Synthesis of unsaturated organoselenium compounds via the reaction of organic diselenides with 2,3-dichloro-1-propene in the hydrazine hydrate-KOH system

Article abstract of DOI:10.1134/S1070363213090065

Dimethyldiselenide reacts with 2,3-dichloro-1-propene at 20-25 C in the hydrazine hydrate-KOH medium to form 2-chloro-3-methylselanyl-1-propene with 90% yield. Diphenyldiselenide in the reaction with 2,3-dichloro-1-propene, depending on the conditions, ca

Full text of DOI:10.1134/S1070363213090065

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 9, pp. 1660–1665. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © E.P. Levanova, V.A. Grabel’nykh, V.S. Vakhrina, N.V. Russavskaya, A.I. Albanov, L.V. Klyba, О.А. Tarasova, I.B. Rozentsveig,
N.А. Korchevin, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 9, pp. 1434–1439.
Synthesis of Unsaturated Organoselenium Compounds
via the Reaction of Organic Diselenides
with 2,3-Dichloro-1-propene
in the Hydrazine Hydrate–KOH System
E. P. Levanova, V. A. Grabel’nykh, V. S. Vakhrina, N. V. Russavskaya, A. I. Albanov,
L. V. Klyba, О. А. Tarasova, I. B. Rozentsveig, and N. А. Korchevin
A.E. Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
е-mail: venk@irioch.irk.ru
Received August 27, 2012
Abstract—Dimethyldiselenide reacts with 2,3-dichloro-1-propene at 20–25°С in the hydrazine hydrate–KOH
medium to form 2-chloro-3-methylselanyl-1-propene with 90% yield. Diphenyldiselenide in the reaction with
2,3-dichloro-1-propene, depending on the conditions, can give quite selectively four products: 2-chloro-3-
phenylselanyl-1-propene, phenylselanylpropadiene, 1-phenylselanyl-1-propyne, and Z-1,2-bis(phenylselanyl)-
1-propene. The effect of the selenium atom on the reaction direction and the products structure is discussed.
DOI: 10.1134/S1070363213090065
The chemistry of organoselenium compounds has
been actively developing over recent decades [1]. This
is not only due to expansion of their industrial applica-
tions [2] and unique biological activity of some organo-
selenium compounds [3] but also due to wide use of
organoselenium compounds in organic synthesis [4].
Especially large synthetic potential is offered by un-
saturated organic structures containing selenium [5].
temperature, and the redox properties of the system
used to generate chalcogen-containing anions from
elemental chalcogens or organic dichalcogenides [11–13].
The systems based on hydrazine (in the form of
commercially available hydrazine hydrate) are
convenient and highly efficient reductive systems for
activation of elemental chalogens by their conversion
into chalcogenide anions (Yn2–, where Y = S, Se, Te;
n = 1–3) [14]. Sulfur activated to disulfide anions by
the hydrazine hydrate–KОН system reacts with 2,3-
dichloro-1-propene (I) to form bis(2-chloro-1-propene-
3-yl)sulfide via exclusively the chlorine atom at the
sp3-hybridized carbon atom of I [11]. When the
activation of sulfur is carried out in the hydrazine
hydrate–monoethanolamine system (which also ge-
nerates S22– anions), the product of the reaction is bis(2-
chloro-1-propene-3-yl)disulfide [12]. With selenium,
in both reductive systems bis(2-chloro-1-propen-3-yl)-
selenide is the only product [13]. The reaction with
tellurium, priorly activated to ditelluride anions, with I
proceeds just the other way: allene is formed and
elementary tellurium is regenerated, that is, both
chlorine atoms of I take part in the reaction [11].
Reactions of addition of selenols or diselenides to
alkynes [5, 6] as well as the substitution reactions with
selenium nucleophiles are used for the synthesis of
unsaturated selenides. Nucleophilic substitution readily
occurs at the allylic carbon [7], although in the pre-
sence of transition metal complexes [8, 9] or phase
transfer catalysts [10] the substitution of halogen by
organoselenium moiety can proceed also at the sp2-
hybridized carbon atom.
2,3-Dichloro-1-propene (I), containing chlorine
atoms both at the sp3- and sp2-hybridized carbon atoms,
is one of the key reagents for the synthesis of
unsaturated organoselenium compounds. We have
shown that the structure of the products formed in the
reaction of I with the chalcogen-containing nucleo-
philes depends on the nature of the nucleophile,
Recently, we have discovered an unexpected
sequence of transformations in the reaction of
1660

SYNTHESIS OF UNSATURATED ORGANOSELENIUM COMPOUNDS
1661
diphenyldisulfide with I in the hydrazine hydrate–
KОН system [15], namely, the nucleophilic sub-
stitution of chlorine at the allyl position with the PhS
group followed by dehydrochlorination into the allene
derivative, the allene–acetylene rearrangement, and
finally the addition of PhS– anion to the appeared triple
bond. Varying the conditions, each of the products of
this sequence can be selectively obtained.
The increase of reaction (2) temperature to 50°С
resulted in the formation of a complex mixture of
nonidentified products. Noteworthily, dimethyldisulfide
formed a complex mixture of products upon reaction
with I in the hydrazine hydrate–alkali system even at
room temperature.
Similarly to diphenyldisulfide (see [15]), diphenyl-
diselenide II gave the mixture of three products (from
GC, chromato-mass spectrometry, and NMR) upon
reaction with I at 30–35°С: 2-chloro-3-phenylselanyl-
1-propene (IIIb) (36%), 1-phenylselanylpropadiene
(V) (43%), and 1-phenylselanyl-1-propyne (VI) (8%)
Developing these studies, in this work we examined
the possibility of unsaturated organoselenium com-
pounds preparation on the basis of the reaction of I
with dimethyldiselenide and diphenyldiselenide II.
The reactions were performed in the hydrazine hyd-
rate–KОН system in which the Se–Se bond of
diselenides was reductively split. Reduction of
diselenides is not that smooth as of the corresponding
disulfides [14], therefore, in all cases the excess of
alkali was used (R2Se2:KOH = 1:5) [scheme (1)].
1
(yields were calculated from Н NMR) in the molar
ratio IIIb:V:VI = 5:5:1 [scheme (4)].
Cl
PhSeK
I
SePh
−KCl
IIIb
2R2Se2 + N2H4·H2O + 4KOH → 4RSeK + N2 + 5H2O, (1)
(4)
SePh
R = Me, Ph.
SePh
−HCl
The so obtained solutions of potassium selenolate
were introduced in the reaction with I without isolation.
V
VI
According to [15], the ratio of the respective products
of the reaction with diphenyldisulfide was 1.0:3.3:3.3.
Thus, in the case of diphenyldiselenide the reactions of
2-Chloro-3-methylselanyl-1-propene (IIIa) was ob-
tained with 90% yield via the reaction with dimethyl-
diselenide reduced to potassium methaneselenolate at
20–25°С [scheme (2)].
dehydrochlorination
with
the
formation
of
allenylselenide V and isomerization of the latter into
the acetylenic selenide VI were much slower.
Cl
Cl
CH3SeK
(2)
Cl
SeMe
Variation of the reaction conditions allowed altering
its selectivity. When the reaction of diselenide II with
I was performed at –5 to –10°С, the selenide IIIb was
obtained with 85% yield, the allenylselenide V was
found in trace amounts, and selenide VI was absent in
the products. In the same reaction run at 5 to 10°С,
selenide IIIb was formed with 81% yield, selenide V
was obtained with 12% yield, while acetylenic selenide
VI was not detected. The selectivity of acetylenic
selenide formation VI could be substantially increased
by increasing of the KOH:Ph2Se2 molar ratio to 10:1
and by increasing the reaction longer. At 25°С with the
above-mentioned ratio of the reagents, selenide VI was
the major product (58%), allenylselenide V was
formed with 19% yield, selenide IIIb was not detected.
When increasing the time of the reaction to 33 h, the
yield of acetylenic selenide VI was of 59%, and that of
selenide V was of 13%. Thus, with lower concentration
of allenylphenylselenide V in the reaction mixture, the
rate of its isomerization into the corresponding acetyl-
ene VI was notably decreased.
−KCl
I
IIIа
A somewhat unexpected result of this reaction was
the formation of bis(2-chloro-1-propene-3-yl)selenide
(IV) with 5–7% yield. Taking into account the results
of [13], the formation of selenide IV occurred due to
the presence of Sе2– and Se22– anions in the reaction
mixture [scheme (3)].
Cl
Se2−
(3)
2I
Se
−2Cl−
2
IV
In turn, Sе2– or Se22– anions could be generated from
elemental selenium, which was the product of
dimethyldiselenide decomposition, caused by thermal
instability of aliphatic diselenides [16].
Me2Se2 → Me2Se + Se,
2Se + N2H4·H2O + 4KOH → 2K2Se + N2+ 5H2O,
or 4Se + N2H4·H2O + 4KOH → 2K2Se2+ N2+ 5H2O.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

1662
LEVANOVA et al.
In such a protracted reaction (after 33 h), another
genation of multiple bonds in that system was
observed only when the unsaturated compound and the
reducer (hydrazine) were in the same phase [17].
Transfer of compound VI to the water-hydrazine phase
was possible only upon its ionization by the alkali
[scheme (5)].
product was detected in the products mixture, Z-1-
phenylselanyl-1-propene (VII) (yield of 2–3%), which
was apparently formed by hydrogenation of
the acetylenic selenide VI in the hydrazine hydrate–
alkali system. It was previously shown that hydro-
OH−
−
C
VI
CH2
C
SePh
−Η2Ο
−
CH2
SePh
C
C
H
N
CH3
H
CH3
H
SePh
SePh
H
Η2Ο
N2H4
(5)
H
C
C−
C
C
−Ν2Η2
OH−
N
H
H
А
VII
Hydrogenation, apparently, gave rise to anion A
stabilized by selenium atom. Due to steric effects,
exclusively Z-isomer of VII (from NMR) was formed
in the reaction.
tically the same. At reagents molar ratio of 1:5:1 (reac-
tion time 19 h) the only product extracted from the reac-
tion mixture was Z-1,2-bis(phenylselanyl)-1-propene
VIII formed with 65% yield with respect to diselenide
II. Compound VIII was the product of potassium seleno-
phenolate addition to acetylenic selenide VI. Thus, at 60°С
the following transformations occurred [scheme (6)]:
At 60°С, behavior of diphenyldisulfide [15] and di-
phenyldiselenide II in the reaction with I was prac-
CH3
H
+ OH−
PhSeK
PhSeK, H2O
I
IIIb
V
VI
C
C
(6)
−Cl−, −Η2Ο
−ΚCl
−ΚOH
SePh
PhSe
VIII
Formation of the Z-isomer of 1,2-bis(phenyl-
selanyl)-1-propene (VIII) was in accordance with the
rule of trans-addition of nucleophilic reagents to the
triple bond [18]. Selenides V and VI were not detected
in the reaction products.
was advantageous due to the availability of the re-
agents and milder conditions of the process.
The structure of all synthesized compounds was
proved by IR, 1Н, 13С, 77Se NMR spectroscopy and by
chromato-mass spectrometry. Fragmentation of the
allenic and acetylenic selenides V and VI in the mass
spectra was similar to that of the corresponding
sulfides [15]. The ratio of the ions peaks intensities
(М – Н)+/М+ (estimated from the signal corresponding
to 80Se isotope) equaled 2.0 for compound V and 0.4
for compound VI, which supported the analogy of
transformations of the molecular ions upon electron
impact declared in [15].
Reaction (6) proceeded with full conversion of
dichloropropene I but the yield of compound VIII was
far from quantitative. Therefore, after the extractive
separation of bis(phenylselanyl)-1-propene VIII, the
water-hydrazine layer was treated with methyl iodide,
and selenoanisole IX was obtained with the yield of
23% with respect to Ph2Se2 [scheme (7)].
PhSeK + CH3I
PhSeCH3
(7)
−KI
IX
Thus, the reaction of organic diselenides with 2,3-
dichloro-1-propene I in the hydrazine hydrate–KOH
system could be used as a convenient method for
preparation of chlorinated allylselenides, allenyl-
selenides, propynylselenides, and diselanyl-substituted
propenes. Those compounds are prospective for organo-
selenium synthesis applications due to high reactivity
of the unsaturated species.
Taking into account the amount of potassium
selenophenolate unreacted according to Eq. (6), the
yield of compound VIII was 84%.
1-Phenylselanyl-1-propyne (VI) was earlier prepared
in a multistage synthesis via the derivative of 1,2,3-
selenadiazole [19]. The method suggested in this work
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SYNTHESIS OF UNSATURATED ORGANOSELENIUM COMPOUNDS
1663
EXPERIMENTAL
Bis(2-chloro-1-propen-3-yl)selenide (IV) was
1
identified by GC, GC–MS, and Н, 13С, 77Se NMR
IR spectra were recorded in thin layer using Bruker
methods by comparison with the reference specimen
[13].
1
IFS-25 spectrometer. Н, 13С, 77Se NMR spectra were
registered with Bruker DPX 400 spectrometer at
400.13, 100.62 and 76.31 МHz, respectively, in CDCl3
solutions, internal standards being HMDS (1Н, 13С) or
Me2Se (77Se). Electron impact mass spectra were
obtained with Shimadzu GCMS–QP5050A chromato-
mass spectrometer (column SPB-5, 60000×0.25 mm,
quadruple mass analyzer, energy of ionization 70 eV,
ionic source temperature of 190°С, range of detected
masses 34-650 Da). The values of m/z of ions contain-
ing Se and Cl atoms were given for the signals cor-
responding to 80Se and 35Cl isotopes. Relative inten-
sities Irel were calculated taking into account the peaks
of all isotopes.
Reaction of 2,3-dichloro-1-propene (I) with di-
phenyldiselenide (II). Diselenide II (6.0 g, 0.019 mol)
was added in several portions to the solution of 5.38 g
(0.096 mol) of KOH in 24 ml of hydrazine hydrate at
45–50°С. The reaction mixture was heated at 85–90°С
for 3 h, then cooled to 30–35°С, and 4.26 g (0.038 mol)
of 2,3-dichloro-1-propene I was added dropwise. The
resulting mixture was stirred for 7 h (30–35°С), cooled
to room temperature, and extracted with СН2Сl2 (3×
50 ml); the combined extracts were dried with MgSO4,
and the solvent was removed. From the GLC, GC–MS
1
and H NMR data, the residue (7.0 g) contained three
products IIIb, V, and VI in the ratio of 1.7:1.7:0.3
(yields are given in the discussion part).
The reactions were monitored and the liquid pro-
ducts were analyzed with LKhM 80-MD-2 chro-
matograph (column 2000×3 mm, liquid phase DC-550,
5% on Chromaton N-AW-HMDS, in the linear tem-
perature programming mode, 12 deg/min, as gas carrier
was helium).
2-Chloro-3-phenylselanyl-1-propene (IIIb) was
obtained with the highest yield from 7.0 g (0.022 mol)
of diphenyldiselenide II, 6.27 g (0.112 mol) of KOH,
28 ml of hydrazine hydrate, and 4.97 g (0.045 mol) of
dichloropropene I. The splitting of Ph2Sе2 was
performed as described above, the reaction of the so
prepared PhSеK solution with compound I was per-
formed for 7.5 h at –5 to –10°С. The reaction mixture
was treated with СН2Сl2. After removal of the solvent,
8.84 g of the residue was obtained, containing selenide
IIIb and traces of allenic selenide V. Pure selenide
IIIb was obtained by vacuum distillation, bp 85–86°С
(1.5 mm Hg), being a colorless liquid turning yellow
2-Chloro-3-methylselanyl-1-propene (IIIа). Freshly
distilled dimethyldiselenide (2.0 g, 0.0106 mol) was
added dropwise upon stirring at 45–50°С to the
solution of 2.97 g (0.053 mol) of KOH in 13.5 ml of
hydrazine hydrate. The reaction mixture was stirred at
this temperature for 2 h, then cooled to 20-25°С, and
2.35 g (0.0212 mol) of 2,3-dichloro-1-propene I was
added. The mixture was further stirred for 7 h, diluted
with water (30 ml), and extracted with СН2Сl2 (2×
30 ml); the extract was dried over MgSO4 and the solvent
was removed to obtain 3.58 g of the residue, which
1
upon storage. IR spectrum, ν, cm–1: 1624 (νC=C). H
2
NMR, δ, ppm: 3.64 s (2Н, CH2Sе, JH–Se 14 Hz), 5.02
1
contained (GLC, chromato-mass and H NMR) 3.24 g
br.s, 5.08 br.s (2Н, Н2С=), 7.23 m (3H, Hm, Hp), 7.47
1
m (2H, Ho). 13С NMR, δC, ppm: 36.12 (СH2Se, JС–Se
(90%) of compound IIIа and 0.18 g (7%) of bis(2-
chloro-1-propen-3-yl)selenide (IV). Compound IIIа
was isolated by vacuum distillation, bp 92–94°С
(82 mm Hg). IR spectrum, ν, cm–1: 3104, 2998, 2925,
2858, 2820, 1625 (νC=C), 1527, 1419, 1273, 1194,
68 Hz), 114.40 (Н2С=), 128.00 (Сp), 128.81 (Сi), 129.28
(Сm), 134.36 (Сo), 138.86 (ClС=). 77Se NMR, δ, ppm:
339.0 t, (2JSe–H 14 Hz). Mass spectrum, m/z: 232 [M],
197 (M – Cl), 157 (PhSe), 115 (PhC3H2), 91 (C7H7), 77
(Ph). Found, %: С 46.71; Н 3.78; Se 34.61; Cl 15.30.
С9Н9SeCl. Calculated, %: С 46.68; Н 3.92; Se 34.10;
Cl 15.31.
1
1099, 828, 713, 648, 620, 506, 470. Н NMR, δ, ppm:
2
2.0 s (3Н, МеSе, JH–Se 11 Hz), 3.37 s (2Н, СH2Se,
2JH–Se 14 Hz), 5.22 br.s, 5.26 br.s (2Н, СН2=). 13С
1
NMR, δC, ppm: 4.64 (МеSе, JС–Se 63 Hz), 32.05
1
(СH2Se, JС–Se 66 Hz), 113.49 (=СН2), 139.11 (СlС=).
1-Phenylselanylpropadiene (V) was isolated by
vacuum distillation, bp 94°С (2.5 mm Hg). Colorless
liquid, rapidly turning yellow. IR spectrum, ν, cm–1:
77Se NMR, δ, ppm: 122.72. Mass spectrum, m/z (Irel,
%): 170 [M] (15), 153 (M – CH3 – H2) (3), 135
(M – Cl) (5), 119 (M – CH3 – Cl) (4), 107 (C2H3Se) (3),
94 (CH2Se) (43), 75 (C3H4Cl) (16), 53 (11). Found, %:
С 28.56; Н 4.47; Se 45.72; Cl 20.49. С4Н7SeCl. Cal-
culated, %: С 28.34; Н 4.16; Se 46.58; Cl 20.91.
1
1942 (νC=C=C). H NMR, δ, ppm: 4.74 d (2Н, Н2С=,
4
2
4JH–Н 6.2 Hz), 6.02 t (1Н, =СН–, JH–Н 6.2 Hz, JSe–H
20.1 Hz), 7.23 m (3Н, Нm, Нр), 7.51 m (2Н, Но). 13С
NMR, δC, ppm: 77.12 (СН2=), 77.40 (=СН–), 127.28
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

1664
LEVANOVA et al.
(Ср), 129.21 (Сm), 132.02 (Со), 134.40 (Сi), 207.91
(=С=). 77Se NMR, δ, ppm: 352.4 (2JSe–H 20.1 Hz). Mass
spectrum, m/z: 196 [M], 195 (M – Н), 157 (PhSe), 115
(PhC3H2), 91 (C7H7), 77 (Ph). Found, %: С 55.85; Н
4.43; Se 40.19. С9Н8Se. Calculated, %: С 55.40; Н
4.13; Se 40.47.
stirred at this temperature for 19 h, then cooled to 25°С,
diluted with water (30 ml), and extracted with СН2Сl2
(2×50 ml). The extract was dried over MgSO4, the
solvent was removed to give 5.1 g (64%) of crude
1
product VIII. IR spectrum, ν, cm–1: 1639 w (νC=C). H
4
NMR, δ, ppm: 2.12 d (3Н, СН3, JН–Н 1.2 Hz), 6.89 d
4
(1Н, =СH, JН–Н 1.2 Hz), 7.34 m, 7.61 m (10 Н,
1-Phenylselanyl-1-propyne (VI) was obtained
with the highest yield (68%) via the reaction of 6.0 g
(0.019 mol) of diphenyldiselenide, 10.76 g (0.192 mol)
of KOH, 48 ml of hydrazine hydrate, and 4.26 g
(0.038 mol) of dichloropropene I (33 h at 20–25°С).
Product VI was isolated by vacuum distillation of the
residue after removal of solvent from the extract, bp
95–96°С (2.5 mm Hg). Colorless liquid, rapidly
turning yellow. IR spectrum, ν, cm–1: 2191 (w) (νC≡C).
1H NMR, δ, ppm: 2.05 s (3Н, СН3), 7.25 m (5Н, Рh).
2С6Н5). 13С NMR, δС, ppm: 27.00 (СН3), 124.71 (СН=,
2
1JC–Se 100.8 Hz, JC–Se 19.7 Hz, 133.18 [=C(Me)–Se].
Aromatic signals are given first for the PhSe group in
the geminal position to the methyl group: Ср (127.31,
127.80), Сm (129.23, 129.32), Со (132.40, 2JC–Se 11.1 Hz,
2
1
134.16, JC–Se 10.9 Hz), Сi (119.69, JC–Se 70.2 Hz,
1
131.27, JC–Se 99.3 Hz). Mass spectrum, m/z: 354 [M],
314 (Ph2Se2), 234 (Ph2Se), 197 (M – PhSe), 182
(M – PhSe – CH3), 157 (PhSe), 116 (PhC3H3), 115
(PhC3H2), 77 (Ph). Found, %: С 51.89; Н 4.23; Se 44.15.
С15Н14Se2. Calculated, %: С 51.15; Н 4.01; Se 44.84.
1
13С NMR, δС, ppm: 5.63 (СН3), 57.00 (≡С–Se, JC–Se
2
174.1 Hz), 99.83 (Me–C≡, JC–Se 32.6 Hz), 126.91
2
(Ср), 128.89 (Со, JC–Se 14.6 Hz), 129.49 (Сm), 130.61
Methylselanylbenzene (selenoanisole) (IX). Methyl
iodide (2.71 g, 0.019 mol) was added dropwise upon
stirring to the water-hydrazine raffinate obtained after
extraction of compound VIII. The reaction mixture
was extracted with СН2Сl2 (2×30 ml), the extract was
dried over MgSO4, and the solvent was removed to
(Сi). 77Se NMR, δ, ppm: 269.2. Mass spectrum, m/z:
196 [M], 195 (M – Н), 115 (PhC3H2), 77 (Ph). Found,
%: С 55.25; Н 4.27; Se 40.36. С9Н8Se. Calculated, %:
С 55.40; Н 4.13; Se 40.47.
Dehydrochlorination of 2-chloro-3-phenylselanyl-
1-propene (IIIb). At 25°С, 2.09 g (0.009 mol) of IIIb
was added dropwise to the solution of 0.55 g (0.01 mol)
of KOH in 9 ml of hydrazine hydrate. The reaction
mixture was stirred at 35–38°С for 7.5 h, cooled and
extracted with СН2Сl2 (3×10 ml). The extract was
dried over MgSO4, and the solvent was removed to
give 1.36 g of the residue containing (GLC, GC–MS,
1
give 1.8 g (23%) of selenoanisole IX. H NMR, δ,
2
ppm: 2.28 s (3Н, СН3, JH–Se 11.0 Hz), 7.13 m (1Н,
Hp), 7.19 m (2H, Hm), 7.37 m (2Н, Но). 13С NMR, δС,
1
ppm: 7.14 (СН3, JС–Se 63.6 Hz), 125.96 (Ср), 128.87,
130.32 (Со, Сm), 131.78 (Сi, 1JC–Se 104.1 Hz) [21]. 77Se
NMR, δ, ppm: 200.9 [22]. Mass spectrum, m/z: 172
[M].
1
and H NMR) 0.51 g of allenylselenide V and 0.85 g
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(СН3–СН=) 6.7 Hz], 6.43 d.q (1Н, SeCН=, JНС=СН
4
8.7 Hz, JН–Н 1.2 Hz), 7.16–7.27 m (3Н, Нm.p), 7.48 m
(2Н, Но) (cf. [20]). 77Se NMR, δ, ppm: 383.8. Mass
spectrum, m/z: 198 [M], 183 (M – СН3), 157 (PhSe),
117 (PhC3H4), 105 (СН3Se), 91 (C7H7), 78 (C6H6)·, 77
(Ph).
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