Rearrangement of 4-oxoalkane-1,1,2,2-tetracarbonitriles in the directed synthesis of aryl-substituted 2-(3-cyano-5-hydroxy-1,5-dihydro-2H-pyrrol-2-ylidene)malononitriles

Article abstract of DOI:10.1007/s10593-017-2170-1

[Figure not available: see fulltext.] 3-Aryl-4-oxoalkane-1,1,2,2-tetracarbonitriles were synthesized by the interaction of 2-aryl ketones with tetracyanoethylene. Directed rearrangement of them in acetic acid in the presence of ammonium acetate led to the

Full text of DOI:10.1007/s10593-017-2170-1

DOI 10.1007/s10593-017-2170-1
Chemistry of Heterocyclic Compounds 2017, 53(9), 1057–1060
Rearrangement of 4-oxoalkane-1,1,2,2-tetracarbonitriles
in the directed synthesis of aryl-substituted 2-(3-cyano-5-hydroxy-
1,5-dihydro-2H-pyrrol-2-ylidene)malononitriles
Mikhail Yu. Belikov1*, Sergey V. Fedoseev1,
Mikhail Yu. Ievlev1, Oleg V. Ershov1
1 Chuvash State University named after I. N. Ulyanov ,
15 Moskovskiy Ave., Cheboksary 428015, Russia; е-mail: belikovmil@mail.ru
Submitted June 15, 2017
Accepted after revison September 9, 2017
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2017, 53(9), 1057–1060
3-Aryl-4-oxoalkane-1,1,2,2-tetracarbonitriles were synthesized by the interaction of 2-aryl ketones with tetracyanoethylene. Directed rear-
rangement of them in acetic acid in the presence of ammonium acetate led to the formation of 2-(3-cyano-5-hydroxy-1,5-dihydro-2H-
pyrrol-2-ylidene)malononitriles containing an aryl substituent in conjugation with the acceptor buta-1,3-diene-1,1,3-tricarbonitrile moiety.
Keywords: 2-aryl ketones, buta-1,3-diene-1,1,3-tricarbonitrile moiety, 4-oxoalkane-1,1,2,2-tetracarbonitriles, tetracyanoethylene, rear-
rangement.
Derivatives of tricyanofuran (TCF) and tricyanopyrrole
(TCP) containing in their structure the acceptor buta-1,3-
diene-1,1,3-tricarbonitrile (BDTC) moiety belong to an
important group of heterocyclic compounds with signifi-
cant practical use (Fig. 1). Derivatives of these compounds
are promising components of luminescent sensors and
labels,1-3 nonlinear optical materials,4-8 solar cells,9-12 and
solid-state fluorescent dyes.13 Therefore, the development
of methods for the synthesis of five-membered hetero-
cycles with a BDTC fragment continues to be of interest.
As we demonstrated earlier, 1-(2-oxocyclohexyl)ethane-
1,1,2,2-tetracarbonitriles synthesized from cyclohexanones
and tetracyanoethylene (TCNE) can undergo rearrange-
ment in the presence of ammonium acetate to hydroxy-
tricyanopyrrole (HTCP) derivatives.14 It should be noted
that the variant of the reaction of TCNE with ketones
possessing an active methylene group developed by us14
has advantages over the known method described in the
paper of Australian authors,15 where TCNE was used as the
starting compound for HTCP synthesis. First, only 1,3-di-
carbonyl compounds were used in the reaction with
TCNE,15 which greatly limits this method in terms of
directed introduction of substituents into the HTCP
structure. Secondly, the article15 reports that the reaction of
TCNE with monoketones is unsuitable for obtaining HTCP
structures. However, as we were able to show,14 the way
out of this situation is the isolation of adducts of
tetracyanoethylene with ketones, 4-oxoalkane-1,1,2,2-tetra-
carbonitriles, which, as it turned out, are able to rearrange
into HTCP. In the case of 1,3-dicarbonyl compounds,
isolation of intermediate adducts with TCNE is impossible
or difficult.15
The HTCP derivatives (Fig. 1), like the TCF and TCP
derivatives, contain the BDTC fragment in their structure
and are the closest structural analogs of the latter among
the known compounds. The key difference between HTCP
and derivatives of TCF and TCP is the presence of a
geminal amino alcohol moiety in their structure, which
makes these compounds sufficiently functional for further
directed modifications. However, there are only few
references to HTCP structures in the literature,14–17 while
TCF and TCP are well studied. The most important
direction in the design of derivatives of TCF and TCP of
practical significance is the development of methods for the
synthesis of compounds containing aromatic (hetero-
Figure 1. Structures containing the BDTC moiety.
0009-3122/17/53(09)-1057©2017 Springer Science+Business Media New York
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Chemistry of Heterocyclic Compounds 2017, 53(9), 1057–1060
Scheme 1
CH(CN)
2
NC CN
Ar
CN
AcOH (70%)
AcONH4
40–50°C, rt, 3 h
56–79%
Ar
Ar
CN
Ar
Ar
CN
TCNE, HCl
1,4-dioxane
70–91%
CN
CN
N
NH
CN
CN
R
HO
R
R
CN
N
H
O
A
R
O
R
O
H2N
O
1a h
2a h
B
3a h
–
–
–
aromatic) or unsaturated substituents in conjugation with
the BDTC moiety (substituent R, Fig. 1). It is the
chromophores with these structural elements that in most
cases find application in the areas described above.
Table 1. The structure and yields of compounds 3
Compound
Ar
Ph
R
Yield, %
56
Ph
3a
In this regard, the aim of the study was to explore the
possibility of realizing the rearrangement of tetracyano-
ethylated cyclohexanones described by us in the directed
synthesis of HTCP derivatives containing an aromatic
substituent next to the BDTC acceptor. The main task of
the study was to develop an approach where the structure
of the resulting chromophore would be set from the
beginning by selecting an appropriate precursor. The
fruitfulness of using aryl-substituted substrates obtained in
directed synthesis was demonstrated by the team of Nobel
laureate W. E. Moerner in the synthesis of TCP derivatives,
which turned out to be useful as fluorescent labels for the
visualization of individual biomolecules.18,19
Ph
64
69
74
73
3b
3c
3d
3e
2-Th
To achieve our goal, we chose aryl-substituted ketones
1a–h at the initial stage as the reactants in the reaction with
tetracyanoethylene. These compounds were selected in
such a way that their structure contained an aromatic
(heteroaromatic) substituent bonded to the carbonyl group
via the methylene unit (Ar substituent in structures 1a–h,
Scheme 1). Just such arrangement of the substituents in the
case of a successful rearrangement guarantees the synthesis
of HTCP derivatives in which the aryl fragment will be in
conjugation with the BDTC fragment. As a result, a series
of 3-aryl-substituted 4-oxoalkane-1,1,2,2-tetracarbonitriles
2a–h was synthesized with yields of 70–91% based on the
reaction of aryl ketones 1a–h with tetracyanoethylene in
1,4-dioxane in the presence of catalytic amounts of
hydrochloric acid (Scheme 1). Compounds 2e–g were
obtained for the first time.
The rearrangement of tetracarbonitriles 2a–h was
carried out in a 70% aqueous acetic acid medium in the
presence of a threefold excess of ammonium acetate, result-
ing in the synthesis of a number of HTCP derivatives, 2-(4-
aryl-3-cyano-5-hydroxy-1,5-dihydro-2H-pyrrol-2-ylidene)-
malononitriles 3a–h. The isolated yields were 54–79%
(Scheme 1, Table 1).
From the point of view of structural changes, the process
in Scheme 1 is the rearrangement of the propane-1,1,2,2-
tetracarbonitrile moiety of compounds 2a–h into the 2-amino-
buta-1,3-diene-1,1,3-tricarbonitrile moiety of the inter-
mediate structures B, in which intramolecular cyclization
of amine and carbonyl groups is realized with the
formation of the final pyrroles 3a–h. The proposed reaction
mechanism is either analogous to the previously described
process of the rearrangement of tetracyanoethylated
cyclohexanones involving the direct rearrangement of
compounds 2a–h into compounds B,14 or the formation of
compounds B preceded by the derivatives of dihydrofuran
A, which are rearranged according to the scheme described
in the publication15 (Scheme 1).
4-BrC6H4
Me
Bn
79
58
54
3f
3g
3h
Ph
Ph
The structure of HTCP derivatives 3a–h was confirmed
using IR, 1H and 13C NMR spectroscopy and mass
spectrometry. The mass spectra are characterized by the
presence of peaks of molecular ions with an intensity of
1
14–100%. In H NMR spectra, the proton signals of the
gem-amino alcohol fragment formed during the
rearrangement are characteristic: the downfield singlet
signals of NH protons manifest at 10.81–11.22 ppm,
whereas the peaks of hydroxy group protons are observed
in the 7.36–8.07 ppm region. In 13C NMR spectra of
compounds 3a–h, downfield signals of the C-2 and C-4
atoms of the BDTC fragment at 167.5–170.8 and 160.1–
161.1 ppm, respectively, a set of three carbon signals of
cyano groups at 111.9–115.0 ppm, as well as the
characteristic upfield signal of the α-C atom of the C(CN)2
fragment in the 45.1–46.7 ppm range is present.
To conclude, a method has been developed for the
synthesis of hydroxytricyanopyrrole derivatives having an
increased chain of conjugation due to the combination of
an aromatic substituent with the acceptor buta-1,3-diene-
1,1,3-tricarbonitrile moiety which is based on the
rearrangement of 3-aryl-4-oxoalkane-1,1,2,2-tetracarbo-
nitriles. The presented variant of the method for the
preparation of hydroxytricyanopyrrole derivatives is more
promising in comparison with the previously described
one, since it allows to obtain the hydroxytricyanopyrrole
derivatives of the given structure by selecting substituents
in the starting 4-oxoalkane-1,1,2,2-tetracarbonitriles.
1058

Chemistry of Heterocyclic Compounds 2017, 53(9), 1057–1060
Experimental
the corresponding 4-oxoalkane-1,1,2,2-tetracarbonitrile 2a–h
(1 mmol) in 70% aqueous AcOH (4 ml). The obtained
mixture was heated with stirring to 40–50°С until complete
dissolution of ketone 2. The mixture was allowed to cool to
room temperature, and stirring at room temperature
continued for 3 h. The formed precipitate was filtered off,
washed on filter with water followed by cold isopropanol.
The solid was dried in a vacuum desiccator over CaCl2
until constant mass. When ketones 2e,h were used, no
precipitate was formed. In these cases the reaction mixture
was diluted with water (8 ml), the formed precipitate
filtered and purified by column chromatography on silica
gel (eluent EtOAc–hexane, 2:1). Products were isolated by
evaporating the solvent under reduced pressure.
IR spectra were registered on a FSM-1202 Fourier
spectrometer with a thin film of the sample suspension in
petroleum jelly. 1H and 13C NMR spectra were acquired on
a Bruker DRX-500 spectrometer (500 and 125 MHz,
respectively) in DMSO-d6, (compounds 3a–h) and in
acetone-d6 (compounds 2e–h) with TMS as internal
standard. Mass spectra were recorded on a Finnigan МАТ
INCOS-50 system (70 eV ionization energy). Elemental
analysis was performed on a vario MICRO cube CHN-
analyzer. Melting points were determined on an OptiMelt
MPA100 apparatus. Monitoring of the reaction progress
and assessment of the purity of synthesized compounds
was done by TLC on Sorbfil PTSH-AF-A-UF plates
(eluent EtOAc–hexane, 9:1, visualization under UV light,
in iodine chamber, or by thermal decomposition). Known
compounds 2a,с,20 2b,d,21 and 2h22 were synthesized
according to published methods.
2-(3-Cyano-5-hydroxy-4,5-diphenyl-1,5-dihydro-2H-
pyrrol-2-ylidene)malononitrile (3а). Yield 181 mg (56%),
yellow powder, mp 230–231°С (decomp.) (mp 215–220°С17).
1
IR spectrum, ν, cm–1: 3466 (OH), 2219 (C≡N). H NMR
spectrum, δ, ppm: 7.29–7.36 (3H, m, H Ph); 7.44–7.54 (5H,
m, H Ph); 7.84–7.87 (2H, m, H Ph); 8.07 (1H, s, OH); 11.22
(1H, s, NH). 13C NMR spectrum, δ, ppm: 46.5; 96.1; 102.7;
112.7; 113.7; 114.8; 125.7; 128.3; 128.6; 128.8; 129.0;
132.8; 137.1; 160.8; 170.8. Mass spectrum, m/z (Irel, %): 324
[M]+ (52). Found, %: C 74.11; H 3.70; N 17.30.
C20H12N4O. Calculated, %: C 74.06; H 3.73; N 17.27.
2-[3-Cyano-4-(2,5-dimethylthiophen-3-yl)-5-hydroxy-
5-phenyl-1,5-dihydro-2H-pyrrol-2-ylidene]malononitrile
(3b). Yield 229 mg (64%), yellow powder, mp 180–181°С
(decomp.). IR spectrum, ν, cm–1: 3463 (OH), 2221 (C≡N).
1H NMR spectrum, δ, ppm: 2.27 (3H, s, CH3); 2.34 (3H, s,
CH3); 6.59 (1H, s, H thiophene); 7.32–7.36 (3H, m, H Ph);
7.38–7.42 (2H, m, H Ph); 7.81 (1H, s, OH); 11.08 (1H, s,
NH). 13C NMR spectrum, δ, ppm: 14.6; 15.2; 46.2; 95.8;
103.69; 112.1; 113.7; 114.7; 123.8; 125.6; 126.6; 128.3;
128.9; 136.3; 137.0; 143.1; 161.1; 169.3. Mass spectrum,
m/z (Irel, %): 358 [M]+ (84). Found, %: C 67.05; H 3.91;
N 15.64. C20H14N4OS. Calculated, %: C 67.02; H 3.94;
N 15.63.
Synthesis of 3-aryl-4-oxoalkane-1,1,2,2-tetracarbo-
nitriles 2e–g (General method). TCNE (0.64 g, 5 mmol)
and two drops of concentrated HCl (0.10–0.15 g) were added
to a solution of the respective 2-arylethanone 1 (5 mmol) in
1,4-dioxane (20 ml). The formed colored solution was
stirred at 30–40°С for 2–3 min until complete dissolution
of TCNE. Then the reaction mixture was stirred at room
temperature for 2–3 days, controlling the presence of TCNE
(formation of a blue complex with hydroquinone). After no
more TCNE could be detected, the mixture was cooled to 0–
5°С, cold water (100 ml) was added, and the mixture stirred
vigorously until homogeneous suspension was obtained. The
formed precipitate was filtered off, washed on filter with
water and a cold mixture of water–isopropanol, 5:1.
4-(2,5-Dimethylthiophen-3-yl)-4-oxo-3-(thiophen-2-yl)-
butane-1,1,2,2-tetracarbonitrile (2e). Yield 1.38 g (76%),
white powder, mp 99–100°С (decomp.). IR spectrum,
ν, cm–1: 2244 (C≡N), 1701 (C=O). H NMR spectrum,
1
δ, ppm: 2.31 (3H, s, CH3); 2.71 (3H, s, CH3); 5.80 (1H, s,
CH); 5.97 (1H, s, CH); 7.18–7.21 (2H, m, H thiophene);
7.49–7.51 (1H, m, H thiophene); 7.74–7.77 (1H, m, H thio-
phene). Found, %: C 59.34; H 3.30; N 15.39. C18H12N4OS2.
Calculated, %: C 59.32; H 3.32; N 15.37.
2-[3-Cyano-5-hydroxy-4,5-bis(2,5-dimethylthiophen-
3-yl)-1,5-dihydro-2H-pyrrol-2-ylidene]malononitrile
(3c). Yield 270 mg (69%), yellow powder, mp 182–183°С
(decomp.). IR spectrum, ν, cm–1: 3472 (OH), 2218 (C≡N).
1H NMR spectrum, δ, ppm: 2.21 (3H, s, CH3); 2.28 (3H, s,
CH3); 2.32 (3H, s, CH3); 2.38 (3H, s, CH3); 6.57 (1H, s,
H thiophene); 6.59 (1H, s, H thiophene); 7.58 (1H, s, OH);
11.12 (1H, s, NH). Mass spectrum, m/z (Irel, %): 392 [M]+
(100). Found, %: C 61.24; H 4.19; N 14.28. C20H16N4OS2.
Calculated, %: C 61.20; H 4.11; N 14.27.
3-(4-Bromophenyl)-4-oxopentane-1,1,2,2-tetracarbo-
nitrile (2f). Yield 1.55 g (91%), white powder, mp 144–
145°С (decomp.). IR spectrum, ν, cm–1: 2251 (C≡N), 1698
1
(C=O). H NMR spectrum, δ, ppm: 2.24 (3H, s, CH3); 5.25
(1H, s, CH); 5.60 (1H, s, CH); 7.50–7.53 (2H, m, H Ar); 7.81–
7.84 (2H, m, H Ar). Found, %: C 52.85; H 2.63; N 16.44.
C15H9BrN4O. Calculated, %: C 52.81; H 2.66; N 16.42.
4-Oxo-3,5-diphenylpentane-1,1,2,2-tetracarbonitrile
(2g). Yield 1.44 g (85%), white powder, mp 94–95°С
(decomp.). IR spectrum, ν, cm–1: 2248 (C≡N), 1697 (C=O).
1H NMR spectrum, δ, ppm (J, Hz): 3.80 (1H, d, J = 17.0,
CH2); 3.98 (1H, d, J = 17.0, CH2); 5.27 (1H, s, CH); 5.55
(1H, s, CH); 7.07–7.09 (2H, m, H Ph); 7.25–7.30 (3H, m,
H Ph); 7.54–7.56 (2H, m, H Ph); 7.62–7.66 (3H, m, H Ph).
Found, %: C 74.56; H 4.14; N 16.59. C21H14N4O.
Calculated, %: C 74.54; H 4.17; N 16.56.
2-[5-(5-Chloro-2-methylthiophen-3-yl)-3-cyano-4-(2,5-di-
methylthiophen-3-yl)-5-hydroxy-1,5-dihydro-2H-pyrrol-
2-yl-idene]malononitrile (3d). Yield 305 mg (74%), yellow
powder, mp 202–203°С (decomp.). IR spectrum, ν, cm–1:
1
3464 (OH), 2213 (C≡N). H NMR spectrum, δ, ppm: 2.24
(3H, s, CH3); 2.34 (3H, s, CH3); 2.39 (3H, s, CH3); 6.69
(1H, s, H thiophene); 6.92 (1H, s, H thiophene); 7.75 (1H,
s, OH); 11.05 (1H, s, NH). 13C NMR spectrum, δ, ppm:
13.7; 14.6; 15.3; 46.7; 95.1; 103.7; 111.9; 113.5; 114.5;
123.0; 123.8; 125.9; 127.0; 131.3; 136.7; 137.3; 143.5;
160.7; 167.5. Mass spectrum, m/z (Irel, %): 412 [M(Cl35)]+
(14). Found, %: C 55.29; H 3.14; N 13.56. C19H13ClN4OS2.
Calculated, %: C 55.27; H 3.17; N 13.57.
Synthesis of 2-(4-aryl-3-cyano-5-hydroxy-1,5-dihydro-2H-
pyrrol-2-ylidene)malononitriles 3a–h (General method).
AcONH4 (231 mg, 3 mmol) was added to a suspension of
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Chemistry of Heterocyclic Compounds 2017, 53(9), 1057–1060
2-[3-cyano-5-(2,5-dimethylthiophen-3-yl)-5-hydroxy-
References
4-(thiophen-2-yl)-1,5-dihydro-2H-pyrrol-2-ylidene]malono-
nitrile (3e). Yield 266 mg (73%), yellow powder, mp 159–
160°С (decomp.). IR spectrum, ν, cm–1: 3470 (OH), 2216
(C≡N). 1H NMR spectrum, δ, ppm: 2.28 (3H, s, CH3); 2.32
(3H, s, CH3); 6.67 (1H, s, H thiophene); 7.33–7.35 (1H, m,
H thiophene); 7.82 (1H, s, OH); 7.99–8.00 (1H, m, H thio-
phene); 8.20–8.22 (1H, m, H thiophene); 11.11 (1H, s, NH).
Mass spectrum, m/z (Irel, %): 364 [M]+ (100). Found, %:
C 59.33; H 3.30; N 15.40. C18H12N4OS2. Calculated, %:
C 59.32; H 3.32; N 15.37.
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Yield 269 mg (79%), yellow powder, mp 195–196°С (decomp.).
1
IR spectrum, ν, cm–1: 3468 (OH), 2225 (C≡N). H NMR
spectrum, δ, ppm: 1.49 (3H, s, CH3); 7.36 (1H, s, OH); 7.86–
7.89 (2H, m, H Ar); 7.94–7.97 (2H, m, H Ar); 10.81 (1H, s,
NH). 13C NMR spectrum, δ, ppm: 24.1; 45.6; 94.6; 102.3;
112.3; 113.6; 115.0; 126.9; 130.5; 132.5; 137.1; 160.2; 170.3.
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[M(Br79)]+ (19). Found, %: C 52.84; H 2.62; N 16.47.
C15H9BrN4O. Calculated, %: C 52.81; H 2.66; N 16.42.
2-(5-Benzyl-3-cyano-5-hydroxy-4-phenyl-1,5-dihydro-2H-
pyrrol-2-ylidene)malononitrile (3g). Yield 196 mg (58%),
yellow powder, mp 175–176°С (dec.). IR spectrum, ν, cm–1:
3465 (OH), 2209 (C≡N). 1H NMR spectrum, δ, ppm
(J, Hz): 3.12 (1H, d, J = 13.4, CH2); 3.41 (1H, d, J = 13.4,
CH2); 6.73–6.75 (2H, m, H Ph); 7.16–7.22 (4H, m, H Ph);
7.51–7.58 (2H, m, H Ph); 7.79 (1H, s, OH); 8.03–8.06 (2H,
m, H Ph); 10.95 (1H, s, NH). 13C NMR spectrum, δ, ppm:
43.3; 45.1; 97.2; 101.7; 112.1; 113.2; 114.7; 127.4; 128.0;
128.6; 128.9; 129.5; 129.7; 132.8; 133.6; 160.2; 170.6.
Mass spectrum, m/z (Irel, %): 338 [M]+ (36). Found, %:
C 74.57; H 4.15; N 16.59. C21H14N4O. Calculated, %:
C 74.54; H 4.17; N 16.56.
2-[3-Cyano-5-(2,5-dimethylthiophen-3-yl)-5-hydroxy-
4-phenyl-1,5-dihydro-2H-pyrrol-2-ylidene]malononitrile
(3h). Yield 193 mg (54%), yellow powder, mp 168–169°С
(decomp.). IR spectrum, ν, cm–1: 3469 (OH), 2214 (C≡N).
1H NMR spectrum, δ, ppm: 2.26 (6H, m, 2CH3); 6.65 (1H,
s, H thiophene); 7.50–7.54 (2H, m, H Ph); 7.56–7.60 (1H,
m, H Ph); 7.80 (1H, s, OH); 7.88–7.91 (2H, m, H Ph);
11.20 (1H, s, NH). 13C NMR spectrum, δ, ppm: 13.7; 14.5;
46.2; 95.5; 101.6; 112.5; 113.5; 114.6; 125.5; 126.8; 128.1;
128.7; 128.9; 132.9; 134.4; 134.7; 160.1; 170.1. Mass
spectrum, m/z (Irel, %): 358 (62) [M]+. Found, %: C 67.04;
H 3.91; N 15.67. C20H14N4OS. Calculated, %: C 67.02;
H 3.94; N 15.63.
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The study was carried out with the financial support of
the Russian Foundation for Basic Research (project no 16-
33-60156 mol_a_dk).
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