Reactions of naphthalen-2-ol Mannich bases with β-aminoacrylonitriles and methyl 3-morpholinoacrylate

Article abstract of DOI:10.1007/s10593-020-02695-4

[InlineMediaObject not available: see fulltext.]3-Amino-2,3-dihydro-1H-benzo[f]chromenes and 2-[(2-hydroxynaphthalen-1-yl)methyl]-2,3-dihydro-1H-benzo[f]chromene-2-carbonitriles were obtained via the reaction of naphthalen-2-ol Mannich bases with β-aminoa

Full text of DOI:10.1007/s10593-020-02695-4

DOI 10.1007/s10593-020-02695-4
Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
Reactions of naphthalen-2-ol Mannich bases
with β-aminoacrylonitriles and methyl 3-morpholinoacrylate
Anton V. Lukashenko1, Dmitry V. Osipov1,
Vitaly А. Osyanin1*, Yuri N. Klimochkin1
1 Samara State Technical University,
244 Molodogvardeyskaya St., Samara 443100, Russia; е-mail: VOsyanin@mail.ru
Submitted February 4, 2020
Accepted March 3, 2020
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2020, 56(5), 529–536
3-Amino-2,3-dihydro-1H-benzo[f]chromenes and 2-[(2-hydroxynaphthalen-1-yl)methyl]-2,3-dihydro-1H-benzo[f]chromene-2-carbo-
nitriles were obtained via the reaction of naphthalen-2-ol Mannich bases with β-aminoacrylonitriles and methyl 3-morpholinoacrylate as
products of [4+2] cycloaddition of push-pull olefins to the corresponding 1,2-naphthoquinone 1-methide. The reaction of 3-amino-
3-phenylacrylonitrile with Mannich bases leads to the formation of 1,4-dihydropyridine-3,5-dicarbonitriles.
Keywords: 2,3-dihydro-1H-benzo[f]chromene, 1,4-dihydropyridine, naphthalen-2-ol, 1,2-naphthoquinone 1-methide, push-pull olefin,
Diels–Alder reaction.
Push-pull enamines R2N–C=C–EWG, where EWG is an
electron-withdrawing group, are widely used in the
synthesis of heterocycles. This is due to the high
polarization1 of the C=C bond and the presence of several
nonequivalent electrophilic and nucleophilic centers within
the structure.2 At the same time, similar enamines are
rarely used as two-carbon synthons for the construction of
six-membered heterocycles.3
One of the main reactions that o-quinone methides enter
into is the Diels–Alder reaction.4 The products of this reac-
tion, substituted chromanes and chromenes, in many cases
attract much more interest than noncondensed 4H-pyrans.5
To date, no method to synthesize chromane systems with a
wide range of substituents has been developed, and the
existing methods are often applicable only to a narrow
range of substrates and require hard-to-access and
expensive reagents and catalysts. At the same time,
however, the presence of diverse functional groups in such
systems makes them promising precursors for both further
chemical transformations and research in medicinal
chemistry. In addition, the relevance of developing novel
methods for the synthesis of chromane and chromene
derivatives is dictated by the presence of a large number of
natural and biologically active compounds among them.6
When trying to carry out the reaction between
1-[(dimethylamino)methyl]naphthalen-2-ol (1a) and various
β-aminoacrylonitriles 2a–e in aprotic solvents (MeCN,
1,4-dioxane) or in AcOH, unsatisfactory results were
obtained. In aprotic solvents, the reaction does not take
place, whereas in AcOH a complex mixture of unidentified
products forms. At the same time, heating equimolar
amounts of β-aminoacrylonitriles 2a–e and Mannich base
1a under reflux in DMF for 1 h (method I) afforded
mixtures of benzochromane-2-carbonitriles 3a–d and 2-[(2-
hydroxynaphthalen-1-yl)methyl]-2,3-dihydro-1H-benzo[f]-
chromene-2-carbonitriles 4a–d, which were preparatively
separated by column chromatography (Table 1).
When 2 equiv of Mannich base 1a was subjected to a
reaction with enaminonitriles 2a–c (Table 1, method II),
the yields of products 3a–c decrease as expected, but
benzochromanes 3a–c do not disappear completely, even
increasing the reaction time to 12 h. At the same time, upon
a slow addition of an equimolar amount of Mannich base
1a to a DMF solution of nitrile 2a–d heated to 150°С
(method III), benzochromane-2-carbonitriles 3a–d
selectively are formed.
The reaction mechanism, apparently, involves the
generation of reactive 1,2-naphthoquinone 1-methide A via
0009-3122/20/56(5)-0529©2020 Springer Science+Business Media, LLC
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Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
β-position of the dihydropyran ring3a–e is not observed in
this case. The absence of product 4e with diphenylamino
group can be explained by steric factors.
Table 1. Yields of the products of the reaction of Mannich base
1a with β-aminoacrylonitriles 2a–e
CN
NR2
NMe2
OH
Benzochromanes 4b–d were also obtained in high yields
upon heating 3-amino-2,3-dihydro-1H-benzo[f]chromene-
2-carbonitriles 3b–d with an equimolar amount of Mannich
base 1a under reflux in DMF in the presence of 1 equiv of
piperidine as the base facilitating the opening of the
dihydropyran ring in compounds 3b–d (Table 1, method V).
The more volatile NHMe2 generated from Mannich base 1a
turned out to be less effective, and as a result of prolonged
heating under reflux in DMF in the absence of piperidine,
product 4b was isolated only in 23% yield (method IV).
O
3a–e
+
1a
+
Method I–III
– NHMe2
NC
CN
NHR2
2a–e
OH
O
NR2
4a–d
Scheme 1
CN
N
Method IV
+
1a
4b
O
3b
Method V
4b–d
3b–d +
1a
2–4 a NR2 = NEt2, b NR2 = pyrrolidin-1-yl, c NR2 = piperidin-1-yl,
d NR2 = morpholin-4-yl, e NR2 = NPh2
Product yields, %
Method*
3a / 4a
41 / 18
24 / 54
72 / –
–
3b / 4b
43 / 17
29 / 51
80 / –
3c / 4c
46 / 15
30 / 48
83 / –
–
3d / 4d
52 / 16
–
3e / 4e
I
78 / –
II
–
–
–
–
A similar reaction of methyl 3-morpholinoacrylate (5)
with naphthalen-2-ol Mannich bases 1а–с leads to the
formation of cycloadducts 6a–c containing no products
with two naphthalene fragments as impurities even when
using 2 equiv of Mannich base 1а–с (Scheme 2).
III
IV
V
84 / –
–
– / 23
–
– / 81
– / 77
– / 74
* Method I: naphthalen-2-ol 1а (300 mg, 1.5 mmol), nitrile 2a–e (1.5 mmol),
DMF, reflux, 1 h.
Method II: naphthalen-2-ol 1а (600 mg, 3 mmol), nitrile 2a–c (1.5 mmol),
DMF, reflux, 1 h.
Scheme 2
Method III: naphthalen-2-ol 1а (300 mg, 1.5 mmol) was added to a solu-
tion of nitrile 2a–d (1.5 mmol) in DMF at 150°С over 30 min.
Method IV: benzochromane 3b (278 mg, 1.0 mmol), naphthalen-2-ol 1а
(200 mg, 1.0 mmol), DMF, reflux, 12 h.
Method V: benzochromane 3b–d (1.0 mmol ), naphthalen-2-ol 1а (200 mg,
1.0 mmol), piperidine (0.1 ml, 1.0 mmol), DMF, reflux, 1 h.
thermolysis of Mannich base 1a followed by [4+2] cyclo-
addition of enaminonitrile 2a–e to it as the dienophile. It
should be noted that push-pull enaminonitriles rarely play
the role of the dienophile.3f Benzochromanes 4a–d are
probably formed as a result of the opening of the
dihydropyran ring by the action of NHMe2, the source of
which is the starting Mannich base 1a, and addition of
another molecule of 1,2-naphthoquinone 1-methide A to
the resulting push-pull olefin B. Moreover, the second
equivalent of 1,2-naphthoquinone 1-methide A, necessary
for the formation of product 4a–d, is most likely formed
directly from Mannich base 1a, rather than as a result of
retro-Diels–Alder reaction from cycloadduct 3a–d (Scheme 1).
It is interesting to note that the elimination of the secondary
amine from the initial cycloadducts characteristic of
derivatives containing an acyl, formyl, or nitro group in the
The IR spectra of compounds 3a–е contain a low-
intensity absorption band of the CN group in the region of
2241–2251 cm–1, whereas the absorption band of the C=O
group in the spectra of compounds 6a–c appears at 1732–
1734 cm–1. In the 1H NMR spectra of compounds 3a–d and
6a–c, the 3-CH proton signal appears at 4.86–5.01 ppm in
the form of a doublet with 3JH(2)–H(3) = 9.2 Hz (in the case of
compound 3е, a doublet is observed at 4.74 ppm with
3JH(2)–H(3) = 9.8 Hz), which is typical for trans-2,3-disubsti-
tuted chromanes.7 The formation of such diastereomers is
most likely a consequence of the trans configuration of the
starting olefins. The signals of the 1-CH2 and 2-CH protons
in the spectra of compounds 3a–d and 6a–c are observed in
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Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
Figure 1. Molecular structures of compounds 4b,c with atoms represented as thermal vibration ellipsoids of 30% probability (dotted
lines indicate intramolecular hydrogen bonds).
the 3.15–3.72 ppm range in the form of complex multi-
plets. In the 13C NMR spectra of compounds 3a–d and 6a–c,
the С-1 atom resonates at 26.3–27.9 ppm, the С-2 atom –
at 28.7–30.0 ppm (in the case of nitriles 3a–e), and 40.9–
42.0 ppm (in the case of esters 6a–c), whereas the signal in
the 85.3–93.6 ppm range can be attributed to the C-3 atom.
In the 13C NMR spectra of esters 6a–c, the carbon atom of
the C=O group appears at 172.9–175.6 ppm; in the spectra
of compounds 3a–e, the carbon atom of the CN group is
observed in the region of 119.2–119.9 ppm.
Ac2O to the C=C bond in the absence of a catalyst.8 The
gas chromato-mass spectrometry data of the reaction
product of compounds 1a and 2d indicate the formation of
benzochromane 7 in the form of a mixture of geometric
isomers 7a,b in about 1:1 ratio, which indicates the low
selectivity of the attack by the acetate anion on the cationic
intermediate D from opposite sides. It was not possible to
preparatively separate the isomer mixture.
The IR spectrum of 2-acetyl-2-cyano-2,3-dihydro-
1H-benzo[f]chromen-3-yl acetate (7) contains an intense
absorption band of the CN group at 2222 cm–1 and
absorption bands of the C=O groups at 1789 and 1751 cm–1.
1H and 13C NMR spectra of isomers 7a,b are identical. The
protons 1-CH2 and 3-CH appear as doublets at 3.97 and
7.84 ppm, respectively (4JH(1)–H(3) = 1.4 Hz). In the 13C NMR
spectrum, the C-1 carbon atom resonates at 23.4 ppm, the
signals of the carbon atoms of the C=O groups appear at
165.5 and 169.5 ppm. The mass spectra of isomers 7a,b are
also almost identical and contain the molecular ion (m/z
309) and a number of fragmentation ions characteristic of
the benzochromane fragment. The gas chromatogram
contains two peaks with different retention times (13.25
and 13.32 min).
Upon heating 3-amino-3-phenylacrylonitrile (8) with
naphthalen-2-ol derivatives 1a,d,e, 1,4-dihydropyridines 9a–c
are formed instead of benzochromanes or benzochromenes.
Apparently, Mannich base 1a,d,e undergoes the retro-
Mannich reaction, leading to naphthalen-2-ol (10), which
can be detected in the reaction mixture, and the iminium
cation. The iminium cation adds to the conjugated system
of enaminonitrile 8 with the formation of intermediate E,
which then reacts with another molecule of the push-pull
olefin 8, forming the protonated form of dicyanodiene
diamine F. Subsequent heterocyclization and deamination
lead to 1,4-dihydropyridines 9a–c (Scheme 4). A similar
The IR spectra of benzochromanes 4a–d contain a
number of absorption bands in the 3000–3400 cm–1 range,
corresponding to vibrations of O–H bonds, and a weak-
intensity absorption band in the region of 2232–2236 cm–1,
1
corresponding to the CN group. In the H NMR spectra of
compounds 4a–d, OH protons and 3-CH protons resonate
as singlets in the 10.15–11.22 and 4.29–5.26 ppm ranges,
respectively. The 13C NMR spectra of compounds 4a–d are
characterized by the signals of two CH2 groups at
correspondingly 28.8–30.4 and 35.5–36.8 ppm, as well as
C-2 and C-3 atoms at 39.2–40.9 and 91.2–95.4 ppm,
respectively.
The structures of benzochromanes 4b,c were confirmed
by X-ray structural analysis data (Fig. 1). According to
X-ray structural analysis data, an intramolecular hydrogen
bond is formed between the hydrogen atom of the OH
group and the nitrogen atom of the amino group, the length
of which is 2.051 Å (compound 4b) and 1.935 Å
(compound 4c).
A slightly different type of transformation is observed
upon heating of 1-[(dimethylamino)methyl]naphthalen-2-ol
(1a) and enaminonitrile 2d in Ac2O: the resulting
cycloadduct C eliminates a molecule of morpholine, and
then Ac2O adds at the C=C bond (Scheme 3). There are
practically no examples in the literature of the addition of
531

Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
Scheme 3
Scheme 4
route is described in the literature for the synthesis of
2,6-diphenyl-1,4-dihydropyridine-3,5-dicarbonitriles from
3-amino-3-phenylacrylonitrile in comparable yields,
including the use of different aldehydes as electrophiles.9
Conducting the reaction in boiling DMF leads to a complex
mixture of unidentifiable products.
The IR spectra of 2,6-diphenyl-1,4-dihydropyridine-3,5-di-
carbonitriles 9a–c contain absorption bands of the N–H
bond in the region of 3213–3298 cm–1 and of the С≡N
bonds in the 2198–2206 cm–1 region. In the 13C NMR spectra,
the carbon atoms of the CN groups resonate at 119.1–
120.0 ppm, and the signals of the C-3,5 carbon atoms
associated with them appear in the 79.8–83.9 ppm range.
To conclude, we have shown that N,N-disubstituted
β-enaminonitriles and esters act as dienophiles in reactions
with 1,2-naphthoquinone 1-methide precursors, which leads
to the formation of benzochromane derivatives.
Experimental
IR spectra were registered on a Shimadzu IR Affinity-1
spectrometer with a Specac Diamond ATR GS10800-B
1
attachment. H, 13C NMR spectra (400 and 100 MHz,
1
1
respectively), as well as COSY, H–13C HMBC, H–13C
HMQC spectra (compound 7) and DEPT experiments were
acquired on a JEOL JNM-ECX400 spectrometer in
DMSO-d6 (compounds 4b–d, 6a,c, and 9b,c) or CDCl3
(compounds 3a–e, 4a, 6b, 7, and 9a), using the residual
1
solvent signals (DMSO-d6: 2.50 ppm for Н, 39.5 ppm for
1
13С nuclei; СHCl3: 7.26 ppm for Н, 77.2 ppm for 13С
nuclei) as internal standard. Mass spectra were recorded on
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Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
a Finnigan Trace DSQ GC-MS system (EI ionization, 70 eV;
52.3 (2CH3СH2); 86.1 (C-3); 111.6; 119.5 (CH); 119.9
(CN); 120.2 (CH); 123.6 (CH); 126.5 (CH); 128.8 (CH);
129.4 (CH); 129.8; 131.0; 152.1 (C-4a). Found, %:
C 77.20; H 7.26; N 9.88. C18H20N2O. Calculated, %:
C 77.11; H 7.19; N 9.99.
BPX-5MS column (0.32 mm × 30 m, stationary phase
thickness 0.25 μm); temperature program: 1 min at 80°С,
ramp to 350°С at 20°С/min rate, 5 min at 350°С; carrier
gas helium, 1.5 ml/min flow). Elemental analysis was
performed on a Euro Vector EA-3000 CHNS-analyzer.
Melting points were determined by the capillary method on
an SRS OptiMelt MPA100 apparatus. Merck Silica gel 60,
0.04–0.063 mm, was used for column chromatography.
TLC was performed on Merck Silica gel 60 F254 plates,
eluent CH2Cl2, visualization under UV light or in I2 vapor.
Mannich bases 1a–e,10 push-pull β-aminoacrylonitriles
2a–e,11 acrylate 5,12 and nitrile 813 were obtained by known
methods.
trans-3-(Pyrrolidin-1-yl)-2,3-dihydro-1H-benzo[f]chro-
mene-2-carbonitrile (3b). Yield 179 mg (43%, method I),
122 mg (29%, method II), 335 mg (80%, method III),
colorless crystals, mp 123–125°С. IR spectrum, ν, cm–1:
2245 (CN), 1620, 1601, 1510, 1468, 1406, 1246, 1180,
1
1115, 1020, 932, 816, 741. H NMR spectrum, δ, ppm
(J, Hz): 1.52–1.60 (4H, m, 2СH2); 3.18–3.22 (4H, m,
2СH2N); 3.25–3.34 (2H, m, 1-CH2); 3.61–3.71 (1H, m,
2-CН); 4.86 (1H, d, J = 9.2, 3-CH); 7.14 (1H, d, J = 8.8,
H Ar); 7.41–7.45 (1H, m, H Ar); 7.55–7.60 (1H, m, H Ar);
7.64 (1H, d, J = 8.4, H Ar); 7.74–7.79 (2H, m, H Ar).
13C NMR spectrum, δ, ppm: 22.5 (2CH2); 27.9 (C-1); 29.3
(C-2); 51.4 (2СH2N); 88.9 (C-3); 111.3; 118.9 (CH); 119.8
(CN); 120.6 (CH); 123.1 (CH); 127.2 (CH); 128.8 (CH);
129.8 (CH); 129.9; 131.5; 153.4 (C-4a). Found, %:
C 77.59; H 6.59; N 9.93. C18H18N2O. Calculated, %:
C 77.67; H 6.52; N 10.06.
Synthesis of 2,3-dihydro-1H-benzo[f]chromene-2-carbo-
nitriles 3a–e and 2-[(2-hydroxynaphthalen-1-yl)methyl]-
2,3-dihydro-1H-benzo[f]chromene-2-carbonitriles
4a–d
(General procedure). Method I. A mixture of β-amino-
acrylonitrile 2a–e (1.5 mmol) and Mannich base 1a (300 mg,
1.5 mmol) in DMF (10 ml) was heated under reflux for 1 h.
DMF was evaporated under reduced pressure, and the
residue was separated by column chromatography (SiO2,
eluent CHCl3–EtOH, 15:1), followed by recrystallization
from EtOH (compounds 3a–e) or EtOH–DMF, 5:1
(compounds 4a–d).
trans-3-(Piperidin-1-yl)-2,3-dihydro-1H-benzo[f]chro-
mene-2-carbonitrile (3c). Yield 202 mg (46%, method I),
131 mg (30%, method II), 364 mg (83%, method III),
colorless crystals, mp 149–151°С. IR spectrum, ν, cm–1:
2247 (CN), 1622, 1601, 1584, 1514, 1491, 1460, 1433,
1404, 1290, 1250, 1186, 1155, 1117, 1069, 1018, 945, 868,
822, 754. 1H NMR spectrum, δ, ppm (J, Hz): 2.20–2.23 (2H,
m, СH2СH2СH2); 2.35–2.38 (4H, m, СH2СH2СH2); 3.30–3.47
(2H, m, 1-CH2); 3.60–3.65 (1H, m, 2-CН); 3.78–3.82 (4H,
m, 2СH2N); 4.72 (1H, d, J = 9.2, 3-CH); 7.02 (1H, d,
J = 8.8, H Ar); 7.35–7.39 (1H, m, H Ar); 7.49–7.54 (1H,
m, H Ar); 7.66 (1H, d, J = 8.8, H Ar); 7.70 (1H, d, J = 8.4,
H Ar); 7.76 (1H, d, J = 7.6, H Ar). 13C NMR spectrum,
δ, ppm: 25.3 (CH2CH2CH2); 26.8 (CH2CH2CH2); 27.9
(C-1); 28.7 (C-2); 55.8 (2СH2N); 86.5 (C-3); 111.0; 118.9
(CH); 119.5 (CN); 121.4 (CH); 124.0 (CH); 127.2 (CH);
129.1 (CH); 129.4 (CH); 130.0; 132.4; 151.2 (C-4a).
Found, %: C 78.10; H 6.99; N 9.43. C19H20N2O.
Calculated, %: C 78.05; H 6.90; N 9.58.
Method II. A mixture of β-aminoacrylonitrile 2a–c
(1.5 mmol) and Mannich base 1a (600 mg, 3.0 mmol) in
DMF (15 ml) was heated under reflux for 1 h. Isolation and
purification of products was carried out similarly to
method I.
Method III. A solution of Mannich base 1a (300 mg,
1.5 mmol) in DMF (5 ml) was added dropwise with stirring
to a solution of β-aminoacrylonitrile 2a–d (1.5 mmol) in
DMF (10 ml) at 150°С over 30 min. DMF was evaporated
under reduced pressure, the residue was dissolved in EtOH
(10 ml), and the mixture was kept at –20°С for 24 h. The
precipitate was filtered off and recrystallized from EtOH.
Method IV. A mixture of nitrile 3b (280 mg, 1.0 mmol)
and Mannich base 1a (200 mg, 1.0 mmol) in DMF (10 ml)
was heated under reflux for 12 h. DMF was evaporated
under reduced pressure, and the residue was recrystallized
from EtOH.
trans-3-(Morpholin-4-yl)-2,3-dihydro-1H-benzo[f]chro-
mene-2-carbonitrile (3d). Yield 230 mg (52%, method I),
371 mg (84%, method III), colorless crystals, mp 152–154°С.
IR spectrum, ν, cm–1: 2241 (CN), 1622, 1599, 1404, 1275,
1231, 1190, 1118, 1069, 1022, 935, 860, 822, 812, 800,
Method V. A mixture of nitrile 3b–d (1.0 mmol),
Mannich base 1a (200 mg, 1.0 mmol), and piperidine
(0.1 ml, 1 mmol) in DMF (10 ml) was heated under reflux
for 1 h. Isolation and purification of the product was
carried out similarly to method IV.
1
768, 744. H NMR spectrum, δ, ppm (J, Hz): 2.84–2.91
trans-3-(Diethylamino)-2,3-dihydro-1H-benzo[f]chro-
mene-2-carbonitrile (3а). Yield 172 mg (41%, method I),
100 mg (24%, method II), 303 mg (72%, method III),
colorless crystals, mp 106–108°С. IR spectrum, ν, cm–1:
2251 (CN), 1626, 1601, 1516, 1435, 1406, 1398, 1358,
1294, 1275, 1231, 1190, 1109, 1076, 1020, 955, 935, 860,
(2H, m, СH2N); 3.03–3.09 (2H, m, СH2N); 3.32–3.52 (2H,
m, 1-CH2); 3.62–3.67 (1H, m, 2-CН); 3.77–3.86 (4H, m,
2СH2O); 4.74 (1H, d, J = 9.2, 3-CH); 7.05 (1H, d,
J = 9.0, H Ar); 7.37–7.41 (1H, m, H Ar); 7.50–7.55 (1H,
m, H Ar); 7.67 (1H, d, J = 8.9, H Ar); 7.71 (1H, d, J = 8.2,
H Ar); 7.78 (1H, d, J = 7.8, H Ar). 13C NMR spectrum, δ, ppm:
27.8 (C-1); 28.7 (C-2); 47.8 (2СH2N); 67.0 (2СH2O); 91.0
(C-3); 110.0; 118.6 (CH); 119.2 (CN); 121.7 (CH); 124.2
(CH); 127.2 (CH); 128.7 (CH); 129.2 (CH); 129.3; 132.0;
151.8 (C-4a). Found, %: C 73.38; H 6.08; N 9.40.
C18H18N2O2. Calculated, %: C 73.45; H 6.16; N 9.52.
1
812, 802, 770, 746. H NMR spectrum, δ, ppm (J, Hz):
1.29 (6H, t, J = 7.2, 2CH3CH2); 3.15–3.30 (2H, m, 1-CH2);
3.40 (4H, q, J = 7.2, 2CH3CH2); 3.58–3.72 (1H, m, 2-CН);
5.01 (1H, d, J = 9.2, 3-CH); 7.10 (1H, d, J = 8.8, H Ar);
7.41–7.45 (1H, m, H Ar); 7.50–7.54 (1H, m, H Ar); 7.65
(1H, d, J = 9.1, H Ar); 7.71–7.76 (2H, m, H Ar). 13C NMR
spectrum, δ, ppm: 13.0 (2CH3); 27.4 (C-1); 29.3 (C-2);
trans-3-(Diphenylamino)-2,3-dihydro-1H-benzo[f]chro-
mene-2-carbonitrile (3e). Yield 440 mg (78%, method I),
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Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
colorless crystals, mp 225–227°С. IR spectrum, ν, cm–1:
(2R*,3R*)-2-[(2-Hydroxynaphthalen-1-yl)methyl]-
3-(piperidin-1-yl)-2,3-dihydro-1H-benzo[f]chromene-
2-carbonitrile (4c). Yield 102 mg (15%, method I), 322 mg
(48%, method II), 346 mg (77%, method V), colorless
crystals, mp 235–237°С. IR spectrum, ν, cm–1: 3200–3000
(OH), 2234 (CN), 1620, 1597, 1468, 1408, 1281, 1215,
1180, 1161, 1134, 1094, 1082, 997, 968, 824, 810, 746.
1H NMR spectrum, δ, ppm (J, Hz): 1.51–1.55 (2H, m,
СH2СH2СH2); 1.64–1.69 (4H, m, СH2СH2СH2); 2.84–2.87
(4H, m, 2СH2N); 3.22 (1H, d, J = 16.7, 1-СHA); 3.39 (1H,
d, J = 14.2, СHAAr); 3.69 (1H, d, J = 16.7, 1-СHB); 3.92
(1H, d, J = 14.2, СHBAr); 5.00 (1H, s, 3-CH); 7.10 (1H, d,
J = 8.9, H Ar); 7.25–7.34 (3H, m, H Ar); 7.37–7.52 (3H,
m, H Ar); 7.71 (1H, d, J = 9.0, H Ar); 7.76 (1H, d, J = 8.9,
H Ar); 7.79–7.82 (2H, m, H Ar); 8.18 (1H, d, J = 8.7, H Ar);
10.15 (1H, s, OH). 13C NMR spectrum, δ, ppm: 24.6
(CH2CH2CH2); 26.2 (CH2CH2CH2); 28.8 (СH2); 36.5 (СH2);
39.2 (C-2); 52.8 (2СH2N); 95.4 (C-3); 111.4; 113.8; 118.7
(CH); 118.9 (CH); 121.6 (CH); 122.1; 123.0 (CH); 124.0
(CH); 124.2 (CH); 126.6 (CH); 127.5 (CH); 128.8; 129.0
(2CH); 129.1 (CH, C Ar); 129.6 (CH); 132.4; 134.7; 152.3
(C-4a); 154.8 (C–OH). Found, %: C 80.36; H 6.33; N 6.14.
C30H28N2O2. Calculated, %: C 80.33; H 6.29; N 6.25.
(2R*,3R*)-2-[(2-Hydroxynaphthalen-1-yl)methyl]-
3-(morpholin-4-yl)-2,3-dihydro-1H-benzo[f]chromene-
2-carbonitrile (4d). Yield 108 mg (16%, method I), 325 mg
(48%, method II), 335 mg (74%, method V), colorless
crystals, mp 238–240°С. IR spectrum, ν, cm–1: 3400–3000
(OH), 2941, 2862, 2236 (CN), 1620, 1599, 1510, 1468,
1400, 1285, 1225, 1157, 993, 864, 812, 771, 754, 746.
1H NMR spectrum, δ, ppm (J, Hz): 3.22–3.29 (5H, m,
2СH2N, 1-СHA); 3.42 (1H, d, J = 14.4, СHAAr); 3.61 (1H,
d, J = 16.4, 1-СHB); 3.85 (1H, d, J = 14.4, СHBAr); 3.91–
3.94 (4H, m, 2СH2O); 5.23 (1H, s, 3-CH); 7.06 (1H, d, J = 8.8,
H Ar); 7.22–7.32 (3H, m, H Ar); 7.41–7.48 (3H, m, H Ar);
7.68 (1H, d, J = 8.8, H Ar); 7.73 (1H, d, J = 8.8, H Ar);
7.75–7.79 (2H, m, H Ar); 8.16 (1H, d, J = 8.4, H Ar); 10.15
(1H, s, OH). 13C NMR spectrum, δ, ppm: 30.4 (СH2); 36.8
(СH2); 40.9 (C-2); 48.8 (2СH2N); 67.6 (2СH2O); 92.3 (C-3); 112.4;
115.0; 119.9 (CH); 120.1 (CH); 122.8 (CH); 122.9; 124.2
(CH); 125.3 (2CH); 127.0 (CH); 128.6 (CH); 130.0; 130.1
(CH); 130.2 (2CH); 130.3 (CH); 131.2; 133.6; 135.9; 153.6
(C-4a); 155.9 (C–OH). Found, %: C 77.38; H 5.87; N 6.20.
C29H26N2O3. Calculated, %: C 77.31; H 5.82; N 6.22.
2247 (CN), 1624, 1591, 1499, 1468, 1398, 1256, 1215,
1
1182, 1138, 1074, 955, 816, 762, 745, 700, 685. H NMR
spectrum, δ, ppm (J, Hz): 3.13 (1H, ddd, J = 11.7, J = 9.8,
J = 6.4, 2-CH); 3.50 (1H, dd, J = 16.5, J = 11.7) and 3.60
(1H, dd, J = 16.5, J = 6.4, 1-CH2); 6.01 (1H, d, J = 9.8,
3-CH); 7.13–7.19 (3H, m, H Ar); 7.31–7.43 (9H, m, H Ar);
7.51–7.56 (1H, m, H Ar); 7.70 (2H, d, J = 8.7, H Ar); 7.79
(1H, d, J = 7.6, H Ar). 13C NMR spectrum, δ, ppm: 27.7 (C-1);
30.0 (C-2); 85.3 (C-3); 109.8; 118.8 (CH); 119.2 (CN); 121.7
(CH); 124.3 (CH); 124.7 (2CH); 124.8 (4CH); 127.3 (CH);
128.7 (CH); 129.2 (CH); 129.3; 129.5 (4CH); 131.9; 145.2
(2C-1 Ph); 151.4 (C-4a). Found, %: C 82.90; H 5.30; N 7.32.
C26H20N2O. Calculated, %: C 82.95; H 5.36; N 7.44.
(2R*,3R*)-3-(Diethylamino)-2-[(2-hydroxynaphthalen-
1-yl)methyl]-2,3-dihydro-1H-benzo[f]chromene-2-carbo-
nitrile (4a). Yield 118 mg (18%, method I), 354 mg (54%,
method II), colorless crystals, mp 223–225°С. IR spectrum,
ν, cm–1: 3400–3100 (OH), 2232 (СN), 1620, 1597, 1510,
1468, 1450, 1408, 1281, 1234, 1215, 1180, 1134, 1094,
1020, 997, 968, 860, 825, 810, 772, 764, 756, 748.
1H NMR spectrum, δ, ppm (J, Hz): 1.15–1.18 (6H, m,
2СH3CH2); 1.87 (2H, br. s, CH3CH2); 1.95 (2H, br. s,
CH3CH2); 3.13 (1H, d, J = 16.5) and 3.68 (1H, d, J = 16.5,
1-СH2); 3.75 (1H, d, J = 15.4) and 3.98 (1H, d, J = 15.4,
СH2Ar); 4.29 (1H, s, 3-CH); 7.07 (1H, d, J = 8.7, H Ar);
7.18 (1H, d, J = 8.7, H Ar); 7.29–7.44 (4H, m, H Ar); 7.62
(1H, d, J = 8.7, H Ar); 7.69–7.75 (3H, m, H Ar); 7.80 (1H,
d, J = 8.0, H Ar); 8.09 (1H, d, J = 8.4, H Ar); 11.22 (1H, s,
OH). 13C NMR spectrum, δ, ppm: 23.8 (2CH3); 29.6 (СH2);
35.5 (СH2); 39.8 (C-2); 46.9 (2CH3CH2); 92.2 (C-3);
110.5; 110.8; 118.1 (CH); 120.2 (CH); 121.6 (CH); 122.1;
122.8 (CH); 123.1 (CH); 124.1 (CH); 126.9 (CH); 127.0
(CH); 128.7 (CH); 129.1 (2CH); 129.2; 129.5; 130.6 (CH);
132.3; 135.0; 151.2 (C-4a); 155.5 (C–OH). Found, %:
C 79.85; H 6.55; N 6.33. C29H28N2O2. Calculated, %:
C 79.79; H 6.47; N 6.42.
(2R*,3R*)-2-[(2-Hydroxynaphthalen-1-yl)methyl]-
3-(pyrrolidin-3-yl)-2,3-dihydro-1H-benzo[f]chromene-
2-carbonitrile (4b). Yield 110 mg (17%, method I), 331 mg
(51%, method II), 100 mg (23%, method IV), 352 mg
(81%, method V), colorless crystals, mp 229–231°С.
IR spectrum, ν, cm–1: 3200–3000 (OH), 2234 (СN), 1622,
1597, 1468, 1402, 1285, 1225, 1209, 1180, 1157, 1084,
995, 951, 864, 824, 810, 772, 754, 746. 1H NMR spectrum,
δ, ppm (J, Hz): 1.83 (4H, br. s, 2СH2); 3.15–3.23 (4H, m,
2СH2N); 3.29 (1H, d, J = 16.7, 1-СHA); 3.44 (1H, d,
J = 14.2, СHAAr); 3.64 (1H, d, J = 16.7, 1-СHB); 3.88 (1H,
d, J = 14.2, СHBAr); 5.26 (1H, s, 3-CH); 7.09 (1H, d,
J = 8.9, H Ar); 7.24–7.35 (3H, m, H Ar); 7.43–7.50 (3H,
m, H Ar); 7.70 (1H, d, J = 8.9, H Ar); 7.75 (1H, d, J = 8.9,
H Ar); 7.78–7.81 (2H, m, H Ar); 8.21 (1H, d, J = 8.5,
H Ar); 10.17 (1H, s, OH). 13C NMR spectrum, δ, ppm: 24.7
(2CH2); 29.2 (СH2); 35.6 (СH2); 40.9 (C-2); 47.6 (2СH2N);
91.2 (C-3); 111.3; 113.8; 118.7 (CH); 118.9 (CH); 121.7
(CH); 121.8; 123.0 (CH); 124.1 (2CH); 126.5 (CH); 127.4
(CH); 128.8; 128.9 (CH); 129.0 (2CH); 129.1; 129.6 (CH);
132.4; 134.7; 152.1 (C-4a); 154.9 (C–OH). Found, %:
C 80.05; H 6.11; N 6.32. C29H26N2O2. Calculated, %:
C 80.16; H 6.03; N 6.45.
Synthesis of methyl trans-3-(morpholin-4-yl)-2,3-di-
hydro-1H-benzo[f]chromene-2-carboxylates 6a–c (General
method). A mixture of methyl 3-morpholinoacrylate (5)
(260 mg, 1.5 mmol) and Mannich base 1a–c (1.5 mmol) in
DMF (5 ml) was heated under reflux for 3 h. DMF was
evaporated under reduced pressure, and the residue was
recrystallized twice from EtOH.
Methyl trans-3-(morpholin-4-yl)-2,3-dihydro-1H-benzo-
[f]chromene-2-carboxylate (6a). Yield 360 mg (73%),
colorless crystals, mp 179–181°С. IR spectrum, ν, cm–1:
2845, 1732 (С=О), 1624, 1599, 1433, 1400, 1290, 1263,
1
1029, 1159, 1117, 953, 808, 764. H NMR spectrum,
δ, ppm (J, Hz): 2.65–2.72 (2H, m, СH2N); 2.96–3.03 (2H,
m, СH2N); 3.17–3.26 (2H, m, 1-CH2); 3.32–3.42 (1H, m,
2-CН); 3.49–3.61 (4H, m, 2СH2O); 3.70 (3H, s, СH3); 4.68
(1H, d, J = 9.2, 3-CH); 7.03 (1H, d, J = 8.9, H Ar); 7.31–
534

Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
7.36 (1H, m, H Ar); 7.45–7.50 (1H, m, H Ar); 7.68 (1H, d,
J = 8.5, Н-10). 13C NMR spectrum, δ, ppm: 20.4 (CH3);
21.3 (CH3); 23.4 (С-1); 98.9 (С-2); 117.6 (CN); 121.7
(C-5); 122.4 (C-10b); 123.5 (C-10); 125.7 (C-8); 127.0
(C-9); 129.1 (C-7); 129.4 (C-6); 132.0 (C-6a); 132.5
(C-10a); 146.2 (C-3); 147.4 (C-4a); 165.5 (C=O); 169.5
(C=O). Mass spectrum, m/z (Irel, %): 309 [M]+ (5), 268
[M–СH2=C=O]+ (30), 226 [M–2CH2=C=O]+ (95), 225
[M–CH2=C=O, –CH3CO]+ (80), 196 (42), 180 (22), 169
(24), 168 (34), 157 (65), 144 (90), 139 (52), 128 (65), 115 (48),
43 [CH3CO]+ (100). Found, %: C 69.82; H 4.98; N 4.42.
C18H15NO4. Calculated, %: C 69.89; H 4.89; N 4.53.
Synthesis of 2,6-diphenyl-1,4-dihydropyridine-3,5-di-
carbonitriles 9a–c (General method). A mixture of 3-amino-
3-phenylacrylonitrile (8) (150 mg, 1.0 mmol) and Mannich
base 1a,d,e (1.0 mmol) in AcOH (3 ml) was heated under
reflux for 1 h. The solution was cooled to room tempera-
ture, the precipitate was filtered off, washed with ice-cold
MeOH (1 ml), and air-dried at room temperature.
2,6-Diphenyl-1,4-dihydropyridine-3,5-dicarbonitrile (9a).
Yield 187 mg (66%), colorless crystals, mp 226–227°С
(mp 228–229°С (AcOH)9). IR spectrum, ν, cm–1: 3298 (NH),
3055, 2927, 2893, 2198 (CN), 1627 (C=C), 1477, 1276, 767.
1H NMR spectrum, δ, ppm: 3.57 (2H, s, 4-CH2); 6.07 (1H,
br. s, NH); 7.46–7.52 (6H, m, H Ph); 7.54–7.58 (4H, m, H Ph).
13C NMR spectrum, δ, ppm: 27.8 (C-4); 79.8 (C-3,5); 119.1
(2СN); 127.4 (4СH); 129.5 (4CH); 131.5 (2CH); 132.7 (2C);
149.4 (C-2,6). Found, %: C 80.60; H 4.65; N 14.72.
C19H13N3. Calculated, %: C 80.54; H 4.62; N 14.83.
2,4,6-Triphenyl-1,4-dihydropyridine-3,5-dicarbonitrile
(9b). Yield 250 mg (70%), colorless crystals, mp 305–307°С
(mp 305–306°С (AcOH)9). IR spectrum, ν, cm–1: 3213
(NH), 3097, 2962, 2777, 2198 (CN), 1639 (C=C), 1496,
1284, 694. 1H NMR spectrum, δ, ppm: 4.67 (1H, s, 4-CH);
7.45–7.51 (10H, m, H Ph); 7.58–7.63 (5H, m, H Ph); 10.12
(1H, s, NH). 13C NMR spectrum, δ, ppm: 42.9 (C-4); 83.9
(C-3,5); 120.0 (2СN); 128.1 (2СH); 128.5 (CH); 129.0
(4CH); 129.3 (4CH); 129.7 (2CH); 131.3 (2CH); 132.8
(2C); 144.5 (C Ph); 149.6 (C-2,6). Found, %: C 83.48;
H 4.70; N 11.50. C25H17N3. Calculated, %: C 83.54;
H 4.77; N 11.69.
4-(3-Nitrophenyl)-2,6-diphenyl-1,4-dihydropyridine-
3,5-dicarbonitrile (9c). Yield 275 mg (68%), colorless
crystals, mp 275–278°С. IR spectrum, ν, cm–1: 3217 (NH),
3097, 2924, 2777, 2206 (CN), 1639 (C=C), 1527 (NO2),
1496, 1346 (NO2), 1284, 1182, 836, 690. 1H NMR
spectrum, δ, ppm (J, Hz): 5.05 (1H, s, 4-CH); 7.46–7.54
(6H, m, H Ph); 7.61–7.64 (4H, m, H Ph); 7.78–7.83 (1H,
m, H Ar); 7.99 (1H, d, J = 7.8, H Ar); 8.24 (1H, d, J = 8.2,
H Ar); 8.29 (1H, s, H Ar); 10.29 (1H, s, NH). 13C NMR
spectrum, δ, ppm: 42.1 (C-4); 83.0 (C-3,5); 119.7 (2СN);
122.6 (СH); 123.6 (CH); 129.0 (4CH); 129.3 (4CH); 131.5
(3CH); 132.6 (2C); 135.0 (CH); 146.3; 148.8; 150.3
(C-2,6). Found, %: C 74.30; H 3.94; N 13.79. C25H16N4O2.
Calculated, %: C 74.25; H 3.99; N 13.85.
X-ray structural analysis of compounds 4b,c was
performed on an STOE STADIVARI PILATUS 100K
single crystal diffractometer (CuKα radiation, λ 1.5418 Å)
at 295(2) K. Crystals were grown as colorless prisms from
MeOH–CH2Cl2, 1:2 mixture by slow evaporation of the
solvent at room temperature. Single crystals of compounds
J = 8.9, H Ar); 7.77–7.81 (2H, m, H Ar). 13C NMR
spectrum, δ, ppm: 26.3 (C-1); 40.9 (C-2); 48.1 (2СH2N);
52.4 (CH3); 67.1 (2СH2O); 92.6 (C-3); 112.5; 119.0 (CH);
122.6 (CH); 124.0 (CH); 127.2 (CH); 128.5 (CH); 128.8
(CH); 129.1; 132.7; 151.9 (C-4a); 173.0 (C=O). Found, %:
C 69.79; H 6.44; N 4.15. C19H21NO4. Calculated, %:
C 69.71; H 6.47; N 4.28.
Methyl trans-8-bromo-3-(morpholin-4-yl)-2,3-dihydro-
1H-benzo[f]chromene-2-carboxylate (6b). Yield 470 mg
(77%), colorless crystals, mp 243–245°С. IR spectrum,
ν, cm–1: 1734 (С=О), 1603, 1489, 1443, 1391, 1236, 1190,
1
1115, 978, 885, 822, 750, 702. H NMR spectrum, δ, ppm
(J, Hz): 2.85–2.89 (2H, m, СH2N); 3.04–3.07 (2H, m,
СH2N); 3.29–3.44 (2H, m, 1-CH2); 3.59–3.64 (1H, m,
2-CН); 3.78–3.87 (4H, m, 2СH2O); 3.95 (3H, s, СH3); 4.72
(1H, d, J = 9.2, 3-CH); 7.20 (1H, d, J = 8.8, H Ar); 7.63
(1H, d, J = 8.8, H Ar); 7.65–7.70 (2H, m, H Ar); 7.97 (1H,
s, H-7). 13C NMR spectrum, δ, ppm: 27.8 (C-1); 41.3
(C-2); 47.7 (2СH2N); 52.8 (CH3); 67.1 (2СH2O); 90.9
(C-3); 110.0; 116.6; 118.7; 121.7 (CH); 124.2 (CH); 127.2
(CH); 128.7 (CH); 129.2 (CH); 132.0; 152.8 (C-4a); 175.6
(C=O). Found, %: C 56.24; H 5.04; N 3.49. C19H20BrNO4.
Calculated, %: C 56.17; H 4.96; N 3.45.
Methyl trans-8-(adamantan-1-yl)-3-(morpholin-4-yl)-
2,3-dihydro-1H-benzo[f]chromene-2-carboxylate (6c).
Yield 560 mg (81%), colorless crystals, mp 293–295°С.
IR spectrum, ν, cm–1: 2895 (СH Ad), 2847 (СH Ad), 1732
(С=О), 1603, 1439, 1396, 1263, 1236, 1204, 1190, 1161,
1
1121, 980, 810. H NMR spectrum, δ, ppm (J, Hz): 1.59–
1.68 (6H, m, 3CH2 Ad); 1.93 (6H, br. s, 3CH2 Ad); 1.99
(3H, br. s, 3CH Ad); 2.63–2.68 (2H, m, СH2N); 2.82–2.88
(2H, m, СH2N); 3.26–3.34 (2H, m, 1-CH2); 3.40–3.51 (1H,
m, 2-CН); 3.84–3.92 (4H, m, 2СH2O); 3.97 (3H, s, СH3);
4.72 (1H, d, J = 9.2, 3-CH); 7.03 (1H, d, J = 8.8, H Ar);
7.36–7.39 (1H, m, H Ar); 7.49–7.51 (1H, m, H Ar); 7.65
(1H, d, J = 8.8, H Ar); 7.69 (1H, d, J = 8.4, H Ar).
13C NMR spectrum, δ, ppm: 26.4 (C-1); 28.3 (3CH Ad);
35.9 (3CH2 Ad); 39.5 (3CH2 Ad); 41.1 (C Ad); 42.0 (C-2);
48.3 (2СH2N); 52.6 (CH3); 66.9 (2СH2O); 93.6 (C-3);
112.0; 117.8 (CH); 123.4 (CH); 125.4 (CH); 127.6; 128.8
(CH); 129.3 (CH); 130.0; 131.7; 152.4 (C-4a); 172.9
(C=O). Found, %: C 75.51; H 7.69; N 3.12. C29H35NO4.
Calculated, %: C 75.46; H 7.64; N 3.03.
2-Acetyl-2-cyano-2,3-dihydro-1H-benzo[f]chromen-
3-yl acetate (7), a mixture of geometric isomers 7a,b in a
1:1 ratio. A solution of β-enaminonitrile 2d (210 mg,
1.5 mmol) and Mannich base 1a (310 mg, 1.5 mmol) in
Ac2O (5 ml) was heated under reflux for 10 h. The mixture
was cooled to –20°С, the formed precipitate was filtered
off and washed with EtOH (1 ml). The product was
recrystallized from EtOAc. Yield 222 mg (48%), colorless
crystals, mp 115–120°С. IR spectrum, ν, cm–1: 2222 (CN),
1789 (C=O), 1751 (C=O), 1643, 1438, 1373, 1203, 1165,
1
1134, 1064, 910, 767. H NMR spectrum, δ, ppm (J, Hz):
2.15 (3H, s, СH3); 2.42 (3H, s, СH3); 3.97 (2H, d, J = 1.4,
1-CН2); 7.27 (1H, d, J = 8.9, Н-5); 7.48 (1H, ddd, J = 8.2,
J = 7.1, J = 1.4, Н-8); 7.54 (1H, ddd, J = 8.2, J = 7.1, J = 1.4,
Н-9); 7.82 (1H, d, J = 8.5, Н-6); 7.84 (1H, d, J = 1.4,
3-CН); 7.87 (1H, dd, J = 7.6, J = 1.4, Н-7); 7.96 (1H, d,
535

Chemistry of Heterocyclic Compounds 2020, 56(5), 529–536
Lobanov, P. S. Russ. Chem. Rev. 2015, 84, 601. [Usp. Khim.
4b,c with linear dimensions of 0.2 × 0.2 × 0.2 mm were
selected for studies. Crystallographic data for compound 4b
(C29H26N2O2, M 434.52): crystals are triclinic, space symmetry
2015, 84, 601.] (d) Riyadh, S. M.; Abdelhamid, I. A.; Al-
Matar, H. M.; Hilmy, N. M.; Elnagdi, M. H. Heterocycles
2008, 75, 1849. (e) Abu-Shanab, F. A.; Sherif, S. M.;
Mousa, S. A. S. J. Heterocycl. Chem. 2009, 46, 801.
(f) Kostyuk, A. N.; Volochnyuk, D. M.; Sibgatulin, D. A.
Synthesis 2008, 161. (g) Gaber, H. M.; Bagley, M. C.;
Muhammad, Z. A.; Gomha, S. M. RSC Adv. 2017, 7, 14562.
(h) Govindh, B.; Diwakar, B. S.; Murthy, Y. L. N. Org.
Commun. 2012, 5, 105. (i) Bondock, S.; Abd El-Gaber, T.;
Fadda, A. A. Curr. Org. Chem. 2011, 15, 753. (j) Dotsenko, V. V.;
Frolov, K. A.; Chigorina, E. A.; Khrustaleva, A. N.; Bibik, E. Yu.;
Krivokolysko, S. G. Russ. Chem. Bull., Int. Ed. 2019, 68, 691.
[Izv. Akad. Nauk, Ser. Khim. 2019, 691.]
‾
group P1; a 8.5164(5), b 11.5518(6), c 12.9967(8) Å;
α 111.498(4), β 90.825(5), γ 107.522(4)°; V 1123.20(12) Å3;
Z 2; dcalc 1.285 g·cm–3; μ 0.756 mm–1; F(000) 460. Diffrac-
tion data were collected within 3.692° ≤ θ ≤ 72.857° range;
sphere segment –10 ≤ h ≤ 10, –14 ≤ k ≤ 14, –16 ≤ l ≤ 10.
4020 independent reflections were collected, of which 1832
had I > 2σ(I). The structure was solved by the direct
methods and refined by the least squares technique in the
full-matrix anisotropic approximation to R1 0.0558
(wR2 0.1218). The positions of all hydrogen atoms were
calculated geometrically and refined according to the
"rider" model.
3. (a) Lukashenko, A. V.; Osyanin, V. A.; Osipov, D. V.;
Klimochkin, Yu. N. J. Org. Chem. 2017, 82, 1517.
(b) Lukashenko, A. V.; Osipov, D. V.; Osyanin, V. A.;
Klimochkin, Yu. N. Russ. J. Org. Chem. 2016, 52, 1817. [Zh.
Org. Khim. 2016, 52, 1824.] (c) Lukashenko, A. V.;
Osyanin, V. A.; Osipov, D. V.; Klimochkin, Yu. N. Chem.
Heterocycl. Compd. 2016, 52, 711. [Khim. Geterotsikl.
Soedin. 2016, 52, 711.] (d) Korzhenko, K. S.; Osipov, D. V.;
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Crystallographic data for compound 4c (C30H28N2O2,
‾
M 448.54): crystals are triclinic, space symmetry group P1;
a 10.1409(9), b 10.8089(9), c 13.0232(11) Å; α 65.400(6),
β 69.311(7), γ 65.190(7)°; V 1150.22(19) Å3; Z 2;
d
calc 1.295 g·cm–3; μ 0.756 mm–1; F(000) 476. Diffraction
data were collected within 3.824° ≤ θ ≤ 72.856° range;
sphere segment –12 ≤ h ≤ 10, –13 ≤ k ≤ 12, –14 ≤ l ≤ 16.
3874 independent reflections were collected, of which 1620
had I > 2σ(I). The structure was solved by the direct
methods and refined by the least squares technique in the
full-matrix anisotropic approximation to R1 0.0438 (wR2
0.0750). The positions of all hydrogen atoms were
calculated geometrically and refined according to the
"rider" model.
The calculations were performed using the SHELXL
software package.14 The full set of X-ray structural data for
compounds 4b,c was deposited at the Cambridge
Crystallographic Data Center (deposits CCDC 1942274
and CCDC 1942630, respectively).
1
Supplementary information file containing H and 13C
NMR spectra for compounds 3a–e, 4a–d, and 6a–c, as well
1
1
as COSY, H–13C HMBC, and H–13C HMQC spectra for
compound 7, is available at the journal website at http://
link.springer.com/journal/10593.
This study was supported by the Russian Foundation for
Basic Research (project 18-33-20249). The authors are
grateful to V. B. Rybakov (Moscow State University) for
performing X-ray structural analysis.
References
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2018, 16, 7806.
14. Sheldrick, G. M. Acta Crystallogr., Sect. A: Found.
Crystallogr. 2008, A64, 112.
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