N,N,N′,N′-tetramethylethylene-diaminium-N,N′-disulfonic acid trifluoroacetate and pyridinium-N-sulfonic acid hydrogen sulfate as highly effective dual-functional catalysts for the preparation of N,N′-alkylidene bisamides

Article abstract of DOI:10.1515/znb-2019-0064

In this research, Br?nsted-acidic ionic liquids N,N,N′,N′-tetramethylethylene-diaminium-N,N′-disulfonic acid trifluoroacetate ([TMEDSA][TFA]₂) and pyridinium-N-sulfonic acid hydrogen sulfate ([Py-SO₃H][HSO₄]) have been introduced as dual-functional catalysts for the green, simple and effective preparation of N,N′-alkylidene bisamides by the reaction of primary amides (2 eq.) with arylaldehydes (1 eq.) under solvent-free conditions. The reaction results and conditions of the catalysts have been compared with the previously reported ones. [TMEDSA][TFA]₂ and [Py-SO₃H][HSO₄] were superior to the previously reported catalysts in terms of two or more of these factors: Reaction times (10-45 min), yields (86-98%), temperature and the reaction conditions. Additionally, a plausible and attractive mechanism based on dual functionality of the catalysts has been proposed.

Full text of DOI:10.1515/znb-2019-0064

Z. Naturforsch. 2019; 74(9)b: 641–647
ZNa,hNra,NKo′r,dNro′-sTtaemtir*a, AmbdeotlhkayrilmetZharye*leanndeM-dositaamfa Kinariaummi -N,N′-disulfonic acid
trifluoroacetate and pyridinium-N-sulfonic acid hydrogen sulfate
as highly effective dual-functional catalysts for the preparation
of N,N′-alkylidene bisamides
https://doi.org/10.1515/znb-2019-0064
state, aptitude to solve a wide range of compound classes,
appropriate electrochemical window, catalyzation of
various organic transformations and their capability to
be functionalized for different purposes [1–10]. Among
the ILs, Brønsted acids have been particularly found to be
effective catalysts in several organic syntheses [4–10].
In many organic transformations, utilization of toxic
and volatile organic solvents is inevitable, which is not
satisfactory from a green chemistry point of view. An
effectual way to solve this problem is to perform reactions
under solvent-free conditions. This can also enhance yield
and selectivity, saves energy and time, increases reaction
rates, makes synthesis easier and prevents or minimizes
waste and by-products [11–15].
Received March 12, 2019; accepted July 2, 2019
Abstract: In this research, Brønsted-acidic ionic liq-
uids
N,N,N′,N′-tetramethylethylene-diaminium-N,N′-
disulfonic acid trifluoroacetate ([TMEDSA][TFA]2) and
pyridinium-N-sulfonic acid hydrogen sulfate ([Py-SO3H]
[HSO4]) have been introduced as dual-functional catalysts
for the green, simple and effective preparation of N,N′-
alkylidene bisamides by the reaction of primary amides
(2 eq.) with arylaldehydes (1 eq.) under solvent-free condi-
tions. The reaction results and conditions of the catalysts
have been compared with the previously reported ones.
[TMEDSA][TFA]2 and [Py-SO3H][HSO4] were superior to
the previously reported catalysts in terms of two or more
of these factors: reaction times (10–45 min), yields (86–
98%), temperature and the reaction conditions. Addition-
ally, a plausible and attractive mechanism based on dual
functionality of the catalysts has been proposed.
Amide and bisamide functionalities are part of the
framework of many pharmacological, biological, chemi-
cal and industrial molecules [16–23]. Bisamides are vital
moieties for introducing gem-diaminoalkyl fragments in
retro-inverse pseudo-peptide derivatives [19, 20]. Addi-
Keywords: Brønsted-acidic ionic liquid; N,N,N′,N′- tionally, these compounds are used in the synthesis of
tetramethylethylene-diaminium-N,N′-disulfonic acid trif- peptidomimetic materials [21, 22], and as ligands in the
luoroacetate ([TMEDSA][TFA]2); N,N′-alkylidene bisamide; Ullmann reaction leading to potentially pharmacologi-
pyridinium-N-sulfonic acid hydrogen sulfate ([Py-SO3H] cally active compounds [23]. Bisamides are also applied
[HSO4]); solvent-free.
as antitumor [24] and insecticide [25] agents. Applications
in polymerizations [26] and in the separation of xylene
isomers [27] have also been reported. A literature survey
shows that a practical method for the preparation of N,N′-
alkylidene bisamides includes the reaction of primary
amide (2 eq.) with aldehydes (1 eq.). Various catalysts have
been reported for this synthesis, such as hydroxyapatite
[28], phosphotungstic acid [29], nano-SnCl4·SiO2 [30],
H14[NaP5W29MoO110] [31], B(HSO4)3 [32], NiFe2O4@SiO2-PPA
[33], CH3COCl [34], HPVAC-20 (heteropoly-11-tungsto-1-
vanadophosphoric acid supported on activated natural
clay) [35], ZnCl2/SiO2 [36] and sulfonated carbon/nano-
titania composite (C/TiO2-SO3H) [37]. Nevertheless, many
of the reported methods have restrictions such as, for
example, long reaction times, moderate yields, harsh
reaction conditions and the utilization of volatile and
harmful organic solvents.
1 Introduction
Ionic liquids (ILs) have attracted great attention for their
use as attractive reaction media, reagents and cata-
lysts in organic synthesis. The inimitable properties of
ILs, which caused their wide applications in this field,
include thermal and chemical stability, non-volatility,
non-flammability, broad temperature range of the liquid
*Corresponding authors: Zahra Kordrostami
and Abdolkarim Zare, Department of Chemistry, Payame Noor
University, PO Box 19395-3697, Tehran, I.R. Iran,
e-mail: zr.kordrostami@gmail.com (Z. Kordrostami);
abdolkarimzare@pnu.ac.ir, abdolkarimzare@yahoo.com (A. Zare)
Mostafa Karami: Department of Chemistry, Payame Noor University,
PO Box 19395-3697, Tehran, I.R. Iran
In this research, we have used two Brønsted-acidic
ILs, namely N,N,N′,N′-tetramethylethylene-diaminium-
N,N′-disulfonic acid trifluoroacetate ([TMEDSA][TFA]2)
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642ꢀ ꢀZ. Kordrostami et al.: Effective preparation of N,N′-alkylidene bisamides
Table 1:ꢀEffect of the catalyst quantity and temperature on the
and pyridinium-N-sulfonic acid hydrogen sulfate
([Py-SO3H][HSO4]), as highly efficient and general dual-
functional catalysts for the solvent-free preparation of
N,N′-alkylidene bisamides from primary amides (2 eq.)
and arylaldehydes (1 eq.), thereby overcoming several of
the above-mentioned limitations.
model reaction shown in Scheme 1.
Entryꢁ Catalyst
ꢁ
Amount ofꢁ Temperatureꢁ Timeꢁ Yield
catalyst
(mol.%)
(°C) (min) (%)a
1
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
–
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
–ꢂ
5ꢂ
90ꢂ
90ꢂ
100ꢂ Trace
30ꢂ 85
20ꢂ 96
16ꢂ 96
25ꢂ 82
15ꢂ 96
60ꢂ 87
40ꢂ 93
35ꢂ 94
65ꢂ 76
32ꢂ 94
2
[TMEDSA][TFA]2
[TMEDSA][TFA]2
[TMEDSA][TFA]2
[TMEDSA][TFA]2
[TMEDSA][TFA]2
3
10ꢂ
13ꢂ
10ꢂ
10ꢂ
13ꢂ
15ꢂ
20ꢂ
15ꢂ
15ꢂ
90ꢂ
4
90ꢂ
80ꢂ
2 Results and discussion
5
6
100ꢂ
90ꢂ
To find optimal reaction conditions, the condensation
of benzamide (2 mmol) and benzaldehyde (1 mmol) was
chosen as a model reaction (Scheme 1) and investigated
in the presence of different amounts of [TMEDSA][TFA]2
or [Py-SO3H][HSO4] in the temperature range of 80–100°C
under solvent-free conditions. These results are summa-
rized in Table 1. As shown in Table 1, the reaction was effi-
ciently performed using 10 mol.% of [TMEDSA][TFA]2 or
7
[Py-SO3H][HSO4]ꢂ
[Py-SO3H][HSO4]ꢂ
[Py-SO3H][HSO4]ꢂ
[Py-SO3H][HSO4]ꢂ
[Py-SO3H][HSO4]ꢂ
8
90ꢂ
9
90ꢂ
10
11
80ꢂ
100ꢂ
aIsolated yields.
15 mol.% of [Py-SO3H][HSO4] at Tꢀ=ꢀ90°C (Table 1, entries times. Furthermore, [TMEDSA][TFA]2 and [Py-SO3H][HSO4]
3 and 8). Increasing the amounts of catalyst or the tem- effectively catalyze the reaction when benzaldehyde and
perature slightly reduces the reaction times in the case of arylaldehydes possess electron-withdrawing, electron-
both catalysts (Table 1, entries 4, 6, 9 and 11), and the yield releasing substituents or halogens in ortho, meta or para
slightly enhanced in the case of [Py-SO3H][HSO4] (Table 1, positions. Nevertheless, [TMEDSA][TFA]2 gave the desired
entries 9 and 11). Nevertheless, 90°C was selected as the N,N′-alkylidene bisamides in often higher yields and in
optimal temperature for both catalysts. Moreover, 10 and shorter reaction times as compared to [Py-SO3H][HSO4].
15 mol.% were chosen as the optimal catalyst amounts for According to the results reported in Table 2, both ILs are
[TMEDSA][TFA]2 and [Py-SO3H][HSO4], respectively. These highly efficient and general catalysts for the synthesis.
conditions were deliberately chosen because perform-
The ILs are dual-functional catalysts having both acidic
ing reactions using less catalyst at lower temperatures is (SO3H) and basic sites (trifluoroacetate and hydrogen sulfate
more in compliance with green-chemistry protocols. The are weak bases; see Figs. 1 and 2) [5, 9]. Thereby [TMEDSA]
solvent-free reaction was also examined at Tꢀ=ꢀ90°C in the [TFA]2 and [Py-SO3H][HSO4] can be used as efficient, general
absence of a catalyst whereby the reaction did not sig- catalysts for reactions which need both acidic and basic
nificantly progress even after long reaction time (Table 1, catalysts simultaneously, for example, the synthesis of
entry 1).
N,N′-alkylidene bisamides. This topic is elaborated in a pro-
After finding the optimal reaction conditions, amides posed reaction mechanism with [TMEDSA][TFA]2 as cata-
were reacted with various aldehydes using [TMEDSA] lyst (Scheme 2). First, amide is activated by the basic group
[TFA]2 or [Py-SO3H][HSO4] as catalysts in order to appraise of [TMEDSA][TFA]2 and added to the activated aldehyde by
their scope and effectiveness. The respective results the acidic site of the catalyst to afford intermediate I (trif-
are depicted in Table 2. As is shown there, benzamide, luoroacetate assists to bind a proton from the amide NH2).
acetamide and acrylamide in the presence of both cata- Then, the acidic IL helps to remove a molecule of H2O from I
lysts afford the products in high yields and short reaction to give intermediate II (trifluoroacetate assists for removing
O
O
O
O
catalyst
NH2
H
+
2
N
N
solvent-free
H
H
Scheme 1:ꢀThe model reaction used for the screening of the reaction conditions.
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Z. Kordrostami et al.: Effective preparation of N,N′-alkylidene bisamidesꢃ
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Table 2:ꢀThe synthesis of N,N′-alkylidene bisamides catalyzed by [TMEDSA][TFA]2 (10 mol.%) or [Py-SO3H][HSO4] (15 mol.%).
O
Ar
O
O
O
[TMEDSA][TFA]2 or [Py-SO3H][HSO4]
2
+
N
N
solvent-free, T = 90 °C
R
Ar
NH2
R
R
H
H
H
Comp. no.
R
Ar
[TMEDSA][TFA]2
Yield (%)a
96
[Py-SO3H][HSO4]
Yield (%)a
93
M.p. (°C) (Lit.)
Time (min)
Time (min)
1a
1b
1c
1d
1e
1f
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
CH3
C6H5
20
40
216–218
(217–219 [31])
260–262
(259–261 [32])
230–232
(232–235 [32])
258–260
(256–257 [32])
250–252
(252–254 [37])
196–198
(199–200 [37])
224–226
(224–226 [33])
227–229
(226–228 [29])
228–230
(230–232 [29])
239–241
(242–244 [33])
235–237
(238–240 [34])
272–274
(270–272 [33])
271–273
4-O2NC6H4
3-O2NC6H4
2-O2NC6H4
4-ClC6H4
2,4-Cl2C6H3
3-BrC6H4
4-FC6H4
13
10
25
20
30
15
10
35
25
25
20
35
40
96
98
92
98
91
92
95
93
95
90
94
88
91
30
40
35
40
30
30
20
40
35
35
35
40
45
97
93
90
95
87
90
95
92
89
88
91
90
86
1g
1h
1i
4-CH3OC6H4
4-CH3C6H4
C6H5
1j
1k
1l
CH3
4-O2NC6H4
4-CH3C6H4
4-O2NC6H4
1m
1n
CH3
(270–272 [34])
240–242
CH2=CH
aIsolated yields.
O
F3C
N
O
Basic site
O
O
S
O
O
Acidic site
Acidic site
H
Acidic site
H
H
O
O
O
O
S
N
Basic site
S
O
O
O
S
N
O
[Py-SO3H][HSO4]
Fig. 2:ꢀThe acidic and basic sites of [Py-SO3H][HSO4].
Acidic site
Basic site
H
O
O
F3C
O
H2O by attracting a proton). Intermediate II is activated by
the catalyst to accept a nucleophile, whereupon the second
amide (which is activated by the catalyst anion) is added
[TMEDSA][TFA]2
Fig. 1:ꢀThe acidic and basic sites of [TMEDSA][TFA]2.
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ꢀZ. Kordrostami et al.: Effective preparation of N,N′-alkylidene bisamides
NMe2
SO2
Me2N
CF3CO2
SO3H
O
O
CF3
H
O
O
O
O
O
[TMEDSA][TFA]2
[TMEDSA][TFA]2
H
H2N
N
R
Ar
Ar
R
H
H
H
OH
O
Ar
N
R
H
(I)
[TMEDSA][TFA]2
NMe2 CF3CO2
Me2N
O2S
O
SO3H
H
H
O
O
N
R
Ar
O
O
H
F3C
_
H2O
O
Ar
N
(II)
R
[TMEDSA][TFA]2
NMe2
SO2
Me2N
SO3H
CF3CO2
O
O
H
F3C
O
H
N
H
O
O
R
O
N
[TMEDSA][TFA]2
Ar
R
H2N
R
O
Ar
O
N
N
H
R
R
H
N,N′-Alkylidene bisamide
Scheme 2:ꢀThe proposed mechanism for the synthesis of N,N′-alkylidene bisamides.
to it leading to the product. [Py-SO3H][HSO4] can also cata- accelerate all steps of the reaction mechanism. Further-
lyze the reaction in this way. The mechanism is supported more, the higher effectiveness of [TMEDSA][TFA]2 with
by the literature [33]. In fact, high efficacy of both catalysts respect to [Py-SO3H][HSO4] can be related to having more
can be attributed to dual functionality of them, and capa- basic sites (two instead of one, respectively) while both ILs
bility to activate the electrophiles and the nucleophiles to have two acidic sites (see Figs. 1 and 2).
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Table 3:ꢀResults and reaction conditions obtained with [TMEDSA][TFA]2 and [Py-SO3H][HSO4] in comparison with previously reported catalysts.
Catalyst
Conditions
Time range
Yields (%)
Ref.
[TMBSED][TFA]2
[Py-SO3H][HSO4]
Hydroxyapatite
Phosphotungstic acid
Nano-SnCl4·SiO2
H14[NaP5W29MoO110
B(HSO4)3
Solvent-free, 90°C
Solvent-free, 90°C
CH3CN, reflux
10–40 min
20–45 min
3 h
88–98
86–97
87–95
44–94
71–96
42–95
83–96
52–93
80–98
85–96
70–89
80–94
–
–
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
Toluene, reflux
20–72 h
n-Hexane, reflux
CH3OH, reflux
Solvent-free, 100°C
CH3OH, reflux
CH3CN, r.t.
Solvent-free, 110°C
Solvent-free, 80°C
Solvent-free, 100°C
0.81–5.1 h
50–120 min
15–45 s
40–130 min
5–25 min
25–45 min
25–40 min
0.5–3 h
]
NiFe2O4@SiO2-PPA
CH3COCl
HPVAC-20
ZnCl2/SiO2
C/TiO2-SO3H
Finally, we compared the effectiveness and the reac- believe that the preparation of them from fresh N,N,N′,N′-
tion conditions of our catalysts with those reported in the tetramethylethylene-diamine or pyridine is more eco-
literature, the results being shown in Table 3. The data nomic, greener and easier than their regeneration.
clearly demonstrate that [TMEDSA][TFA]2 and [Py-SO3H]
[HSO4] are superior to the reported catalysts in terms of
two or more of these factors: reaction times, yields, tem-
perature and/or reaction conditions.
4 Experimental section
4.1 General
3 Conclusion
All chemicals were purchased from Merck or Fluka Chemi-
In summary, we have reported the efficient synthe- cal Companies. [TMEDSA][TFA]2 and [Py-SO3H][HSO4] were
sis of N,N′-alkylidene bisamides in the presence of two synthesized according to reported procedures (Schemes 3
Brønsted-acidic ILs, namely N,N,N′,N′-tetramethylethylene- and 4) [9, 10]. All known compounds were identified by
diaminium-N,N′-disulfonic acid trifluoroacetate and comparison of their melting points and/or spectral data
pyridinium-N-sulfonic acid hydrogen sulfate. The advan- with those reported in the literature. Melting points were
tages of the presented methodologies over previous ones are recorded on Büchi B-545 apparatus in open capillary
effectiveness, generality, high yields, relatively short reac- tubes. Progress of the reactions was monitored by thin-
tion times, cleaner reaction profile, utilization of solvent- layer chromatography (TLC) using silica gel SIL G/UV
free conditions, ease of product isolation and purification, 254 plates. FT-IR spectra were run using Shimadzu IR-60
simple preparation and dual-functionality of the catalysts apparatus. 1H NMR (500 MHz) and 13C NMR (125 MHz) were
and good compliance with green-chemistry protocols.
run on Bruker Avance DPX, FT-NMR spectrometers (δ in
Although in our previous work we were able to ppm). Mass spectra were recorded on a 5975C VL MSD
regenerate similar catalysts as employed here [38], we model with its triple-axis detector.
Me
SO3H
Me
CH2Cl2
10°C
ClSO3H
2 Cl−
NMe2
N
+
Me2N
N
r. t.
Me
HO3S
Me
Me
SO3H
Me
CF3COOH
r. t. 60°C
N
[CF3COO]2
N
Me
HO3S
Me
[TMEDSA][TFA]2
Neat
Scheme 3:ꢀThe preparation of [TMEDSA][TFA]2.
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ꢀZ. Kordrostami et al.: Effective preparation of N,N′-alkylidene bisamides
CH2Cl2
r. t.
H2SO4
60°C
Neat
+
[HSO4]−
+
Cl
+
ClSO3H
N
N
r. t.
N
SO3H
SO3H
[Py-SO3H][HSO4]
Scheme 4:ꢀThe synthesis of [Py-SO3H][HSO4].
25°C, TMS): δꢀ=ꢀ21.3, 59.2, 127.0, 128.1, 128.9, 129.4, 132.2,
134.5, 137.5, 138.0, 166.1.
4.2 General procedure for the preparation of
N,N′-alkylidene bisamides
A mixture of amide (2 mmol), arylaldehyde (1 mmol) and
[TMEDSA][TFA]2 (0.050 g, 0.10 mmol) or [Py-SO3H][HSO4] 4.3.4 N,N′-(4-Nitrophenylmethylene)diacrylamide (1n)
(0.038 g, 0.15 mmol) was vigorously stirred by a small rod
1
at Tꢀ=ꢀ90°C. After the reaction was completed as monitored IR (KBr): νꢀ=ꢀ1221, 1346, 1505, 1557, 1625, 1665, 3270 cm−1. – H
by TLC, the reaction mixture was cooled to room tempera- NMR (500 MHz, DMSO-d6, 25°C, TMS): δꢀ=ꢀ5.69 (dd, Jꢀ=ꢀ1 .7,
ture, and the resulting precipitate was recrystallized from 10.4 Hz, 2H, vinyl CH), 6.19 (dd, Jꢀ=ꢀ1.7, 17.2 Hz, 2H, vinyl
EtOH (96%) to give the pure product.
CH), 6.36 (d, Jꢀ=ꢀ10.2 Hz, 1H, vinyl CH), 6.39 (d, Jꢀ=ꢀ10.2 Hz,
1H, vinyl CH), 6.77 (t, Jꢀ=ꢀ7.6 Hz, 1H, methine CH), 7.64 (d,
Jꢀ=ꢀ8.7 Hz, 2H, HAr), 8.27 (d, Jꢀ=ꢀ8.7 Hz, 2H, HAr), 9.07 (d,
Jꢀ=ꢀ7.6 Hz, 2H, NH). – C NMR (125 MHz, DMSO-d6, 25°C,
TMS): δꢀ=ꢀ57.8, 124.0, 127.1, 128.3, 131.4, 147.5, 147.7, 164.6.
13
4.3 Selected spectral data of the
synthesized N,N′-alkylidene bisamides
+
–MS (EI, 70 eV): m/z (%)ꢀ=ꢀ275 (0.4) [M] .
4.3.1 N,N′-(4-Chlorophenylmethylene)dibenzamide (1e)
1H NMR (500 MHz, DMSO-d6, 25°C, TMS): δꢀ=ꢀ7.03 (t, 5 Supplementary information
Jꢀ=ꢀ7.6 Hz, 1H, methine CH), 7.45–7.58 (m, 7H, HAr), 7.57
(t, Jꢀ=ꢀ7.3 Hz, 2H, HAr), 7.94 (d, Jꢀ=ꢀ7.3 Hz, 4H, HAr), 9.10 (d, Selected original spectra of the synthesized N,N′-
13
Jꢀ=ꢀ7.4 Hz, 2Hm NH). – C NMR (125 MHz, DMSO-d6, 25°C, alkylidene bisamides have been given in the Supplemen-
TMS): δꢀ=ꢀ58.9, 128.2, 128.8, 128.9, 129.2, 132.3, 132.9, 134.3, tary information available online (https://doi.org/10.1515/
139.9, 166.3.
znb-2019-0064).
Acknowledgment: The authors acknowledge the support
of this work by the Research Council of Payame Noor
University.
4.3.2 N,N′-(4-Fluorophenylmethylene)dibenzamide (1h)
1H NMR (500 MHz, DMSO-d6, 25°C, TMS): δꢀ=ꢀ7.04 (t,
Jꢀ=ꢀ7.6 Hz, 1H, methine CH), 7.22 (t, Jꢀ=ꢀ8.8 Hz, 2H, HAr),
7.49 (t, Jꢀ=ꢀ7.8 Hz, 4H, HAr), 7.53–7.58 (m, 4H, HAr), 7.94 (d, References
13
Jꢀ=ꢀ7.4 Hz, 4H, HAr) 9.09 (d, Jꢀ=ꢀ7.6 Hz, 2H, NH). – C NMR
[1] P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, Wiley-
(125 MHz, DMSO-d6, 25°C, TMS): δ (ppm) 58.9, 128.2, 128.9,
VCH, Weinheim, 2008.
129.2, 129.3, 132.2, 134.4, 137.1, 137.2, 161.3, 163.3, 166.3.
[2] A. Hasaninejad, A. Zare, M. Shekouhy, J. Ameri Rad, J. Comb.
Chem. 2010, 12, 844.
[3] M. A. Zolfigol, A. Khazaei, A. R. Moosavi-Zare, A. Zare, H. G. Kru-
ger, Z. Asgari, V. Khakyzadeh, M. Kazem-Rostami, J. Org. Chem.
2012, 77, 3640.
4.3.3 N,N′-(4-Methylphenylmethylene)dibenzamide (1j)
1H NMR (500 MHz, DMSO-d6, 25°C, TMS): δꢀ=ꢀ2.30 (s, 3H,
CH3), 7.02 (t, Jꢀ=ꢀ7.7 Hz, 1H, methine CH), 7.20 (d, Jꢀ=ꢀ8.0 Hz,
2H, HAr), 7.37 (d, Jꢀ=ꢀ8.1 Hz, 2H, HAr), 7.49 (t, Jꢀ=ꢀ7.3 Hz, 4H,
HAr), 7.56 (t, Jꢀ=ꢀ7.3 Hz, 2H, HAr), 7.92 (d, Jꢀ=ꢀ7.8 Hz, 4H, HAr),
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13
8.99 (2H, d, Jꢀ=ꢀ7.8 Hz, NH). – C NMR (125 MHz, DMSO-d6,
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Z. Kordrostami et al.: Effective preparation of N,N′-alkylidene bisamidesꢃ
ꢃ647
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Supplementary Material: The online version of this article offers
supplementary material (https://doi.org/10.1515/znb-2019-0064).
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