Selenocyanation of Aryl and Styryl Methyl Ketones in the Presence of Selenium Dioxide and Malononitrile: An Approach for the Synthesis of α-Carbonyl Selenocyanates

Article abstract of DOI:10.1021/acs.joc.0c02630

A convenient method has been developed for the synthesis of α-carbonyl selenocyanates from aryl methyl ketones/styryl methyl ketones using selenium dioxide as the selenating agent under simple reaction conditions. This reaction has notable advantages over the traditional methods in terms of accessibility and affordability of the starting materials. The method features the interaction of aryl methyl ketones/styryl methyl ketones with selenium dioxide and malononitrile to afford a series of α-carbonyl selenocyanates in moderate to good yields.

Full text of DOI:10.1021/acs.joc.0c02630

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Note
Selenocyanation of Aryl and Styryl Methyl Ketones in the Presence
of Selenium Dioxide and Malononitrile: An Approach for the
Synthesis of α‑Carbonyl Selenocyanates
Ibakyntiew D. Marpna, Kmendashisha Wanniang, Tyrchain Mitre Lipon, O. Risuklang Shangpliang,
and Bekington Myrboh*
Cite This: J. Org. Chem. 2021, 86, 1980−1986
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ABSTRACT: A convenient method has been developed for the
synthesis of α-carbonyl selenocyanates from aryl methyl ketones/styryl
methyl ketones using selenium dioxide as the selenating agent under
simple reaction conditions. This reaction has notable advantages over
the traditional methods in terms of accessibility and affordability of the
starting materials. The method features the interaction of aryl methyl
ketones/styryl methyl ketones with selenium dioxide and malononi-
trile to afford a series of α-carbonyl selenocyanates in moderate to
good yields.
synthesis of structurally diverse α-carbonyl selenocyanates
rganoselenium compounds have attracted a great deal of
Ointerest in recent years because of their unique biological under mild reaction conditions is therefore highly required.
Recently, we have demonstrated the versatility of selenium
dioxide as a selenating agent in the synthesis of α-oxo-
selenoamides from aryl methyl ketones and secondary
amines.11 As part of our ongoing research on the synthetic
utility of selenium dioxide in organic synthesis,11,12 we wish to
report here a direct and efficient one step protocol for the
selenocyanation of aryl methyl ketones/styryl methyl ketones
by selenium dioxide and malononitrile to give the α-carbonyl
selenocyanates (Scheme 1d).
To identify the optimum reaction conditions, 4-methyl-
acetophenone (1b) was taken as the model substrate and
allowed to react with malononitrile (2) and selenium dioxide
by varying the solvent used, reaction temperature, and time.
The results are summarized in Table 1. Thus, when 1 equiv of
4-methylacetophenone (1b), malononitrile (2) and selenium
dioxide was carried out in DMSO at ambient temperature,
TLC of the reaction mixture showed only the presence of
unreacted substrates. The reaction was then heated to 40 °C
for 2 h when a single product spot appeared on the TLC plate.
Workup and purification of the reaction mixture yielded α-
carbonyl selenocyanates (3b) in 40% yield (Table 1, entry 1).
When the amount of selenium dioxide was increased to 2
properties and promising wide applications in organic
synthesis.1 Of the vast number of organoselenium compounds,
the organo-selenocyanate derivatives have shown considerable
potential as active intermediates2 in organic synthesis and have
been extensively studied for their anticancer properties3
besides other important biological activities.4 In particular,
the α-carbonyl selenocyanates are considered to be syntheti-
cally important since the presence of the carbonyl and cyano
functions serve as the basic scaffold for the construction of an
array of selenium containing heterocycles5 and other
selenoorganic compounds.6 Surprisingly only scanty reports
are available in the literature for the synthesis of α-carbonyl
selenocyanates.5e,7−10 The few reported methods includes the
synthesis of α-carbonyl selenocyanates from aromatic alkenes,7
α-haloketones,5e or aryl ketones8 using selenocyanate salts as
the selenocyanate source (Scheme 1a). Kachanov and group
reported a direct reaction of diketones with triselenium
dicyanide to gives dicarbonyl selenocyanate products (Scheme
1b).9 In 2019, Xiao et al. employed selenocyanobenziodox-
olone as the selenocyanating agent for the synthesis of diverse
α-carbonyl selenocyanate compounds from derivatives of
esters, ketones, and N-acetyl-α-arylenamine (Scheme 1c).10
Although these methods are quite efficient for the synthesis of
α-carbonyl selenocyanates, they are accompanied by certain
limitations. The harsh reaction conditions, low substrate scope,
and low product yield limits their scope of applications. The
multistep procedures coupled with high cost of the starting
materials render these methods less easily accessible. There-
fore, the development of alternative synthetic strategies for the
Received: November 5, 2020
Published: December 30, 2020
https://dx.doi.org/10.1021/acs.joc.0c02630
© 2020 American Chemical Society
J. Org. Chem. 2021, 86, 1980−1986
1980

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
a
Scheme 1. Synthesis of α-Carbonyl Selenocyanate
Table 1. Optimization of Reaction Conditions
substrate 2
temp
time
(h)
yield
entry
(equiv)
SeO2(equiv)
solvent
DMSO
(°C)
(%)
1
2
3
4
5
6
7
8
9
1
1
1
2
3
3
3
3
3
3
3
3
3
40
40
40
40
40
55
RT
40
50
50
50
2
2
2
1.5
3
2
5
2
5
40
50
72
55
68
70
trace
50
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
toluene
acetonitrile
THF
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
10
11
5
5
a
Reaction was carried out with 1b (1 mmol, 1 equiv) and 3 mL of
solvent.
gave a moderate yield of 50% while toluene, acetonitrile, and
THF give no product at all even at elevated temperatures
(Table 1, entries 8−11).
With the optimum reaction conditions obtained (Table 1,
entry 3), the generality of the reaction was investigated
employing a wide range of aryl methyl ketone derivatives, and
the results are summarized in Scheme 2. As a whole, the
reaction shows a wide substrate scope with aromatic methyl
ketones (1) and malononitrile (2). Aromatic ketones,
unsubstituted (4-H) or substituted by electron-donating
(e.g., 4-CH3, 4-OCH3, 3-OCH3, 3-CH3, 2-OCH3, 2-CH3) or
electron-withdrawing substituents (e.g., 4-NO2, 3-NO2) were
successfully converted to their desired products (3a, 70%; 3b,
72%; 3c, 75%; 3d, 62%; 3h, 65%; 3i, 65%; 3k, 73%; 3l, 67%)
in moderate to good yield. The solid product of 3a formed a
well defined crystal where its XRD data (included in the
Supporting Information) further strengthen the structure of
the final product. The reaction also proceeded smoothly with
the halo substituted ketones (e.g., 4-Cl, 4-Br, 4-F, 3-Cl, 2-Cl, 2-
Br) to afford the corresponding products (3e, 70%; 3f, 67%;
3g, 79%; 3j, 71%; 3m, 66%; 3n, 55%) in good to excellent
yield. Furthermore, the yield of the product was not affected by
the steric hindrance on the ring system of the ketones where
the disubstituted 1o and 1p and trisubstituted ketones 1q give
products (3o, 70%; 3p, 69%; and 3q; 72%) in excellent yield.
We further extent our curiosity to the behavior of heteroaryl
methyl ketones toward this reaction. With a large amount of
content, we found the promising conversions of the heteroaryl
methyl ketones (1r and 1s) to the expected products 3r and 3s
in 72% and 77% yield. The reaction was extended to six
membered nitrogen heterocycles, such as 2-acetylpyridine and
4-acetylpyridine, and resulted in an inextricable mass, thus
failing to afford the targeted products. Similarly, the current
method was ineffective toward aliphatic methyl ketones leading
to the formation of multiple products.
equiv, there was an improvement in product formation to 50%
yield (Table 1, entry 2). Ultimately, it was found that
increasing the amounts of malononitrile 2 from 1 equiv to
1.5 equiv and that of selenium dioxide from 2 equiv to 3 equiv,
the optimum yield of the product was obtained at 72% (Table
1, entry 3). Further increase in the amount of substrate 2 or
selenium dioxide did not increase the yield of the product any
further. Similarly, any decrease or increase in the reaction time
or temperature did not show any improvement in the yield of
the product (Table 1, entries 4−6). It was noted that when the
reaction was carried out at room temperature for 5 h, only a
trace amount of the product formation was observed (Table 1,
entry 7). To further investigate the possibility of increasing the
product yield, a series of solvents were examined where DMF
Encouraged by these results, we next turned our attention
toward styryl methyl ketones which when the reaction was
carried out at 50 °C afforded 5a in 62% yields (Scheme 3). In a
similar fashion the p-substituted, o-substituted styryl methyl
ketone readily gave the selenocyanate products in satisfactory
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https://dx.doi.org/10.1021/acs.joc.0c02630
J. Org. Chem. 2021, 86, 1980−1986

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Note
a
Scheme 2. Substrate Scope of Aryl Methyl Ketones
Scheme 3. Substrate Scope of Styryl/Isobutenyl Methyl
Ketones
a
a
Reaction was carried out with 4a−4i (1 mmol, 1 equiv), 2 (1.5
mmol, 1.5 equiv, 99 mg), and selenium dioxide (3 mmol, 3 equiv, 333
mg) in DMSO at 50 °C for 2 h.
Scheme 4. Plausible Mechanism
ketone followed by the subsequent nucleophilic attack of
enolate ketone 6 on the electrophilic selenium atom of
triselenodicyanide (TSD) (7), a selenocyanating intermediate
formed from the reaction of selenium dioxide and malononi-
trile (2),9,13 which led to the formation of 1-aryl-2-
selenocyanatoethan-1-one 3.
In summary, we have developed a simple and general
method for the selenocyanation of aromatic ketones using
readily available selenium dioxide and malononitrile. Further,
this reaction has the advantage wherein the substrates are all
added together in one-pot bypassing the prepreparation of the
intermediate (TSD), thus providing divergent access to a series
of 1-aryl-2-selenocyanatoethan-1-one and novel 4-aryl-1-
selenocyanatobut-3-en-2-one compounds which are important
synthons and have potential application in selenoorganic
synthesis. In addition, the use of easily available starting
materials, unique versatility, shorter reaction time, and high
a
Reaction was carried out with 1a−1s (1 mmol, 1 equiv), 2 (1.5
mmol, 1.5 equiv, 99 mg), and selenium dioxide (3 mmol, 3 equiv, 333
mg) in DMSO at 40 °C for 2 h.
yields (5b; 58%, 5c; 60%, 5d; 56%, 5e; 63%, 5f; 62%, 5g;
59%). Similarly, the disubstituted styryl methyl ketone 4h gave
the desired product 5h in 62% yield. It may be noted that
when the reaction was extended toward heteroaryl styryl
methyl ketones, no product formation was observed. However,
aliphatic α,β-unsaturated methyl ketone, isobutenyl methyl
ketones (4i) gave the desired product 5i in 46% yield.
The plausible mechanism is depicted in Scheme 4.
Evidently, the first step in the reaction is the enolization of
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https://dx.doi.org/10.1021/acs.joc.0c02630
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The Journal of Organic Chemistry
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Note
yellow solid (172 mg, 72%); mp 123−124 °C IR (KBr): 3447, 2931,
2208, 1653, 1504, 806 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.80 (s,
2H), 7.30−7.24 (m, 2H), 4.87 (s, 2H), 2.38 (s, 3H)) ppm; 13C{1H}
NMR (100 MHz, CDCl3): δ 192.7, 146.2, 131.2, 129.8, 128.8, 102.1,
38.6, 21.8 ppm. MS (ES+) calcd for C10H9NOSe, 238.94, found m/z,
240.20 [M + H]+
substrate scope adds to the operational simplicity of this
method.
EXPERIMENTAL SECTION
■
General Information. Unless otherwise specified, all chemicals
are commercially available without further purification or prepared by
a known procedure. All reactions were carried out in a temperature
control magnetic stirrer using an oil bath. Reactions were monitored
by TLC using precoated aluminum sheets (silica gel 60 F254 0.2 mm
thickness) and visualized by UV fluorescence light at 254 nm using an
appropriate mixture of ethyl acetate and hexane. Column chromatog-
raphy was carried out on silica gel (100−200 mesh) eluting with an
appropriate mixture of ethyl acetate and hexane. IR spectra were
recorded on a PerkinElmer Spectrum 400 FTIR instrument, and the
frequencies are expressed in cm−1. 1H NMR and 13C{1H} NMR
spectra were recorded on a Bruker Avance II-400 spectrometer in
CDCl3 and/or DMSO-d6 where TMS is the internal standard and the
chemical shift are expressed in ppm. Mass spectral data were obtained
with a Waters UPLC−TQD mass spectrometer (ESI-MS). High-
resolution mass spectra (ESI-HRMS) were recorded on an Agilent
6545, quadrupole time-of-flight (Q-TOF). 77Se NMR spectra were
recorded on a ECZR series 600 MHz NMR spectrometer (Jeol,
Japan), where the chemical shifts are expressed in ppm. The melting
points of all synthesized compound are recorded by the open capillary
tube method and are uncorrected. All commercial chemicals were
purchased from Sigma-Aldrich, TCI Chemicals, and Alfa Aesar and
used directly as received.
1-(4-Methoxyphenyl)-2-selenocyanatoethan-1-one (3c).5e The
product was prepared via the general procedure from 4-
methoxyacetophenone (1 mmol, 150 mg). The product was collected
by vacuum filtration over Whatman-41 filter paper and washed with
hexane/ethyl acetate (7:3); yellow solid (191 mg, 75%); mp 102−104
°C; IR (KBr): 3448, 2933, 2149, 1642, 1601, 1568, 1171, 820 cm−1;
1H NMR (400 MHz, CDCl3): δ 7.86 (d, J = 8.8 Hz, 2H), 6.91 (d, J =
8.8 Hz, 2H), 4.85 (s, 2H), 3.83 (s, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3): δ 191.5, 164.8, 131.2, 126.7, 114.3, 102.3, 55.7, 38.6
ppm. MS (ES+) calcd for C10H9NO2Se, 254.98, found m/z, 256.15
[M + H]+
1-(4-Nitrophenyl)-2-selenocyanatoethan-1-one (3d). The prod-
uct was prepared via the general procedure from 4-nitroacetophenone
(1 mmol, 165 mg). The crude was purified by column
chromatography using hexane/ethyl acetate (7:3) as the eluent;
white solid (167 mg, 62%); mp 110−112 °C; IR (KBr): 3445, 2933,
2150, 1666, 1601, 1532, 1178, 888 cm−1; 1H NMR (400 MHz,
CDCl3): δ 8.32 (d, J = 8.8 Hz, 2H), 8.08 (d, J = 9.2 Hz, 2H), 4.85 (s,
2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 191.8, 151.1, 138.0,
129.8, 124.3, 100.9, 37.3 ppm. HRMS (ESI) m/z: [M + H]+ calcd for
C9H7N2O3Se, 270.9622; found 270.9615.
1-(4-Chlorophenyl)-2-selenocyanatoethan-1-one (3e).5e,7,9 The
product was prepared via the general procedure from 4-
chloroacetophenone (1 mmol, 154 mg). The crude was purified by
column chromatography using hexane/ethyl acetate (7:3) as the
eluent; yellow solid (181 mg, 70%); mp 159−160 °C; IR (KBr):
3447, 2932, 2152, 1658, 1589, 1180, 817 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.83 (d, J = 8.8 Hz, 2H), 7.44 (d, J = 8.8 Hz, 2H), 4.83 (s,
2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 192.0, 141.6, 132.0,
130.0, 129.5, 101.6, 38.0 ppm. MS (ES+) calcd for C9H6ClNOSe,
258.93, found m/z, 260.01 [M + H]+
General Procedure for the Synthesis of 1-Aryl-2-selenocya-
natoethan-1-one (3). A mixture of aryl methyl ketones 1 (1 mmol,
1 equiv), malononitrile 2 (1.5 mmol, 1.5 equiv, 99 mg), and selenium
dioxide (3 mmol, 3 equiv, 333 mg) were allowed to stir in 3 mL of
DMSO at a temperature of 40 °C for 2 h in an oil bath. On
completion of the reaction, the mixture was extracted and diluted with
ethyl acetate (10 mL) and then washed with brine (15 mL). The
organic layer was separated and dried over anhydrous sodium sulfate
where it was concentrated to a minimum amount by a rotatory
evaporator. The compounds were then either purify by column
chromatography on silica gel (100−200 mesh) using a mixture of
ethyl acetate and hexane as the eluents or separated by vacuum
filtration followed by washing with an appropriate mixture of ethyl
acetate and hexane to get the product.
General Procedure for the Synthesis of 4-Aryl-1-selenocya-
natobut-3-en-2-one (5). A mixture of styryl methyl ketones 4 (1
mmol, 1 equiv), malononitrile 2 (1.5 mmol, 1.5 equiv, 99 mg), and
selenium dioxide (3 mmol, 3 equiv, 333 mg) were allowed to stir in 3
mL of DMSO at a temperature of 50 °C for 2 h in an oil bath. On
completion of the reaction, the mixture was extracted and diluted with
ethyl acetate (10 mL) and then washed with brine (15 mL). The
organic layer was separated and dried over anhydrous sodium sulfate
where it was concentrated to a minimum amount by a rotatory
evaporator. The compounds were then either purified by column
chromatography on silica gel (100−200 mesh) using a mixture of
ethyl acetate and hexane as the eluents or separated by vacuum
filtration followed by washing with an appropriate mixture of ethyl
acetate and hexane to get the product.
1-(4-Bromophenyl)-2-selenocyanatoethan-1-one (3f).5e,8,7 The
product was prepared via the general procedure from 4-
bromoacetophenone (1 mmol, 199 mg). The product was collected
by vacuum filtration over Whatman-41 filter paper and washed with
hexane/ethyl acetate (7:3); white solid (202 mg, 67%); mp 178−180
1
°C; IR (KBr): 3448, 2932, 2208, 1657, 1583, 1178, 811 cm−1; H
NMR (400 MHz, CDCl3): δ 7.75 (d, J = 8.4 Hz, 2H), 7.61 (d, J = 8.4
Hz, 2H), 4.82 (s, 2H) ppm; 13C{1H} NMR (100 MHz, CDCl3:
DMSO-d6): δ 192.6, 132.6, 132.2, 130.3, 129.7, 102.1, 36.9 ppm. MS
(ES+) calcd for C9H6BrNOSe, 302.88, found m/z, 304.36 [M + H]+
1-(4-Fluorophenyl)-2-selenocyanatoethan-1-one (3g).8,9 The
product was prepared via the general procedure from 4-
fluoroacetophenone (1 mmol, 138 mg). The crude was purified by
column chromatography using hexane/ethyl acetate (8:2) as the
eluent; pink solid (192 mg, 79%); mp 113−114 °C; IR (KBr): 3448,
2934, 2153, 1658, 1595, 1297, 1104, 877 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.93 (dd, J = 5.2 Hz, 2H), 7.14 (t, J = 8.4 Hz, J = 8.8 Hz,
2H), 4.84 (s, 2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 191.6,
166.7 (d,1JC−F = 256.8 Hz), 131.5 (d,3JC−F = 9.7 Hz), 130.2 (d,4JC−F
=
1-Phenyl-2-selenocyanatoethan-1-one (3a).5e,7−9,14 The product
was prepared via the general procedure from acetophenone (1 mmol,
120 mg). The crude was purified by column chromatography using
hexane/ethyl acetate (8:2) as the eluent; white solid (157 mg, 70%);
mp 80−82 °C; IR (KBr): 3448, 2943, 2152, 1665, 1592, 1184, 754
cm−1; 1H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 7.2 Hz, 2H), 7.61
(t, J = 7.2 Hz, J = 7.6 Hz, 1H), 7.46 (t, J = 8 Hz, J = 7.6 Hz, 2H), 4.88
(s, 2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 193.2, 134.9,
133.7, 129.1, 128.7, 101.9, 38.4 ppm. MS (ES+) calcd for C9H7NOSe,
224.97, found m/z, 226.04 [M + H]+.
3.0 Hz), 116.5 (d,2JC−F = 22.0 Hz), 101.7, 38.1 ppm. 19F NMR (400
MHz, CDCl3): δ −101.1 ppm. MS (ES+) calcd for C9H6FNOSe,
242.95, found m/z, 244.03 [M + H]+.
1-(3-Methoxyphenyl)-2-selenocyanatoethan-1-one (3h).8 The
product was prepared via the general procedure from 3-
methoxyacetophenone (1 mmol, 150 mg). The crude was purified
by column chromatography using hexane/ethyl acetate (7:3) as the
eluent; orange solid (165 mg, 65%); mp 110−112 °C; IR (KBr):
3446, 2937, 2155, 1663, 1595, 1192, 861 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.45 (d, J = 7.6 Hz, 1H), 7.38−7.34 (m, 2H), 7.15−7.13
(m, 1H), 4.85 (s, 2H), 3.80 (s, 3H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 193.0, 160.0, 134.9, 130.1, 121.4, 121.4, 112.5, 101.9, 55.5,
38.5 ppm. MS (ES+) calcd for C10H9NO2Se, 254.97, found m/z,
256.30 [M + H]+.
2-Selenocyanato-1-(p-tolyl)ethan-1-one (3b).7,8 The product was
prepared via the general procedure from 4-methylacetophenone (1
mmol, 134 mg). The product was collected by vacuum filtration over
Whatman-41 filter paper and washed with hexane/ethyl acetate (8:2);
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The Journal of Organic Chemistry
pubs.acs.org/joc
Note
1-(3-Nitrophenyl)-2-selenocyanatoethan-1-one (3i). The product
was prepared via the general procedure from 3-nitroacetophenone (1
mmol, 165 mg). The product was collected by vacuum filtration over
Whatman-41 filter paper and washed with hexane/ethyl acetate (7:3);
orange solid (175 mg, 65%); mp 93−94 °C; IR (KBr): 3357, 2934,
2944, 2842, 2149, 1670, 1590, 1120, 780 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.29 (t, J = 8.8 Hz, J = 8.4 Hz, 1H), 6.52 (d, J = 8.4 Hz,
2H), 4.53 (s, 2H), 3.77 (s, 6H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 196.0, 157.8, 132.8, 115.6, 104.0, 101.8, 56.0, 41.0 ppm;
77Se NMR (600 MHz, DMSO) δ: 292.219 ppm. HRMS (ESI) m/z:
[M + H]+ calcd for C11H12NO3Se, 285.9982; found 286.0026.
1-(2,4-Dimethylphenyl)-2-selenocyanatoethan-1-one (3p).8 The
product was prepared via the general procedure from 2,4-
dimethylcetophenone (1 mmol, 148 mg). The crude was purified
by column chromatography using hexane/ethyl acetate (8:2) as the
eluent; white solid (182 mg, 72%); mp 90−91 °C; IR (KBr): 3437,
3020, 2984, 2152, 1660, 1610, 1563, 1190, 809 cm−1; 1H NMR (400
MHz, CDCl3): δ 7.63 (d, J = 7.6 Hz, 1 Hz), 7.07 (d, J = 9.6 Hz, 2H),
4.90 (s, 2H), 2.47 (s, 3H), 2.32 (s, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3): δ 194.5, 144.9, 141.0, 133.6, 131.0, 130.0, 126.9,
102.4, 41.2, 22.3, 21.6 ppm. MS (ES+) calcd for C11H11NOSe, 253.00,
found m/z, 254.14 [M + H]+.
1
2150, 1686, 1572, 1034, 885 cm−1; H NMR (400 MHz, CDCl3): δ
8.73 (s, 1H), 8.48−8.46 (m, 1H), 8.24 (d, J = 7.6 Hz, 1H), 7.72 (t, J =
8.0 Hz, 1H), 4.86 (s, 2H) ppm; 13C{1H} NMR (100 MHz, CDCl3:
DMSO-d6): δ 191.7, 148.3, 135.2, 134.5, 130.4, 128.4, 123.6, 101.8,
35.9 ppm; 77Se NMR (600 MHz, DMSO): δ 210.871 ppm. HRMS
(ESI) m/z: [M + H]+ calcd for C9H7N2O3Se, 270.9622; found
270.9632.
1-(3-Chlorophenyl)-2-selenocyanatoethan-1-one (3j).8 The
product was prepared via the general procedure from 3-
chloroacetophenone (1 mmol, 154 mg). The crude was purified by
column chromatography using hexane/ethyl acetate (8:2) as the
eluent; pink solid (184 mg, 71%); mp 66−67 °C; IR (KBr): 3425,
2933, 2147, 1664, 1571, 1424, 1184, 821 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.87 (t, J = 2.0 Hz, 1H), 7.78−7.75 (m, 1H), 7.59−7.57
(m, 1H), 7.42 (t, J = 8 Hz, 1H) 4.82 (s, 2H) ppm; 13C{1H} NMR
(100 MHz, CDCl3): δ 192.0, 135.5, 135.1, 134.7, 130.5, 128.6, 126.8,
101.4, 37.8 ppm. MS (ES+) calcd for C9H6ClNOSe, 258.93, found m/
z, 260.05 [M + H]+.
1-Mesityl-2-selenocyanatoethan-1-one (3q). The product was
prepared via the general procedure from 2,4,6-trimethylacetophenone
(1 mmol, 162 mg). The crude was purified by column
chromatography using hexane/ethyl acetate (7:3) as the eluent;
brown solid (292 mg, 72%); mp 62−63 °C: IR (KBr): 3357, 2980,
2934, 2150, 1686, 1608, 1445, 1143, 885 cm−1; 1H NMR (400 MHz,
CDCl3): δ 6.82 (s, 2H), 4.43 (s, 2H), 2.23 (s, 3H), 2.17 (s, 6H) ppm;
13C{1H} NMR (100 MHz, CDCl3): δ 202.6, 140.2, 135.1, 133.4,
128.9, 101.1, 41.0, 21.1, 19.4 ppm. HRMS (ESI) m/z: [M + H]+ calcd
for C12H14NOSe, 268.0241; found 268.0230.
1-(2-Methoxyphenyl)-2-selenocyanatoethan-1-one (3k). The
product was prepared via the general procedure from 2-
methoxyacetophenone (1 mmol, 150 mg). The crude was purified
by column chromatography using hexane/ethyl acetate (7:3) as the
eluent; pink solid (186 mg, 73%); mp 64−65 °C; IR (KBr): 3447,
3006, 2948, 2155, 1634, 1595, 1161, 757 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.87 (d, J = 7.6 Hz, 1H), 7.55−7.51 (m, 1H), 7.02−6.95
(m, 2H), 4.81 (s, 2H), 3.92 (s, 3H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 192.9, 159.8, 136.2, 131.4, 123.2, 121.2, 111.8, 102.9, 55.8,
43.2 ppm. HRMS (ESI) m/z: [M + H]+ calcd for C10H10NO2Se,
255.9877; found 255.9872.
1-(Furan-2-yl)-2-selenocyanatoethan-1-one (3r).8 The product
was prepared via the general procedure from 2-acetylfuran (1 mmol,
110 mg). The crude was purified by column chromatography using
hexane/ethyl acetate (8:2) as the eluent; white solid (155 mg, 72%);
mp 99−100 °C; IR (KBr): 3448, 3121, 2939, 2154, 1644, 1561, 1463,
1
1079, 793 cm−1; H NMR (400 MHz, CDCl3): δ 7.68 (s, 1H), 7.36
(d, J = 3.6 Hz, 1H), 6.65−6.64 (m, 1H), 4.60 (s, 2H) ppm; 13C{1H}
NMR (100 MHz, CDCl3): δ 181.3, 150.2, 147.9, 119.5, 113.2, 101.1,
35.2 ppm. MS (ES+) calcd for C7H5NO2Se, 214.94 found m/z, 215.93
[M + H]+
2-Selenocyanato-1-(o-tolyl)ethan-1-one (3l).8 The product was
prepared via the general procedure from 2-methylacetophenone (1
mmol, 134 mg). The crude was purified by column chromatography
using hexane/ethyl acetate (8:2) as the eluent; pink solid (160 mg,
67%); mp 98−100 °C; IR (KBr): 3447, 2970, 2148, 1661, 1564,
1174, 985, 761 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.71 (d, J = 7.2
Hz, 1 Hz), 7.46−7.41(m, 1H), 7.29−7.24 (m, 2H), 4.89 (s, 2H), 2.49
(s, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 195.3, 140.6,
133.7, 132.8, 132.8, 130.5, 126.2, 102.1, 40.9, 22.1 ppm. MS (ES+)
calcd for C10H9NOSe, 238.98, found m/z, 240.07 [M + H]+.
1-(2-Chlorophenyl)-2-selenocyanatoethan-1-one (3m).7 The
product was prepared via the general procedure from 2-
chloroacetophenone (1 mmol, 154 mg). The crude was purified by
column chromatography using hexane/ethyl acetate (7:3) as the
eluent; white solid (170 mg, 66%); mp 84−86 °C; IR (KBr): 3443,
2999, 2943, 2152, 1664, 1591, 1183, 754 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.89 (dd, J = 1.2 Hz, 1H), 7.63−7.59 (m, 1H), 7.46 (t, J =
8.0 Hz, J = 7.6 Hz, 2H), 4.88 (s, 2H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 193.2, 134.8, 133.7, 129.1, 128.7, 101.9, 38.5 ppm. MS
(ES+) calcd for C9H6ClNOSe, 258.93 found m/z, 259.20 [M]+
1-(2-Bromophenyl)-2-selenocyanatoethan-1-one (3n). The
product was prepared via the general procedure from 2-
bromoacetophenone (1 mmol, 199 mg). The crude was purified by
column chromatography using hexane/ethyl acetate (8:2) as the
eluent; white solid (166 mg, 55%); mp 78−79 °C; IR (KBr): 3445,
2-Selenocyanato-1-(thiophen-2-yl)ethan-1-one (3s).8 The prod-
uct was prepared via the general procedure from 2-acetylthiophene (1
mmol, 126 mg). The product was collected by vacuum filtration over
Whatman-41 filter paper and washed with hexane/ethyl acetate (8:2);
yellow solid (177 mg, 77%); mp 100−101 °C; IR (KBr): 3250, 2930,
1
2207, 1632, 1510, 1409, 1172, 943, 744 cm−1; H NMR (400 MHz,
CDCl3): δ 7.80 (d, J = 4.0 Hz, 2H), 7.21 (t, J = 4.4 Hz, 1H), 4.76 (s,
2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 185.4, 140.1, 136.3,
134.3, 128.8, 101.5, 36.8 ppm. MS (ES+) calcd for C7H5NOSSe
230.92, found m/z, 249.15 [M + NH4]+
4-Phenyl-1-selenocyanatobut-3-en-2-one (5a). The product was
prepared via the general procedure from benzylideneacetone (1
mmol, 146 mg). The product was collected by vacuum filtration over
Whatman-41 filter paper and washed with hexane/ethyl acetate (8:2);
brown solid (155 mg, 62%); mp 106−107 °C; IR (KBr): 3454, 3051,
2942, 2208, 1672, 1574, 1150, 1002, 748 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.67 (d, J = 16.4 Hz, 1H), 7.60−7.57 (m, 2H), 7.47−7.42
(m, 3H), 6.82 (d, J = 16.0 Hz, 1H), 4.57 (s, 2H) ppm; 13C{1H} NMR
(100 MHz, CDCl3: DMSO-d6): δ 192.7, 146.7, 133.4, 131.5, 129.1,
128.7, 122.8, 101.9, 38.0 ppm. HRMS (ESI) m/z: [M + H]+ calcd for
C11H10NOSe, 251.9928; found 251.9919.
1-Selenocyanato-4-(p-tolyl)but-3-en-2-one (5b). The product
was prepared via the general procedure from 4-methylbenzylidenea-
cetone (1 mmol, 160 mg). The crude was purified by column
chromatography using hexane/ethyl acetate (8:2) as the eluent; white
solid (153 mg, 58%); mp 108−110 °C; IR (KBr): 3241, 3000, 2913,
2153, 1635, 1601, 1149, 1002, 804 cm−1; 1H NMR (400 MHz,
CDCl3): δ 7.64 (d, J = 16.0 Hz, 1H), 7.48 (d, J = 8.0 Hz, 2H), 7.24
(d, J = 7.6 Hz, 2H), 6.77 (d, J = 16.4 Hz, 1H), 4.57 (s, 2H), 2.40 (s,
3H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 147.0, 142.5,
130.6, 129.9, 128.8, 121.7, 101.9, 38.4, 21.6 ppm. HRMS (ESI) m/z:
[M + H]+ calcd for C12H12NOSe, 266.0084; found 266.0083.
1
2943, 2152, 1664, 1575, 1183, 996, 754 cm−1; H NMR (400 MHz,
CDCl3): δ 7.89 (dd, J = 1.6 Hz, 1H), 7.63−7.59 (m, 1H), 7.46 (t, J =
7.6 Hz, J = 8.0 Hz, 2H), 4.88 (s, 2H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 193.2, 134.8, 133.7, 129.1, 128.7, 101.9, 38.5 ppm. HRMS
(ESI) m/z: [M + H]+ calcd for C9H7BrNOSe, 303.8876; found
303.8849.
1-(2,4-Dimethoxyphenyl)-2-selenocyanatoethan-1-one (3o).
The product was prepared via the general procedure from 2,4-
dimethoxycetophenone (1 mmol, 180 mg). The crude was purified by
column chromatography using hexane/ethyl acetate (7:3) as the
eluent; white solid (199 mg, 70%); mp 94−95 °C; IR (KBr): 3448,
1984
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J. Org. Chem. 2021, 86, 1980−1986

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
4-(4-Methoxyphenyl)-1-selenocyanatobut-3-en-2-one (5c). The
product was prepared via the general procedure from 4-
methoxybenzylideneacetone (1 mmol, 176 mg). The crude was
purified by column chromatography using hexane/ethyl acetate (8:2)
as the eluent; white solid (168 mg, 60%); mp 104−106 °C; IR (KBr):
3448, 3023, 2941, 2152, 1632, 1597, 1510, 1260, 1151, 807 cm−1; 1H
NMR (400 MHz, CDCl3): δ 7.62 (d, J = 16.0 Hz, 1H), 7.54 (d, J =
8.8 Hz, 2H), 6.95 (d, J = 8.8 Hz, 2H), 6.69 (d, J = 16.4 Hz, 1H), 4.56
(s, 2H), 3.86 (s, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ
192.4, 162.5, 146.7, 130.7, 126.0, 120.3, 114.7, 102.0, 55.5, 38.5 ppm.
HRMS (ESI) m/z: [M + H]+ calcd for C12H12NO2Se, 282.0033;
found 282.0028.
4-(4-Fluorophenyl)-1-selenocyanatobut-3-en-2-one (5d). The
product was prepared via the general procedure from 4-
fluorobenzylideneacetone (1 mmol, 164 mg). The crude was purified
by column chromatography using hexane/ethyl acetate (8:2) as the
eluent; white solid (150 mg, 56%); mp 100−102 °C; IR (KBr): 3447,
2996, 2943, 2154, 1645, 1595, 1509, 1235, 1152, 846 cm−1; 1H NMR
(400 MHz, CDCl3): δ 7.64 (d, J = 16.0 Hz, 1H), 7.61−7.57 (m, 2H),
7.13 (t, J = 8.4 Hz, 2H), 6.75 (d, J = 16.0 Hz, 1H), 4.53 (s, 2H) ppm;
13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 164.6 (d,1JC−F = 252.5
Hz), 145.5, 130.8 (d,3JC−F = 8.7 Hz), 129.7(d,4JC−F = 3.3 Hz), 122.4,
122.3, 116.5 (d,2JC−F = 21.9 Hz), 101.7, 38.2 ppm; 19F NMR (400
MHz, CDCl3): δ −106.4 ppm; 77Se NMR (600 MHz, DMSO): δ
196.782 ppm. HRMS (ESI) m/z: [M + H]+ calcd for C11H9FNOSe,
269.9833; found 269.9844.
4-(4-Bromophenyl)-1-selenocyanatobut-3-en-2-one (5e). The
product was prepared via the general procedure from 4-
bromobenzylideneacetone (1 mmol, 225 mg). The crude was purified
by column chromatography using hexane/ethyl acetate (8:2) as the
eluent; brown solid (207 mg, 63%); mp 98−100 °C; IR (KBr): 3446,
2992, 2937, 2154, 1644, 1584, 1154, 1071, 847 cm−1; 1H NMR (400
MHz, CDCl3): δ 7.63−7.57 (m, 3H), 7.45 (d, J = 8.4 Hz, 2H), 6.81
(d, J = 16.4 Hz, 1H), 4.53 (s, 2H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 192.3, 145.4, 132.5, 132.2, 130.0, 126.2, 123.0, 101.6, 38.1
ppm. HRMS (ESI) m/z: [M + H]+ calcd for C11H9BrNOSe,
329.9033; found 329.9012.
4-(4-Chlorophenyl)-1-selenocyanatobut-3-en-2-one (5f). The
product was prepared via the general procedure from 4-
chlorobenzylideneacetone (1 mmol, 180 mg). The crude was purified
by column chromatography using hexane/ethyl acetate (8:2) as the
eluent; white solid (176 mg, 62%); mp 100−102 °C; IR (KBr): 3448,
3056, 2947, 2157, 1643, 1589, 1154, 1088, 806 cm−1; 1H NMR (400
MHz, CDCl3): δ 7.62 (d, J = 16.4 Hz, 1H), 7.52 (d, J = 8.4 Hz, 2H),
7.42 (d, J = 8.0 Hz, 2H), 6.80 (d, J = 16.0 Hz, 1H), 4.53 (s, 2H) ppm;
13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 145.3, 137.7, 131.8,
129.8, 129.5, 123.0, 101.6, 38.2 ppm; 77Se NMR (600 MHz, DMSO):
δ 197.862 ppm. HRMS (ESI) m/z: [M + H]+ calcd for
C11H9ClNOSe, 285.9538; found 285.9560.
CDCl3): δ 193.2, 153.5, 153.3, 142.1, 123.4, 122.6, 119.0, 112.9,
112.4, 102.1, 56.0, 55.8, 38.6 ppm. HRMS (ESI) m/z: [M + H]+ calcd
for C13H14NO3Se, 312.0139; found 312.0143.
4-Methyl-1-selenocyanatopent-3-en-2-one (5i). The product was
prepared via the general procedure from 4-methylpent-3-en-2-one (1
mmol, 98 mg). The crude was purified by column chromatography
using hexane/ethyl acetate (9.5:0.5) as the eluent; yellow oil (92 mg,
46%); IR (KBr): 2982, 2933, 2154, 1674, 1608, 1436, 1385, 1102,
1038, 872 cm−1; 1H NMR (400 MHz, CDCl3): δ 6.17−6.16 (m, 1H),
4.28 (s, 2H), 2.19 (d, J = 1.2 Hz, 3H), 1.98 (d, J = 1.2, 3H) ppm;
13C{1H} NMR (100 MHz, CDCl3): δ 192.0, 162.0, 120.0, 101.7, 41.3,
28.0, 21.4 ppm. HRMS (ESI) m/z: [M + H]+ calcd for C7H10NOSe,
203.9928; found 203.9932.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
■
sı
https://pubs.acs.org/doi/10.1021/acs.joc.0c02630.
Single-crystal XRD data of 3a and copies of H and 13
C
1
NMR of all synthesized compounds (PDF)
Accession Codes
CCDC 2041476 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
■
Bekington Myrboh − Department of Chemistry, North-
Eastern Hill University, Shillong 793022, India;
orcid.org/0000-0001-9349-2216; Email: bmyrboh@
nehu.ac.in
Authors
Ibakyntiew D. Marpna − Department of Chemistry, North-
Eastern Hill University, Shillong 793022, India
Kmendashisha Wanniang − Department of Chemistry, North-
Eastern Hill University, Shillong 793022, India
Tyrchain Mitre Lipon − Department of Chemistry, North-
Eastern Hill University, Shillong 793022, India
O. Risuklang Shangpliang − Department of Chemistry,
North-Eastern Hill University, Shillong 793022, India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.0c02630
4-(2-Chlorophenyl)-1-selenocyanatobut-3-en-2-one (5g). The
product was prepared via the general procedure from 2-
chlorobenzylideneacetone (1 mmol, 180 mg). The crude was purified
by column chromatography using hexane/ethyl acetate (8:2) as the
eluent; yellow solid (168 mg, 59%); mp 86−88 °C; IR (KBr): 3448,
3025, 2935, 2151, 1641, 1588, 1154, 981 cm−1; 1H NMR (400 MHz,
CDCl3): δ 8.09 (d, J = 16.4 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 7.47
(d, J = 8.0 Hz, 1H), 7.42−7.32 (m, 2H), 6.80 (d, J = 16.4 Hz, 1H),
4.61 (s, 2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 192.5, 142.5,
135.7, 132.3, 131.5, 130.4, 127.8, 127.3, 125.1, 101.6, 38.1 ppm.
HRMS (ESI) m/z: [M + H]+ calcd for C11H9ClNOSe, 285.9538;
found 285.9538.
4-(2,4-Dimethoxyphenyl)-1-selenocyanatobut-3-en-2-one (5h).
The product was prepared via the general procedure from 2, 4-
dimethoxybenzylideneacetone (1 mmol, 206 mg). The crude was
purified by column chromatography using hexane/ethyl acetate (8:2)
as the eluent; yellow solid (164 mg, 62%); mp 106−108 °C; IR
(KBr): 3448, 3062, 2941, 2144, 1635, 1603, 1223, 1143, 794 cm−1;
1H NMR (400 MHz, CDCl3): δ 7.98 (d, J = 16.4 Hz, 1H), 7.06−6.99
(m, 2H), 6.89 (d, J = 9.2 Hz, 1H), 6.83 (d, J = 16.4 Hz, 1H), 4.65 (s,
2H), 3.88 (s, 3H), 3.80 (s, 3H) ppm; 13C{1H} NMR (100 MHz,
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors acknowledge SAIF-NEHU, SAIF-CDRI Lucknow,
SAIF-IIT Bombay, and SAIF-IIT Madras for spectral analysis.
The author thanks the financial support of University Grants
Commission (UGC), India, under the Maulana Azad National
Fellowship for Minority (MANF) Scheme. B.M. acknowledges
financial assistance from SERB, DST (Grant SB/EMEQ-006/
3013).
REFERENCES
■
(1) (a) Mugesh, G.; duMont, W. W.; Sies, H. Chemistry of
Biologically Important Synthetic Organoselenium Compounds. Chem.
Rev. 2001, 101, 2125−2125. (b) Mugesh, G.; Singh, H. B.
1985
https://dx.doi.org/10.1021/acs.joc.0c02630
J. Org. Chem. 2021, 86, 1980−1986

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
Heteroatom-Directed Aromatic Lithiation: A Versatile Route to the
Synthesis of Organochalcogen (Se, Te) Compounds. Acc. Chem. Res.
2002, 35, 226−236. (c) Nogueira, C. W.; Zeni, G.; Rocha, J. B. T.
Organoselenium and Organotellurium Compounds: Toxicology and
Pharmacology. Chem. Rev. 2004, 104, 6255−6285. (d) Soriano-
García, M. Organoselenium Compounds as Potential Therapeutic and
Chemopreventive Agents: A Review. Curr. Med. Chem. 2004, 11,
̈
1657−1669. (e) Braga, A. L.; Ludtke, D. S.; Vargas, F.; Braga, R. C.
Catalytic Applications of Chiral Organoselenium Compounds in
Asymmetric Synthesis. Synlett 2006, 2006 (10), 1453−1466.
(2) (a) Fujita, K.-I.; Murata, K.; Iwaoka, M.; Tomoda, S. A
Symmetric Oxyselenenylation of Simple Olefins Using Optically
Active Selenobinaphthyls. Heteroat. Chem. 1995, 6, 247−257.
(b) Zhang, Y.; Wu, D.; Weng, Z. Synthesis of 1,2,2-trifluorovinyl
sulphides and selenides from trifluorovinylation of organic thiocya-
nates and selenocyanates. Org. Chem. Front. 2017, 4, 2226−2229.
(c) Ghosh, T.; Mukherjee, N.; Ranu, B. C. Transition Metal- and
Oxidant-Free Base-Mediated Selenation of Bicyclic Arenes at Room
Temperature. ACS Omega 2018, 3, 17540−17546.
(3) (a) Rao, C. V.; Wang, C-. Q.; Simi, B.; Rodriguez, J. G.; Cooma,
I.; El- Bayoumy, K.; Reddy, B. S. Chemoprevention of Colon Cancer
by a Glutathione Conjugate of 1,4-Phenylenebis(methylene)-
selenocyanate, a Novel Organoselenium Compound with Low
Toxicity. Cancer Res. 2001, 61 (9), 3647−3652. (b) Plano, D.;
Karelia, D. N.; Pandey, M. K.; Spallholz, J. E.; Amin, S.; Sharma, A. K.
Design, Synthesis, and Biological Evaluation of Novel Selenium
(SeNSAID) Molecules as Anticancer Agents. J. Med. Chem. 2016, 59,
(8) Sun, K.; Lv, Y.; Chen, Y.; Zhou, T.; Xing, Y.; Wang, X. A novel
metal-free method for the selenocyanation of aromatic ketones to
afford α-carbonyl selenocyanates. Org. Biomol. Chem. 2017, 15, 4464−
4467. (b) Cui, J.; Wei, M.; Pang, L.; Xiao, J.; Gan, C.; Guo, G.; Xie,
C.; Zhu, Q.; Huang, Z. Oxidative umpolung selenocyanation of
ketones and arenes: Anefficient protocol to the synthesis of
selenocyanate. Tetrahedron 2020, 76, 130978−130984.
(9) Kachanov, A. V.; Slabko, O. Y.; Baranova, O. V.; Shilova, E. V.;
Kaminskii, V. A. Triselenium dicyanide from malononitrile and
selenium dioxide. One-pot synthesis of selenocyanates. Tetrahedron
Lett. 2004, 45, 4461−4463.
(10) Xiao, J.-A.; Li, Y.-C.; Cheng, X.-L.; Chen, W.-Q.; Cui, J.-G.;
Huang, Y.-M.; Huang, J.; Xiao, Q.; Su, W.; Yang, H. Selenocyano-
benziodoxolone: a practical electrophilic selenocyanation reagent and
its application for solid-state synthesis of α-carbonyl selenocyanates.
Org. Chem. Front. 2019, 6, 1967−1971.
(11) Shangpliang, O. R.; Kshiar, B.; Wanniang, K.; Marpna, I. D.;
Lipon, T. M.; Laloo, B. M.; Myrboh, B. Selenium Dioxide As an
Alternative Reagent for the Direct α-Selenoamidation of Aryl Methyl
Ketones. J. Org. Chem. 2018, 83, 5829−5835.
(12) (a) Laloo, B. M.; Mecadon, H.; Rohman, Md. R.; Kharbangar,
I.; Kharkongor, I.; Rajbangshi, M.; Nongkhlaw, R.; Myrboh, B.
Reaction of Selenium Dioxide with Aromatic Ketones in the Presence
of Boron Triflouride Etherate: A Protocol for the Synthesis of
Triarylethanones. J. Org. Chem. 2012, 77, 707−712. (b) Rohman, Md.
R.; Kharkongor, I.; Rajbangshi, M.; Mecadon, H.; Laloo, B. M.; Sahu,
P. R.; Kharbangar, I.; Myrboh, B. One-Pot Synthesis of Unsym-
metrical Benzils by Oxidative Coupling Using Selenium Dioxide and
p-Toluenesulfonic Acid Monohydrate. Eur. J. Org. Chem. 2012, 2012,
320−328. (c) Shangpliang, O. R.; Wanniang, K.; Kshiar, B.; Marpna,
I. D.; Lipon, T. M.; Mizar, P.; Myrboh, B. PTSA-Catalyzed Reaction
of Alkyl/Aryl Methyl Ketones with Aliphatic Alcohols in the Presence
of Selenium Dioxide: A Protocol for the Generation of an α-
Ketoacetals Library. ACS Omega 2019, 4, 6035−6043.
(13) (a) Redon, S.; Obah Kosso, A. R.; Broggi, J.; Vanelle, P. Easy
and efficient selenocyanation of imidazoheterocycles using triseleno-
dicyanide. Tetrahedron Lett. 2017, 58, 2771−2773. (b) Kosso, A.;
Broggi, J.; Redon, S.; Vanelle, P. Convenient and Rapid Synthesis of
3-Selenocyanato-4H-chromen-4-ones. Synlett 2018, 29, 1215−1218.
(c) Redon, S.; Kosso, A. R. O.; Broggi, J.; Vanelle, P. Metal-Free ipso-
Selenocyanation of Arylboronic Acids Using Malononitrile and
Selenium Dioxide. Synthesis 2019, 51, 3758−3764.
́
́
́
́
1946−1959. (c) Ali, W.; Alvarez-Perez, M.; Marc, M. A.; Salardon-
́
́
Jimenez, N.; Handzlik, J.; Domínguez-Alvarez, E. The Anticancer and
Chemopreventive Activity of Selenocyanate-Containing Compounds.
Curr. Pharmacol Rep. 2018, 4, 468−481.
(4) (a) Richie, J. P.; Kleinman, W.; Desai, D. H.; Das, A.; Amin, S.
G.; Pinto, J. T.; El-Bayoumy, K. The organoselenium compound 1,4-
phenylenebis(methylene)selenocyanate inhibits 4-(methylnitrosami-
no)-1-(3-pyridyl)-1-butanone-induced tumorgenesis and enhances
glutathione-related antioxidant levels in A/J mouse lung. Chem.-Biol.
Interact. 2006, 161, 93−103. (b) Nasim, M. J.; Witek, K.; Kincses, A.;
̇
́
́
Abdin, A. Y.; Zesławska, E.; Marc, M. A.; Gajdacs, M.; Spengler, G.;
́
Nitek, W.; Latacz, G.; Karczewska, E.; Kiec-Kononowicz, K.;
Handzlik, J.; Jacob, C. Pronounced activity of aromatic selenocyantes
against multidrug resistant ESKAPE bacteria. New J. Chem. 2019, 43,
6021−6031. (c) Chao, M. N.; Lorenzo-Ocampo, M. V.; Szajnman, S.
H.; Docampo, R.; Rodriguez, J. B. Further insights of selenium-
containing analogues of WC-9 against Trypanosoma cruzi. Bioorg.
Med. Chem. 2019, 27, 1350−1361.
(5) (a) Takahashi, M.; Kurosawa, M. The synthesis of 2-Imino-2,3-
dihydro-1,3,4-selenadiazole Derivatives. Bull. Chem. Soc. Jpn. 1980, 53,
1185−1186. (b) Gramza, J.; Mitchell, R. B.; Dittmer, D. C. Two New
Oxaselenoles from Desyl Selenocyanate. J. Org. Chem. 1984, 49,
2057−2058. (c) Farag, A. M.; Fahmi, A. A.; Abdelhamid, A. O.;
Shawali, A. S.; Algharib, M. S. The Structure of the Diazonium
Coupling Products of Phenyl Thiocyanate and Phenyl Selenocyanate
with Diazotiszed 3-Phenyl-5-Aminopyrazole. J. Heterocycl. Chem.
1987, 24, 1341−1344. (d) Zhou, Y.; Hartmann, H. On the reaction
of ω-selenocyanatoacetophenones with aliphatic amines-formation of
aroyl selenoamides. Phosphorus, Sulfur Silicon Relat. Elem. 1996, 118,
293−299. (e) Bodtke, A.; Kandt, M.; Pfeiffer, W.-D.; Langer, P.
Synthesis of 4-Aryl-2-imino-2H selenazolines by a Reaction of α-
(Selenocyanato)acetophenones With Anilines. Phosphorus, Sulfur
Silicon Relat. Elem. 2007, 182, 209−217.
(14) Maartmann-Moe, K.; Nevstad, G. O.; Songstad, J.; Zingales, R.;
Vikholm, I.; Urso, F.; Weidlein, J.; Zingaro, R. A. The crystal
Structure of the 2-Oxo-2-phenylethyl Esters of Thiocyanic and
Selenocyanic Acid (Phenacyl Thiocyanate and Phenacyl Selenocya-
nate). Acta Chem. Scand. 1986, 40a, 182−189.
(6) (a) Otero, M. D.; Batanero, B.; Barba, F. Electrochemical
preparation of α, α’-dicarbonylselenides. Tetrahedron 2004, 60, 4609−
4612. (b) Hua, G.; Du, J.; Cordes, D. B.; Slawin, A. M. Z.; Woollins, J.
D. Efficient synthesis of novel chalcogen-containing derivatives of
DNA nucleobases. Tetrahedron 2015, 71, 1792−1798.
(7) Nair, V.; Augustine, A.; George, T. G. A Facile CAN-Mediated
Synthesis of Selenocyanates from Arylalkenes and Heteroarenes. Eur.
J. Org. Chem. 2002, 2002, 2363−2366.
1986
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J. Org. Chem. 2021, 86, 1980−1986