)gua-
nidine hydrochloride (3n). Yield 0.82 g (51%), white
powder, mp 219–222°C. IR spectrum, ν, cm–1: 3415
ppm: 12.06 br.s (3H, NH), 9.82 s (3H, OH), 8.63 s
(3H, CH=N), 7.42–7.29 m (9H, Harom), 7.08–6.95 m
13
(3H, Harom). C NMR spectrum (DMSO-d6), δC, ppm:
1
(NH), 1639 (C=N). H NMR spectrum (DMSO-d6), δ,
156.69 (CH=N), 145.32 (CH=N), 142.54 (Carom),
136.44 (Carom), 130.35 (Carom), 120.48 (Carom), 116.76
(Carom), 114.64 (Carom).
ppm: 12.28 br.s (3H, NH), 8.72 s (3H, CH=N), 7.95–
7.69 m (6H, Harom), 7.54–7.31 m (6H, Harom). 13C NMR
spectrum (DMSO-d6), δC, ppm: 167.83 (CH=N),
156.92 (CH=N), 149.28 (Carom), 144.80 (Carom), 141.76
(Carom), 128.93 (Carom), 125.88 (Carom), 113.79 (Carom).
N,N′,N′′-Tris(3-hydroxy-4-methoxybenzyli-
deneamino)guanidine hydrochloride (3j). Yield
0.96 g (71%), white powder, mp 260–263°C. IR spec-
trum, ν, cm–1: 3503 (OH), 3056 (NH), 1644 (C=N).
1H NMR spectrum (DMSO-d6), δ, ppm: 11.95 br.s
(3H, NH), 9.71 s (3H, OH), 8.31 s (3H, CH=N), 7.61–
7.53 m (3H, Harom), 7.27–7.18 m (3H, Harom), 6.90–
6.82 m (3H, Harom), 3.86 s (9H, OCH3). 13C NMR spec-
trum (DMSO-d6), δC, ppm: 151.49 (CH=N), 150.39
(CH=N), 148.86 (Carom), 148.52 (Carom), 125.12 (Carom),
N,N′,N′′-Tris(benzylideneamino)guanidine
hydrochloride (3o). Yield 0.65 g (64%), white
powder, mp 184–186°C. IR spectrum, ν, cm–1: 3388
1
(NH), 1636 (C=N). H NMR spectrum (DMSO-d6), δ,
ppm: 12.10 br.s (3H, NH), 8.75 s (3H, CH=N), 8.06–
7.91 m (6H, Harom), 7.53–7.41 m (9H, Harom). 13C NMR
spectrum (DMSO-d6), δC, ppm: 149.02 (CH=N),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 9 2019

SYNTHESIS OF NOVEL N,N′,N′′-TRIS[ARYL(HETARYL)METHYLIDENE...
1405
1
144.82 (CH=N), 144.20 (Carom), 133.46 (Carom), 131.83
(Carom), 129.52 (Carom), 128.04 (Carom), 125.27 (Carom).
3389 (OH), 3072 (NH), 1642 (C=N). H NMR spec-
trum (DMSO-d6), δ, ppm: 12.01 br.s (3H, NH), 8.78 s
(3H, CH=N), 8.17 d (3H, thiophene, J = 2.7 Hz), 7.91–
7.86 m (3H, HTh), 7.75–7.68 m (3H, HTh). 13C NMR
spectrum (DMSO-d6), δC, ppm: 149.27 (CH=N),
146.63 (CH=N), 136.95 (CTh), 131.00 (CTh), 128.16
(CTh), 126.33 (CTh).
N,N′,N′′-Tris[(E)-3-phenylprop-2-en-1-ylidene-
amino]guanidine hydrochloride (3p). Yield 0.82 g
(68%), yellow powder, mp 178–181°C. IR spectrum, ν,
1
cm–1: 3410 (OH), 3026 (NH), 1634 (C=N). H NMR
spectrum (DMSO-d6), δ, ppm: 12.18 br.s (3H, NH),
8.46 s (3H, CH=N), 7.68–7.57 m (6H, Harom), 7.48–
7.35 m (9H, Harom), 7.24 d (3H, PhCH=, J = 16.0 Hz),
7.02 d.d (3H, Ph–CH=CH, J = 16.1, 9.3 Hz). 13C NMR
spectrum (DMSO-d6), δC, ppm: 152.98 (CH=N),
148.89 (CH=N), 144.46 (Carom), 142.02 (Carom), 135.92
(Carom), 129.25 (Carom), 129.47 (Carom), 127.78 (Carom),
127.74 (PhCH=), 124.60 (PhCH=CH).
N,N′,N′′-Tris[(5-bromothiophen-2-yl)methyli-
deneamino]guanidine hydrochloride (3u). Yield
1.02 g (62%), yellow powder, mp 181–183°C. IR spec-
trum, ν, cm–1: 3313 (OH), 3008 (NH), 1627 (C=N).
1H NMR spectrum (DMSO-d6), δ, ppm: 12.09 br.s
(3H, NH), 8.83 s (3H, CH=N), 7.51 d (3H, HTh, J =
13
4.0 Hz), 7.36 d (3H, HTh, J = 4.0 Hz). C NMR spec-
trum (DMSO-d6), δC, ppm: 148.64 (CH=N), 145.90
(CH=N), 139.36 (CTh), 134.17 (CTh), 132.02 (CTh),
127.54 (CTh).
N,N′,N′′-Tris[(naphthalen-1-yl)methylidene-
amino]guanidine hydrochloride (3q). Yield 0.97 g
(70%), white powder, mp 198–200°C. IR spectrum, ν,
1
cm–1: 3403 (OH), 3047 (NH), 1636 (C=N). H NMR
Single crystals of 3u·H2O were grown by recrystal-
lization from ethanol–water (7:3, v/v). The crystallo-
graphic data and experimental details of the X-ray
diffraction study are summarized in Table 1. Reflection
intensities were measured on a Bruker SMART APEX
2 CCD diffractometer (Mo Kα radiation, l 0.71073 Å,
graphite monochromator) at 293(2) K. The data were
processed using SAINT software [26]. A correction for
absorption was applied using SADABS [27]. The
structure was solved by the direct method and was
refined against F2 by the full-matrix least-squares
method using SHELXTL software package [28, 29].
All non-hydrogen atoms, expect for the solvate mole-
cule, were refined in anisotropic approximation. The
positions of all hydrogen atoms were generated geo-
metrically (Csp3–H 0.96, Csp2–H = 0.93 Å), assigned
isotropic thermal parameters, and allowed to ride on
the respective parent carbon or nitrogen atoms in
the final least-squares refinement cycles. The X-ray
diffraction data for 3u · H2O were deposited to
the Cambridge Crystallographic Data Centre
(CCDC entry no. 18871067) and are available at
www.ccdc.cam.ac.uk/data_request/cif.
spectrum (DMSO-d6), δ, ppm: 12.34 br.s (3H, NH),
8.70 s (3H, CH=N), 8.55–8.40 m (6H, Harom), 8.26–
8.01 m (6H, Harom), 7.79–7.60 m (9H, Harom). 13C NMR
spectrum (DMSO-d6), δC, ppm: 149.94 (CH=N),
144.78 (CH=N), 133.85 (Carom), 131.98 (Carom), 131.47
(Carom), 129.47 (Carom), 128.92 (Carom), 128.00
(Carom), 126.87 (Carom), 126.56 (Carom), 126.09 (Carom),
123.12 (Carom).
N,N′,N′′-Tris[(pyridin-3-yl)methylideneamino]-
guanidine hydrochloride (3r). Yield 0.56 g (57%),
yellow powder, mp 178–180°C. IR spectrum, ν, cm–1:
1
3426 (OH), 3048 (NH), 1635 (C=N). H NMR spec-
trum (DMSO-d6), δ, ppm: 12.54 br.s (3H, NH), 9.22 s
(3H, CH=N), 8.85–8.79 m (3H, Harom), 8.74–8.50 m
13
(6H, Harom), 7.66–7.54 m (3H, Harom). C NMR spec-
trum (DMSO-d6), δC, ppm: 149.92 (CH=N), 149.17
(CH=N), 144.41 (Carom), 142.13 (Carom), 136.13 (Carom),
129.74 (Carom), 124.70 (Carom).
N,N′,N′′-Tris[(thiophen-2-yl)methylideneamino]-
guanidine hydrochloride (3s). Yield 0.68 g (64%),
yellow powder, mp 188–191°C. IR spectrum, ν, cm–1:
1
3464 (OH), 3066 (NH), 1633 (C=N). H NMR spec-
FUNDING
trum (DMSO-d6), δ, ppm: 12.07 br.s (3H, NH), 8.88 s
(3H, CH=N), 7.85 d (3H, HTh, J = 5.0 Hz), 7.69 d (3H,
HTh, J = 3.6 Hz), 7.25–7.14 m (3H, HTh). 13C NMR
spectrum (DMSO-d6), δC, ppm: 148.65 (CH=N),
146.71 (CH=N), 137.54 (CTh), 133.34 (CTh), 131.47
(CTh), 128.64 (CTh).
This project was financially supported by the
National Natural Science Foundation of China (project
no. 21372007).
CONFLICT OF INTERESTS
N,N′,N′′-Tris[(thiophen-3-yl)methylideneamino]-
guanidine hydrochloride (3t). Yield 0.65 g (62%),
yellow powder, mp 195–198°C. IR spectrum, ν, cm–1:
The authors declare the absence of conflict of
interests.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 9 2019

JI et al.
15. Potts, K.T. and Hirsch, C.A., J. Org. Chem., 1968,
1406
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