Iodination and iodonitration of phenylacetylene under solvent-free conditions

Full text of DOI:10.1134/S1070428007010216

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 1, pp. 152–153. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © E.N. Tveryakova, Yu.Yu. Miroshnichenko, I.A. Perederina, M.S. Yusubov, 2007, published in Zhurnal Organicheskoi Khimii, 2007,
Vol. 43, No. 1, pp. 146–147.
SHORT
COMMUNICATIONS
Iodination and Iodonitration of Phenylacetylene
under Solvent-Free Conditions
a
a
b
a, b
E. N. Tveryakova , Yu. Yu. Miroshnichenko , I. A. Perederina , and M. S. Yusubov
a
Tomsk Polytechnical University, Tomsk, Russia
b
Siberian State Medical University, Moskovskii trakt 2, Tomsk, 634050 Russia
e-mail: yusubov@mail.ru
Received December 6, 2005
DOI: 10.1134/S1070428007010216
In the recent time, development of the “green
chemistry” principles has stimulated studies on organic
processes occurring in the absence of a solvent [1]. We
have found that phenylacetylene (I) reacts with molec-
ular iodine on grinding in a mortar without a solvent
for 2–10 min to give 45–90% of trans-1,2-diiodo-1-
phenylethene (II).
formation of INO , concentrated nitric acid was added
to the reaction mixture to enable required redox
reactions.
2
4
HNO
3
+ 2 KI
2 NO
2
+ I
2
+ 2 KNO
3
+ 2 H
2
O
2 NO2
I2 + N O4
N O
2
4
2 INO2
2
I
H
I2, 20°C
By grinding alkyne I with KI and HNO in a mortar
3
Ph
H
we obtained a mixture of diiodostyrene II and iodo-
nitrostyrene III. This result indicates, on the one hand,
that the presence of an oxidant is necessary to generate
Ph
I
I
II
the iodonitrating agent and, on the other, that INO can
The yield of diiodide II depends on the reactant
ratio; the maximal yield was attained when 2 equiv of
alkyne I was added in portions to 1 equiv of iodine.
The absence of by-products in the reaction mixture
allowed us to presume that the yield of diiodo deriva-
tive II may be quantitative when the reaction is per-
formed in a closed system (ball mill) with equimolar
amounts of the reactants. Thus, unlike known methods
for the synthesis of diiodostyrene which require the use
of toxic reagents and complex conditions [2–7], the
solvent-free procedure is extremely simple and easy to
perform.
2
be formed in the absence of an organic solvent. One
more important advantage of the proposed conditions
is that they prevent side processes which accompany
the reaction performed in acetic acid [8, 9].
In order to elucidate the role of nitrate and the
nature of metal cation therein we examined the reac-
tions of phenylacetylene with KI–HNO in the pres-
3
ence of NaNO and Mg(NO ) ·6H O. We found that
3
3 2
2
addition of NaNO does not favor formation of iodo-
3
I
H
I
H
KI–HNO , 20°C
3
Ph
H
+
Addition of sodium nitrate to the reaction mixture
did not change the reaction direction, and no iodo-
nitration product was formed (as in the reaction carried
out in acetic acid [8, 9]). Phenylacetylene turned out
to be inactive toward another iodonitrating system,
Ph
I
Ph
NO2
I
II
III
Reactant ratio
Yield of II, % Yield of III, %
I–KI–HNO
3
1.0 : 2.0 : 4.0
–NaNO
50
39
28
31
KI–NaNO . Presumably, redox transformation of KI
3
I–KI–HNO
3
3
to produce I (which is necessary for generation of the
1.0 : 2.0 : 4.0 : 2.0
I–KI–HNO –Mg(NO
1.0 : 2.0 : 4.0 : 2.0
2
reactive species, nitryl iodide) does not occur in the
absence of glacial acetic acid. In order to promote
3
3
)
2
34
65
152

IODINATION AND IODONITRATION OF PHENYLACETYLENE
153
1
3
nitration product III. By contrast, the yield of com-
pound III increased more than twofold in the presence
of Mg(NO ) ·6H O; correspondingly, the yield of di-
C NMR spectrum, δ
C
, ppm: 113.9 (CI); 127.3, 128.5,
130.3, 138.5 (Carom); 142.9 (CNO
Z)-1-Iodo-2-nitro-1-phenylethene (IIIb). H NMR
spectrum, δ, ppm: 77.50 m (5H, Harom), 7.67 s (1H).
).
2
1
3
2
2
(
iodide II fell down. The reason is that magnesium
nitrate is known [10] to possess a unique ability to
bind N O as Mg(NO ) ·N O adduct, thus holding it
1
3
C NMR spectrum, δ , ppm: 110.3 (CI); 128.8, 129.0,
C
2
4
3 2
2
4
1
31.2, 139.3 (C ); 143.1 (CNO2).
arom
in the reaction mixture.
1
13
The H and C NMR spectra were measured on
Our results clearly demonstrate advantages of the
proposed procedure for the iodonitration of phenyl-
acetylene, as compared to that described previously
a Bruker AV-300 instrument at 300 and 75 MHz, re-
spectively, using CDCl as solvent and TMS as internal
3
reference. The melting points were determined on
a Boetius melting point apparatus. Silica gel L (40–
100 μm, Chemapol) was used for column chromatog-
raphy; TLC analysis was performed on Sorbfil plates
(PTSKh-AF-A-UF and PTSKh-P-A-UF).
[
8, 9]: the reaction is much more selective (two prod-
ucts are formed instead of five as in [8, 9]), the reac-
tion time shortens from 4 h to 5 min, and the tempera-
ture is reduced from 85°C to ambient.
Reaction of phenylacetylene (I) with iodine.
Phenylacetylene (I), 2.0 mmol, was added in portions
over a period of 10 min to 1.0 mmol of iodine under
grinding in an agate mortar at 20°C. The mixture was
extracted with 10 ml of diethyl ether, the extract was
washed with 5.0 ml of a 5% solution of Na S O ,
This study was performed under financial support
by the President of the Russian Federation (program
for support of young Russian scientists, project
no. MK-3236.2004.3) and by the Russian Foundation
for Basic Research (project nos. 06-03-32562a, 06-03-
32735a).
2
2
3
1
0 ml of water, and 50 ml of a saturated solution of
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4
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3
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4
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1
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1
1
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007