Synthesis of 3-adamantylated hydantoins and their 2-thio(seleno) analogs

Article abstract of DOI:10.1007/s10593-019-02507-4

[Figure not available: see fulltext.] A series of 3-(adamantan-1-ylalkyl)-2-(O,S,Se)hydantoins were synthesized in the reaction of (adamantan-1-ylalkyl)heteroallenes with glycine ethyl ester hydrochloride under mild conditions in 75–85% yields. A method was developed for the synthesis of novel adamantan-1-ylalkyl isoselenocyanates, precursors in the synthesis of adamantylated 2-selenohydantoins. For the first time, 3-(adamantan-1-yl)-2-(O,S)hydantoins were synthesized via the reaction of 2-(O,S)hydantoins with 1,3-dehydroadamantane in 1,4-dioxane heated to reflux for 1 h in 75–80% yields.

Full text of DOI:10.1007/s10593-019-02507-4

DOI 10.1007/s10593-019-02507-4
Chemistry of Heterocyclic Compounds 2019, 55(7), 619–622
Synthesis of 3-adamantylated hydantoins
and their 2-thio(seleno) analogs
1
1
2
Vladimir V. Burmistrov , Dmitry А. Pitushkin , Vladimir V. Vasipov ,
1
1
Vladimir S. D'yachenko , Gennady M. Butov *
1
Volzhsky Polytechnic Institute (branch),
Volgograd State Technical University,
4
2a Engelsa St., Volzhsky, 404121, Russia; e-mail: butov@volpi.ru
2
Federal Research Center
N. I. Vavilov All-Russian Research Institute of Plant Genetic Resources (VIR),
4
2–44 Bol'shaya Morskaya St., Saint Petersburg 190121, Russia; e-mail: vl.vasipov@gmail.com
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
019, 55(7), 619–622
Submitted March 3, 2019
Accepted March 25, 2019
2
A series of 3-(adamantan-1-ylalkyl)-2-(O,S,Se)hydantoins were synthesized in the reaction of (adamantan-1-ylalkyl)heteroallenes with
glycine ethyl ester hydrochloride under mild conditions in 75–85% yields. A method was developed for the synthesis of novel adamantan-
1-ylalkyl isoselenocyanates, precursors in the synthesis of adamantylated 2-selenohydantoins. For the first time, 3-(adamantan-1-yl)-
2
-(O,S)hydantoins were synthesized via the reaction of 2-(O,S)hydantoins with 1,3-dehydroadamantane in 1,4-dioxane heated to reflux
for 1 h in 75–80% yields.
Keywords: adamantane derivatives, 1,3-dehydroadamantane, hydantoin, iso(thio,seleno)cyanates, 2-selenohydantoin, 2-thiohydantoin.
1
6
Imidazolidine-2,4-dione (hydantoin) derivatives are
1-adamantyl)methyl]-5-methylthiohydantoin is also known.
1
being studied as anti-inflammatory drugs and ion channel
Data on the synthesis of 3-(adamantan-1-yl)-2-thio-
hydantoin and its 2-seleno analog are absent in the
literature, although methods for synthesizing 3-substituted
thiohydantoins have been known since the end of the 19th
century.
2
3
modulators. Their 2-thio analogs exhibit anticonvulsant,
4
5
6
fungicidal, antiviral, antimutagenic, and immunomodu-
lating activity, as well as show promise for hormone-
independent treatment of prostate cancer. Most studies on
7
8
the biological activity of 2-thiohydantoin derivatives are
devoted to derivatives obtained by condensation with
Synthesis of 3-(adamantan-1-yl)- or 3-(adamantan-
1-ylalkyl)hydantoins, 2-thio-, and 2-selenohydantoins was
carried out in two stages, the reaction of (adamantan-1-yl)-
or (adamantan-1-ylalkyl)heteroallenes 1a–g with glycine
9
10
aldehydes. Glucosidase inhibitors and anticancer drug
11
candidates were found among the derivatives of 2-seleno-
hydantoin.
3
ethyl ester hydrochloride in the presence of Et N, followed
The adamantane skeleton is a very attractive structural
by cyclization of the resulting adamantyl-containing ethyl-,
ethylthio-, or ethylselenoureidoacetates 2a–g into the cor-
responding 3-(adamantan-1-ylalkyl)-2-(О,S,Se)hydantoins
3a–g. 1-Isocyanatoadamantane (1a), 1-isothiocyanato-
adamantane (1b), 1-(isocyanatomethyl)adamantane (1c),
1-(isothiocyanatomethyl)adamantane (1d), 1-(2-isothio-
cyanatoethyl)adamantane (1e), (1-isoselenocyanatomethyl)-
adamantane (1f), and 1-(2-isoselenocyanatoethyl)-
adamantane (1g) were chosen as the precursor
heteroallenes for the synthesis (Scheme 1).
1
2
fragment in medicinal chemistry. Publications on the
synthesis of 1-adamantyl-containing hydantoins are limited
to an example of accessing 3-(adamantan-1-yl)hydantoin
via the reaction of adamantane with hydantoin in fuming
1
3
HNO
3
in 71% yield. Information on adamantane-
14
containing 2-thiohydantoins are presented in the patent in
the form of a 5,5-disubstituted derivative without indicat-
ing its physicochemical or spectral characteristics, as well
as a compound in which the adamantane fragment is
bonded at position 3 of the PEG linker. Not described in
the literature but commercially available 3-[(3-chloro-
1
5
It should be noted that the literature describes a method
for obtaining only 1-adamantyl isoselenocyanate from
0
009-3122/19/55(7)-0619©2019 Springer Science+Business Media, LLC
619

Chemistry of Heterocyclic Compounds 2019, 55(7), 619–622
Scheme 1
1
8
1
-adamantylamine, whereas 1-adamantylalkyl isoseleno-
Scheme 3
cyanates 1f,g remained unknown. They were synthesized
for the first time by us from 1-aminomethyladamantane and
2
-(adamantan-1-yl)ethylamine hydrochlorides, respecti-
vely, by the action of CHCl , Et N, 50% NaOH, and
(Scheme 2).
3
3
2 2
elemental selenium in CH Cl
reaction proceeded ambiguously and was accompanied by
either hydrolysis of the ester group or its decarboxylation.
In this regard, 1,3-dehydroadamantane (1,3-DHA) (6) was
used to introduce the 1-adamantyl group in position 3 of
hydantoin 7a and 2-thiohydantoin 7b, which readily reacts
Scheme 2
25
with NH acids, in particular with different azoles. The
presence of two N–H bonds in the starting 2-(O,S)-
hydantoins did not exclude the formation of two isomeric
products at the H–N(1) and H–N(3) bonds, respectively.
It is known that the acidity of the H–N(3) bond in
compounds 7a,b significantly exceeds the acidity of the
Previously, we obtained the esters of N-(adamantan-
2
0
1
-yl)ureidoacetic
acids
and
N-(adamantan-1-yl)-
2
1
thioureidoacetic acids 2a–e when carrying out the
reaction of ethyl 2-(isocyanato)acetate with hydrochlorides
of adamantylated amines in anhydrous DMF in almost
quantitative yields. At the same time, the formation of
compounds 3a–g was not observed. Considering that the
best yields of thiohydantoins in the reaction of
isothiocyanates with amines are achieved in the DMF–
1
H–N(1) bond. This fact is illustrated by the H NMR
spectra, in which the chemical shifts of protons of the 1-NH
and 3-NH groups are respectively 7.70 and 10.62 ppm for
hydantoin 7a and 9.80 and 11.62 ppm for 2-thiohydantoin
26
7b. Apparently, the chemoselectivity of the reaction
involving 1,3-DHA (6) will be determined by differences
in the NH acidity of these bonds.
2
2
2
H O, 4:1 system, reaction with isothiocyanates 1b,d,e and
isoselenocyanates 1f,g was carried out under similar
conditions in the presence of a twofold molar excess of
Et N for 12 h. In the case of easily hydrolyzable
3
isocyanates 1a,c, the process was first carried out in
anhydrous DMF; 4 h after complete conversion of the
2
isocyanate into urea, H O was added, and the reaction
mixture was left for another 8 h.
The subsequent cyclization of compounds 2a–g
depended on the nature of the bridging group Z separating
the 1-adamantane substituent and the ureido group. When
no bridging group was present, the cyclization of
compounds 2a–g to hydantoins was not observed. When
The reaction of 1,3-DHA (6) with compounds 7a,b was
carried out by heating under reflux in 1,4-dioxane.
Chromato-mass spectrometry analysis showed that
complete conversion of 1,3-DHA (6) is observed after 1 h
with the formation of products 3a,b in 80 and 75% yields,
respectively. Besides, in the case of hydantoin 7a,
compound 8, the addition product to both NH groups of the
substrate 1,3-DHA (6), was found in the reaction mixture
(with m/z 368) (Scheme 4).
Scheme 4
alkyl bridges (Z = CH
2 2 2
and (CH ) ) were present in
3-(adamantan-1-ylalkyl)heteroallenes 1с,d,e,f,g, cyclo-
condensation took place, and the rate of cyclocondensation
of heteroallene with the ethylene bridge was higher.
The inability to obtain compounds 3a,b from
N-(adamantan-1-yl)ureidoacetic and N-(adamantan-1-yl)thio-
ureidoacetic acid esters 2a,b is probably related to the bulk
of the adamantane substituent that lowers the
nucleophilicity of the nitrogen atom N-1, which prevents
the cyclization process from occurring. An attempt to
synthesize (thio)hydantoins 3a,b via reaction of 1-amino-
Thus, a preparatively convenient method for the synthesis
of novel adamantan-1-ylalkyl isoselenocyanate precursors
in the preparation of adamantyl-containing 2-seleno-
hydantoins was developed as a result of the study. The
reaction of (adamantan-1-ylalkyl)heteroallenes with glycine
ethyl ester hydrochloride under mild conditions yields a
series of 3-(adamantan-1-ylalkyl)-2-(O,S,Se)hydantoins,
whereas 3-(adamantan-1-yl)-2-(O,S)hydantoins were first
synthesized by the reaction of (thio)hydantoins with
1,3-dehydroadamantane. Hydantoin yields were 75–85%.
adamantane
4
with heteroallenes 5a,b was also
unsuccessful, and the only reaction products were
compounds 2a,b (Scheme 3).
Experiments on cyclocondensation of (thio)ureido esters
2
HCl,
a,b in boiling EtOH with the addition of concentrated
19 23 24
2 4 3 2
H SO , or CF CO H did not lead to success: the
6
20

Chemistry of Heterocyclic Compounds 2019, 55(7), 619–622
1
3
Experimental
without melting above 250°С (decomp. temp. 250°С ).
1
H NMR spectrum, δ, ppm: 9.68 (1H, s, NH); 3.96 (2H, s,
1
13
13
H and C NMR spectra were acquired on a Bruker
DRX-500 spectrometer (500 and 126 MHz, respectively) in
DMSO-d , with TMS as internal standard. Signals in
C NMR spectra were assigned based on literature
NHCH
δ, ppm: 170.5 (NC(O)CH
(C Ad); 44.3 (CH NH); 40.4 (3CH Ad); 35.4 (3CH
29.5 (3CH Ad). Mass spectrum, m/z (Irel. %): 234 [М]
(42), 178 [Ad–NH–C=O] (85), 135 [Ad] (100). Found,
2
); 2.13–1.57 (15H, m, H Ad). C NMR spectrum,
2
); 157.5 (NC(O)NH); 45.5
Ad);
+
6
2
2
1
3
2
11,27
+
+
data.
Mass spectra were recorded on an Agilent GC
5
975/MSD 7820 GC-MS system with an HP-5MS (30 m)
%: C 66.59; H 7.79; N 12.00. C13
18 2 2
H N O . Calculated, %:
capillary quartz column, He carrier gas. Programmable
C 66.64; H 7.74; N 11.96.
column heating from 80 to 280°С, evaporator temperature
3-(Adamantan-1-yl)-2-thioxoimidazolidin-4-one (3b)
was obtained in the same way as compound 3a from
2-thioxoimidazolidin-4-one (7b) (0.58 g, 5.0 mmol) and
freshly distilled 1,3-DHA (6) (0.8 g, 6.0 mmol). Yield 0.92 g
250°С. Elemental analysis was performed on a PerkinElmer
Series II 2400 Elemental Analyzer.
Precursor 1-isocyanatoadamantane (1a), 1-aminoadaman-
tane (4), ethyl isocyanatoacetate (5a), ethyl isothiocyanato-
acetate (5b), glycine ethyl ester hydrochloride, hydantoin
1
(75%), brown solid, mp 220–222°С. H NMR spectrum,
δ, ppm: 7.40 (1H, s, NH); 2.74 (2H, s, NHCH
2
); 2.13–1.57
(15H, m, Н Ad). C NMR spectrum, δ, ppm: 184.8 (C=S);
171.9 (C=O); 59.3 (CH NH); 48.6 (C Ad); 41.4 (3CH Ad);
36.4 (3CH Ad); 30.5 (3CH Ad). Mass spectrum, m/z
(Irel, %): 250 [М] (73), 135 [Ad] (83), 116 [M–Ad]
(100). Found, %: C 62.42; H 7.22; N 11.24; S 12.77.
OS. Calculated, %: C 62.37; H 7.25; N 11.19; S 12.81.
3-[(Adamantan-1-yl)methyl]imidazolidine-2,4-dione
(3c). Glycine ethyl ester hydrochloride (0.73 g, 5.23 mmol)
and Et N (1.05 g, 10.46 mmol) were added to a solution of
13
(
7а), and 2-thiohydantoin (7b) supplied by Aldrich were
used without purification. 1-Isothiocyanatoadamantane
2
2
8
29
(
1b), 1-(isocyanatomethyl)adamantane (1с), 1-(isothio-
2
2
2
8
+
+
+
cyanatomethyl)adamantane (1d),
ethyl)adamantane (1e), and 1,3-dehydroadamantane (6)
1-(2-isothiocyanato-
2
8
30
were prepared by published methods.
13 18 2
C H N
(
1-Isoselenocyanatomethyl)adamantane (1f). Et
4 ml), СHCl (3 ml), Aliquat 336 (0.3 g), and 50%
aqueous NaOH (8 ml) were added to 1-aminomethyl-
adamantane hydrochloride (5.0 g, 25.0 mmol) in CH Cl
20 ml). The reaction mixture was heated under reflux for
3
N
(
3
3
2
2
1-(isocyanatomethyl)adamantane (1c) (1.00 g, 5.23 mmol)
in anhydrous DMF (8 ml). The reaction mixture was stirred
at room temperature for 4 h until full conversion of the
(
4
h, then fine elemental Se (5.0 g, 63.3 mmol) was added,
and heating under reflux was continued for another 4 h.
After cooling to room temperature, the reaction mixture
2
isocyanate. Then H O (2 ml) was added, and stirring at
room temperature was continued for additional 8 h. The
solvent was removed under reduced pressure, and the
product was recrystallized from EtOH. Yield 1.04 g (80%),
was diluted with CH
unreacted Se was filtered, the organic layer was separated
and dried over Na SO . The drying agent was filtered, and
2 2 2
Cl (30 ml) and H O (30 ml). Any
1
2
4
mp 215–216°С. H NMR spectrum, δ, ppm: 7.97 (1H, s,
the filtrate was evaporated under reduced pressure. The
product was purified by column chromatography on silica
gel, eluent hexane. Yield 3.75 g (59%), light-yellow solid,
NH); 3.91 (2H, s, NHCH
s, Н Ad); 1.67–1.44 (12H, m, Н Ad). C NMR spectrum,
δ, ppm: 172.7 (C=O); 158.3 (C=O); 49.2 (AdCH ); 45.8
(CH NH); 40.3 (3CH Ad); 36.3 (3CH Ad); 34.8 (C Ad)+;
27.7 (3CH Ad). Mass spectrum, m/z (Irel, %): 248 [М]
(10), 135 [Ad] (100). Found, %: C 67.75; H 8.09; N 11.32.
. Calculated, %: C 67.72; H 8.12; N 11.28.
3-[(Adamantan-1-yl)methyl]-2-thioxoimidazolidin-
2
); 3.02 (2H, s, AdCH ); 1.90 (3H,
2
13
2
1
mp 198–199°С. H NMR spectrum, δ, ppm: 3.94 (2H, s,
2
2
CH
2
NCSe); 2.01 (3H, s, Н Ad); 1.73–1.61 (6H, m, Н Ad);
2
+
+
1
.50 (6H, s, Н Ad). Mass spectrum, m/z (Irel, %): 255 [М]
+
+
(
20), 149 [Ad–CH
2
] (100), 135 [Ad] (50). Found, %:
14 20 2 2
C H N O
C 56.65; H 6.70; N 5.55. C12H17NSe. Calculated, %:
C 56.69; H 6.74; N 5.51.
4-one (3d). 1-(Isothiocyanatomethyl)adamantane (1d)
1
-(2-Isothiocyanatoethyl)adamantane (1g) was obtained
in the same way as compound 1f from 2-(adamantan-1-yl)-
ethylamine (2.0 g, 11.2 mmol), СHCl (1,5 ml), Aliquat
36 (0.15 g), elemental Se (5.0 g, 63.3 mmol), and 50%
aqueous NaOH (4 ml) in CH Cl (10 ml). Yield 1.65 g
55%), light-yellow solid, mp 78–79°С. H NMR spectrum,
δ, ppm (J, Hz): 3.60 (2H, t, J = 8.0, CH NCSe); 1.98 (3H,
s, Н Ad); 1.73–1.61 (6H, m, Н Ad); 1.56 (2H, t, J = 8.0,
AdCH ); 1.49 (6H, s, Н Ad). Mass spectrum, m/z (Irel, %):
69 [М+H] (40), 188 [M–Se] (20), 163 [Ad–CH
(1.00 g, 4.83 mmol) was dissolved in DMF (8 ml), and
glycine ethyl ester hydrochloride (0.67 g, 4.83 mmol), Et
(0.97 g, 9.66 mmol), and H O (2 ml) were added. The
3
N
3
2
3
reaction mixture was stirred at room temperature for 12 h.
The solvent was removed under reduced pressure, and the
product was recrystallized from EtOH. Yield 1.08 g (85%),
2
2
1
(
1
2
light-yellow solid, mp >150°С (subl.). H NMR spectrum,
δ, ppm: 7.36 (1H, s, NH); 4.13 (2H, s, NHCH
s, AdCH
2
2
); 3.42 (2H,
); 1.90–1.46 (15H, m, Н Ad). C NMR spectrum,
δ, ppm: 185.1 (C=S); 171.8 (C=O); 56.4 (AdCH ); 48.1
(CH NH); 40.9 (3CH Ad); 36.4 (3CH Ad); 27.9 (C Ad);
27.8 (3CH Ad). Mass spectrum, m/z (Irel, %): 264 [М]
(75), 231[M–S] (15), 207 [Ad–NCS] (14), 191 [Ad–NCO]
13
2
+
+
+
2
2
–CH
2
]
2
+
+
(
70), 149 [Ad–CH
C 58.18; H 7.16; N 5.25. C13
C 58.21; H 7.14; N 5.22.
2
] (3), 135 [Ad] (100). Found, %:
2
2
+
H
19NSe. Calculated, %:
2
+
+
+
+
3-(Adamantan-1-yl)imidazolidine-2,4-dione (3a). Freshly
(3), 135 [Ad] (100). Found, %: C 63.57; H 7.60; N 10.55;
S 12.15. C14 OS. Calculated, %: C 63.60; H 7.63;
N 10.60; S 12.13.
distilled 1,3-DHA 6 (0.8 g, 6.0 mmol) was added to a
solution of imidazolidine-2,4-dione (7а) (0.5 g, 5.0 mmol)
in anhydrous 1,4-dioxane (25 ml). The reaction mixture
was heated under reflux for 1 h. The solvent was removed
under reduced pressure, and the product was recrystallized
20 2
H N
3-[2-(Adamantan-1-yl)ethyl]-2-thioxoimidazolidin-4-one
(3e) was obtained in the same way as compound 3c from
1-(2-isothiocyanatoethyl)adamantane (1e) (1.00 g, 4.52 mmol),
glycine ethyl ester hydrochloride (0.63 g, 4.52 mmol), and
3
from CHCl . Yield 0.93 g (80%), white solid, decomposes
6
21

Chemistry of Heterocyclic Compounds 2019, 55(7), 619–622
Et
solid, mp 180–18°С. H NMR spectrum, δ, ppm: 10.10 (1H,
s, NH); 4.09 (2H, s, NHCH ); 3.69–3.64 (2H, m, NCH );
.92 (3H, s, Н Ad); 1.68–1.48 (12H, m, Н Ad); 1.31–1.26
3
N (0.92 g, 9.04 mmol). Yield 0.94 g (75%), light-yellow
9. (a) Wu, F.; Jiang, H.; Zheng, B.; Kogiso, M.; Yao, Y.; Zhou, C.;
1
Li, X.-N.; Song, Y. J. Med. Chem. 2015, 58, 6899.
(
b) Beloglazkina, E. K.; Majouga, A. G.; Yudin, I. V.;
2
2
Frolova, N. A.; Zyk, N. V.; Dolzhikova, V. D.; Moiseeva, A. A.;
Rakhimov, R. D.; Butin, K. P. Russ. Chem. Bull., Int. Ed.
1
13
(
1
2H, m, AdCH
2
). C NMR spectrum, δ, ppm: 183.1 (C=S);
72.4 (C=O); 76.6 (NHCH CH ); 41.5 (3C, Ad); 40.9
CH ); 31.4 (C Ad);
Ad). Mass spectrum, m/z (Irel, %): 278 [М] (4),
2
006, 55, 1015. [Izv. Akad. Nauk, Ser. Khim. 2006, 978.]
2
2
1
0. Merino-Montiel, P.; López, Ó.; Álvarez, E.; Fernández-
Bolaños, J. G. Tetrahedron 2012, 68, 4888.
(NCH
2
); 36.4 (3CH Ad); 35.2 (NHCH
2
2
+
2
2
[
7.8 (3CH
2
1
1. Ivanenkov, Y. A.; Veselov, M. S.; Rezekin, I. G.;
Skvortsov, D. A.; Sandulenko, Y. B.; Polyakova, M. V.;
Bezrukov, D. S.; Vasilevsky, S. V.; Kukushkin, M. E.;
Moiseeva, A. A.; Finko, A. V.; Koteliansky, V. E.;
Klyachko, N. L.; Filatova, L. A.; Beloglazkina, E. K.; Zyk, N. V.;
Majouga, A. G. Bioorg. Med. Chem. 2016, 24, 802.
+
+
45 [M–S] (100), 143 [M–Ad] (15), 135 [Ad] (12), 117
CH ] (35). Found, %: C 64.68; H 7.99; N 10.02;
S 11.48. C15 OS. Calculated, %: C 64.71; H 7.97;
N 10.06; S 11.52.
-[2-(Adamantan-1-yl)ethyl]-2-selenoxoimidazolidin-
-one (3g) was obtained in the same way as compound 3c
from 1-(2-isoselenocyanatoethyl)adamantane (1g) (0.50 g,
M–AdCH
2
2
22 2
H N
3
1
2. (a) Wanka, L.; Iqbal, K.; Schreiner, P. R. Chem. Rev. 2013,
4
1
13, 3516. (b) Zefirov, N. A.; Hoppe, M.; Kuznetsova, I. V.;
Chernyshov, N. A.; Grishin, Yu. K.; Maloshitskaya, O. A.;
Kuznetsov, S. A.; Zefirova, O. N. Mendeleev Commun. 2018,
28, 308.
1
.86 mmol), glycine ethyl ester hydrochloride (0.26 g,
1
.86 mmol), and Et N (0.38 g, 3.72 mmol). Yield 0.48 g
3
1
(
80%), light-brown solid, decomp. temp. 130°С. H NMR
spectrum, δ, ppm (J, Hz): 7.94 (1H, s, NH); 3.87 (2H, s,
NHCH ); 3.15 (2H, s, AdCH CH ); 1.93–1.47 (15H, m,
Н Ad); 1.20 (2H, д, J = 7.7, AdCH
spectrum, δ, ppm: 171.8 (C=O); 142.5 (C=Se); 44.3
AdCH CH ); 42.0 (CH NH); 41.6 (3CH Ad); 36.5 (3CH
Ad); 34.3 (AdCH CH ); 31.5 (C Ad); 28.0 (3CH Ad).
Mass spectrum, m/z (Irel, %): 326 [М] (11), 245 [M–Se]
1
3. Osipov, D. V.; Demidov, M. R.; Osyanin, V. A.;
Skomorokhov, M. Yu.; Klimochkin, Yu. N. Russ. J. Org.
Chem. 2016, 52, 906. [Zh. Org. Khim. 2016, 52, 911.]
4. Volkmann, R. A.; Jasys, V. J.; Bright, G. M.; Villalobos, A.;
Seymour, P. A. WO Patent 9529909.
2
2
2
1
3
2
2
CH ). C NMR
1
(
2
2
2
2
15. Gustafson, J. L.; Neklesa, T. K.; Cox, C. S.; Roth, A. G.;
Buckley, D. L.; Tae, H. S.; Sundberg, T. B.; Stagg, B.; Hines, J.;
McDonnel, D. P.; Norris, J. D.; Crews, C. M. Angew. Chem.,
Int. Ed. 2015, 54, 9659.
2
2
2
+
+
+
(
2 2
14), 205 [AdCH CH NCO] (32), 135 (100). Found, %:
1
1
1
1
2
6. http://online.aurorafinechemicals.com/info?ID=A17.189.041
7. Aschan, O. Chem. Ber. 1884, 17, 420.
22 2
C 55.42; H 6.79; N 8.65. C15H N OSe. Calculated, %:
C 55.38; H 6.82; N 8.61.
8. Zakrzewski, J.; Huras, B.; Kielczewska, A. Synthesis 2016, 85.
9. Ryczek, J. J. Heterocycl. Chem. 2003, 40, 665.
0. Burmistrov, V. V.; Butov, G. M.; D'yachenko, V. S. Russ. J.
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The work was done with support of the Ministry of
Education and Science of the Russian Federation within
the framework of the baseline of the State Assignment for
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017–2019 (project 4.7491.2017/BCh) on equipment
acquired under the Strategic Development Program of
Volgograd State Technical University for 2012–2016.
22. Jangale, A. D.; Wagh, Y. B.; Tayade, Y. A.; Dalal, D. S.
Synth. Commun. 2015, 45, 1876.
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