Tributyltin aryl selenides as efficient arylselenating agents. Synthesis of diaryl and aryl organyl selenides

Article abstract of DOI:10.1023/A:1013460213633

Tributyltin aryl selenides are highly efficient arylselenating agents in reactions with aryl iodides and aryl triflates under catalysis with Pd and Ni complexes respectively. They also may be used as efficient source of active arylselenolate anion in the

Full text of DOI:10.1023/A:1013460213633

Russian Journal of Organic Chemistry, Vol. 37, No. 10, 2001, pp. 1463 1475. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 10, 2001,
pp. 1532 1544.
Original Russian Text Copyright
2001 by Beletskaya, Sigeev, Peregudov, Petrovskii.
Tributyltin Aryl Selenides as Efficient Arylselenating Agents.
Synthesis of Diaryl and Aryl Organyl Selenides*
I. P. Beletskaya1, A. S. Sigeev1, A. S. Peregudov2, and P. V. Petrovskii2
1Lomonosov Moscow State University, Moskow, 119899 Russia
2Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow
Received February 20, 2001
Abstract Tributyltin aryl selenides are highly efficient arylselenating agents in reactions with aryl iodides
and aryl triflates under catalysis with Pd and Ni complexes respectively. They also may be used as efficient
source of active arylselenolate anion in the presence of fluoride ions in reaction of arylselenation of alkyl
halides and activated aryl fluorides.
Compounds with arylseleno group attract attention
due to wide possibilities of their application. Amino-
substituted diarylselenides are highly efficient anti-
oxidants [1, 2]. Many compounds containing aryl-
selenic and diarylselenic moiety are interesting for
pharmacology [3 5]. Polymers based on diaryl
selenides are potential electroconducting materials
[6 8]. Complexes of arylseleno-substituted tetrathio-
fulvalene exhibit properties of a semiconductor [9].
they are more stable against air oxygen, against
hydrolysis, and do not stink. We showed that the
tributyltin aryl selenides easily prepared by irradia-
tion of a mixture of hexabutyldistannane and the cor-
responding diaryl selenide are efficient arylselenation
reagents in reactions with various substrates, e.g.,
aryl, benzyl, propargyl, allyl, and alkyl halides,
activated aryl fluorides, and also aryl triflates and
aryldiazonium salts. (On the use of Bu3SnSePh as
efficient arylselenating reagents was reported in
preliminary communications [23 25]).
Procedures for introducing arylseleno group into
organic compound are diverse and contain both
electrophilic and nucleophilic arylselenation reactions
[10 20]. Therewith the range of organoselenating
reagents is sufficiently wide but most of them have
various disadvantages, as difficulties in handling,
disposition to hydrolysis or oxidation by oxygen.
Therefore disregarding the versatility of available
organoselenating reagents still remains undying
interest to new easy-to-handle compounds that can
serve as a source of organoseleno group.
Arylselenation of aryl iodides by Bu3SnSePh
catalyzed by palladium complexes. Aryl halides are
among the most widely used substrates for cross-
coupling. The preliminary study was carried out by
an example of phenylselenation of iodobenzene with
Bu3SnSePh (Scheme 1, Table 1).
The reaction progress was monitored by means of
119Sn NMR spectroscopy. The composition and yield
of selenium-containing products were controlled by
77Se NMR spectroscopy.
The possibility to apply triorganyltin organo-
chalcogenides as organoselenating agents is poorly
studied. Several examples are known of the use of
tributyltin organosulfides in the reactions of cross-
coupling with aryl and vinyl bromides catalyzed by
palladium complexes [21, 2]. However in similar
reactions were not used selenium analogs before our
studies. Yet the triorganyltin organoselenides are
notably easier to handle than analogous selenols for
We showed that in the absence of the catalyst no
diphenyl selenide formed even after heating for 30 h.
At the same time the addition of 1.5 5 mol% of
Pd(PPh3)4 resulted in phenylselenation product
formed in high yield. The reaction duration depends
on the catalyst amount. The activity of the Pd(II)
complexes in xylene is considerably lower. Thus in
the presence of PdCl2(PPh3)2 the reaction time is
significantly longer than with Pd(PPh3)4. Yet in going
to more polar solvent, DMF, the rate of reaction
catalyzed by PdCl2(PPh3)2 notably increases and
becomes comparable with that under catalysis with
Pd(PPh3)4. Note that with the latter catalyst the rate
*
The study was carried out under financial support of the
Russian Foundation for Basic Research and Russian Ministry
of Education, program Leading Scientific School (grant
no. 00-15-97406), and Integration of High School with the
Academy of Sciences (grant AO-15).
1070-4280/01/3710-1463$25.00 2001 MAIK Nauka/Interperiodica

1464
BELETSKAYA et al.
Scheme 1.
Scheme 2.
1.5 mol% [Pd]
Table 2. Yields of products obtained by arylselenation of
aryl iodides ArI with tributyltin aryl selenides Bu3SnSeAr
at 100 C in the presence of palladium catalysts
ArI + Bu3SnSeAr
Ia k
ArSeAr
IIa p
5 h, 100 C
Compd.
no.
ArSeAr
Yield,b
%
Method A: [Pd] = Pd(PPh3)4, xylene; method B:
[Pd] = PdCl2(PPh3)2, DMF. I), Ar = Ph (a),
4-MeOC6H4 (b), 4-Me2NC6H4 (c), 4-NO2C6H4 (d),
3-NO2C6H4 (e), 4-BrC6H4 (f), 4-IC6H4 (g), 4-AcC6H4
(h), 4-EtOOCC6H4 (i), 4-pyridyl (j), 1-naphthyl (k);
Methoda
Ar
Ar
IIa Ph
IIa
IIl
IIb 4-MeOC6H4
IIm
IIc 4-Me2NC6H4
IIc
IId 4-NO2C6H4
IIn
IIe 4-NO2C6H4
Ph
A
B
B
A
B
A
B
A
B
A
A
A
A
B
A
B
A
B
B
A
B
B
92 (87)
98 (93)
96 (94)
93 (88)
90 (87)
63 (60)c,
15d
87 (83)
89 (82)
93 (85)
84 (80)
95 (93)
87 (79)
93 (96)
54 (50)
98 (94)
90 (81)
96 (92)
94 (89)
92 (86)
90 (83)
98 (95)
II, Ar
= Ph: Ar = Ph (a), 4-MeOC6H4 (b),
4-Me2NC6H4 (c), 4-NO2C6H4 (d), 3-NO2C6H4 (e),
4-BrC6H4 (f), 4-PhSeC6H4 (g), 4-AcC6H4 (h),
4-EtOOCC6H4 (i), 4-pyridyl (j), 1-naphthyl (k);
4-FC6H4
Ph
4-FC6H4
Ph
Ar
= 4-FC6H4: Ar = Ph (l), 4-MeOC6H4 (m),
4-NO2C6H4 (n), 4-pyridyl (o), 1-naphthyl (p).
Ph
Ph
Scheme 3.
4-FC6H4
Ph
IIf
4-BrC6H4
Ph
Ph
Ph
Products ratio in the reaction mixture ArSePh : Ar2Se:
Ph2Se = 2: 1: 1.
IIg 4-IC6H4e
IIh 4-AcC6H4
IIh
IIi
IIi
IIj
IIj
IIo
Table 1. Effect of catalyst and reaction conditions on
yield of Ph2Se, the product of phenylselenation of
iodobenzene with Bu3SnSePh at 100 Ca
4-EtO2CC6H4
Ph
Ph
Solvent Time, Conversion
4-Py
Catalyst, mol%
h
Bu3SnSePh,b Yield,c
%
%
4-FC6H4
Ph
4-FC6H4
Ph
IIk 1-C10H7
IIp 1-C10H7
IIg 4-PhSeC6H4e
Xylene 30
0
Pd(PPh3)4, 5
Pd(PPh3)4, 3
Pd(PPh3)4, 1.5
Pd(PPh3)4, 1.5
PdCl2(PPh3)2, 1.5 Xylene 30
PdCl2(PPh3)2, 1.5 DMF
PdCl2(MeCN)2, 1.5 Xylene 12
PdCl2(MeCN)2, 1.5 DMF 15
PdCl2(PhCN)2, 1.5 Xylene 12
Xylene
Xylene
Xylene
DMF
1.5
3
5
100
100
100
100
100
100
0
94
92
95
90
93
98
a
5
Method A: 1 mmol of Bu3SnSePh, 1 mmol of ArI, 1.5 mol%
of Pd(PPh3)4, 2 ml of xylene, 5 h; Method B: 1 mmol of
Bu3SnSePh, 1 mmol of ArI, 1.5 mol% of PdCl2(PPh3)2, 2 ml
of DMF, 4 h.
4
<10
0
b
Yield according to 77Se NMR data. Preparative yield is given
in parentheses.
PdCl2(PhCN)2, 1.5 DMF
16
<10
c
d
e
f
Reaction time 12 h.
Reaction time 14 h.
Two equiv of Bu3SnSePh were used.
This aryliodide was synthesized from Bu3SnSePh and
(4-IC6H4N2)2ZnCl4 (Table 4).
a
Reaction conditions: 1 mmol of Bu3SnSePh, 1 mmol of
PhI, 2 ml of solvent.
Conversion of Bu3SnSePh by 119Sn NMR data.
Yield of Ph2Se by 77Se NMR data.
b
c
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TRIBUTYLTIN ARYL SELENIDES AS EFFICIENT ARYLSELENATING AGENTS
1465
of reaction does not change in going to DMF solvent.
Acetonitrile and benzonitrile palladium(II) complexes
are inactive both in xylene and DMF.
accelerated the exchange of anionoide rests, and in
the 119Sn NMR spectra occurred strong broadening of
Bu3SnSePh and BuSnI signals. Reaction monitoring
with the use of 77Se NMR spectra is inconvenient due
to long time of spectra registering. Therefore we
applied to reaction monitoring 19F NMR spectro-
scopy. To this end we synthesized tributyltin aryl
selenide containing fluorine label in the para-position
of the benzene ring. With the use of this compound
we obtained by cross-coupling a number of fluorine-
substituted diaryl selenides. Their synthesis was
carried out by reaction with aryl iodides in the
presence of PdCl2(PPh3)2 affording diaryl selenides
in high yield.
Thus the cross-coupling of iodobenzene and
Bu3SnSePh is efficiently catalyzed by complex
Pd(PPh3)4 in xylene or PdCl2(PPh3)2 in DMF.
Under the given conditions we studied the effect
on the reaction of the substituents in the aryl iodide.
It was established that at the use of both methods
(Scheme 2) were obtained similar results, and diaryl
selenide was formed in high yield (Table 2).
An exception concerned only the reactions of aryl
iodides with strong electron-donor substituents, e.g.
with dimethylamino group. In this case the Pd(II)
complex is of low efficiency. Diaryl selenide IIb was
obtained only with catalysis by Pd(PPh3)4 in moderate
yield. In reaction with ethyl 4-iodobenzoate (Ii) the
catalysis by Pd(PPh3)4 resulted in the disproportiona-
tion of the formed diaryl selenide IIi (Scheme 3) that
reduced the yield of reaction products. Yet in the
presence of PdCl2(PPh3)2 no disproportionation
occurred.
The most probably this reaction follows the
common cross-coupling mechanism [27] (Scheme 4).
Scheme 4.
This reaction was extended to derivatives of
naphthalene and pyridine. With 4-iodopyridine the
Pd(II) catalyst also provided a possibility to obtain
4-(phenylseleno)pyridine in higher yield than with
Pd(O) complex in xylene due to reduced amount of
side products. 4-Bromoiodobenzene reacts selectively
with only iodine substitution.*
With 1,4-diiodobenzene are easily substituted both
iodine atoms to furnish diaryl selenide IIg.
The monitoring of reaction progress we commonly
used was not suitable for reactions performed in
DMF. The coordination with solvent apparently
77Se NMR spectra of compounds of ArSePh
type. Compounds of ArSePh type synthesized in this
study are a convenient object for investigation on
effect of substituents in aryl ligand on the chemical
shifts of 77Se nuclei. It was established that the 77Se
chemical shifts (Table 3) measured for 10 model com-
*
Recently appeared information [26] on cross-coupling of
Bu3SnSePh with bromo- and even chlorobenzene catalyzed
with Pd(PPh3)4 that was in disagreement with our results. We
repeated the described experiments and did not observe the
diphenyl selenide formation along cross-coupling reaction.
This product formed only by disproportionation of the initial
pounds correlated well with Hammett,s
constants
of the substituted aryl radicals, and the slope of the
plot had a positive value: (77Se) = (26.6 4.7)
49.1; r 0.981, s 3.6.
compound along the equation 2Bu3SnSePh
(Bu3Sn)2Se +
This fact evidence that on the shielding of 77Se
nuclei prevailing influence has the paramagnetic
component of the shielding constant. This conclusion
is consistent with the common interpretation of the
chemical shifts in organoselenium compounds [28,
29]. It should be noted that recently were measured
the chemical shifts 77Se for 7 compounds [30].
Correlation treatment of these data provided a notably
worse correlation factor (r 0.934).
Ph2Se. Therefore the yield of reaction product could not be
over 50% (in [26] was indicated yield of 60% for reaction
with PhCl). Our data obtained by means of 119Sn and
77Se NMR showed that in reaction of Bu3SnSePh with chloro-
benzene in the presence of Pd(PPh3)4 formed no Bu3SnCl but
appeared only (Bu3Sn)2Se as was confirmed by comparison
with spectra of an authentic sample. The reaction monitoring
in [26] was performed by GLC that obviously did not allow
revealing the above situation.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

1466
BELETSKAYA et al.
Table 3. Chemical shifts in 77Se NMR spectra (xylene,
additive; the reaction afforded diphenyl selenide in
high yield (Table 4). With no LiBr the main reaction
product was PhSeSePh. Under these conditions
reacted also 1-naphthyl triflate to furnish in good
yield 1-naphthyl phenyl selenide (Table 4). In this
reaction catalysis by palladium is less efficient.
Although on addition of LiBr the yield of di-
phenyl selenide increased, it still remained lower than
at catalysis on nickel complexes.
ppm) and Hammett,s
constants for a series of
synthesized diaryl selenides
Ar
(77Se)
[31]
0.83
0.66
0.268
0.0
0.232
0.44 [32]
0.502
0.45
0.71
0.778
4-Me2NC6H4
4-H2NC6H4
4-CH3OC6H4
Ph
4-BrC6H4
68.6
65.4
61.9
46.5
46.1
39.3
36.5
36.5
28.3
25.7
a
Phenylselenation of aryldiazonium salts with the
use of Bu3SnSePh. Aromatic amines also can be in-
volved into the cross-coupling reaction via transform-
ation thereof into diazonium salts. The common
procedures applying water solutions of diazonium
salts and alkaline solutions of selenophenols are
inconvenient and afford diaryl selenides in moderate
yield [13, 14, 33, 34]. Reaction of ArSeNa with
aryldiazonium tosilates in nonaqueous medium gave
similar results [35].
4-Py
4-AcC6H4
4-EtCOOC6H4
3-NO2COC6H4
4-NO2COC6H4
a
This diaryl selenide was obtained in low yield and char-
acterized only with 77Se NMR spectrum.
We studied reactions of tin selenide with stable
aryldiazonium salts, fluoborates and tetrachloro-
zincates. Both phenyldiazonium fluoborate and the
corresponding double salt with zinc chloride readily
react with Bu3SnSePh at room temperature in polar
Phenylselenation of aryl triflates with the use of
Bu3SnSePh under catalysis with transition metal
complexes. Aryl triflates are interesting substrates
due to the availability of the initial phenols. However
before our study [23] reactions of aryl triflates with
selenium-centered nucleophiles were not known.
Table 4. Conditions of reaction between Bu3SnSePh
and aryl triflates in the presence of palladium or nickel
catalyst at 100 C, and yields of reaction productsa
Scheme 5.
Yield,
c
Ar
Catalyst
Solvent
DMF
%
As model compound we selected phenyl triflate as
the most accessible compound. It was found that
phenylselenation of PhOTf occurred readily in
butanol in the presence of NiCl2(PPh3)2 with LiBr as
Ph
Ph
Ph
Ph
Ph
Ph
Ph
1-C10H8
PdCl2(PPh3)2
10
17 100
0
0
LiBrd DMF
60
56
10
20
26f
LiBrd Dioxane 35 62
Xylene 20 20
Pd(PPh3)4
NiCl2(PPh3)2
Dioxane 17 25
i-PrOH 5e 100
LiBrd BuOH
LiBrd BuOH
12 100 80 (78)
12 100 78 (75)
a
Reaction conditions: 1 mmol of ArOTf, 1 mmol of Bu3SnSePh,
2 ml of solvent.
b
c
Conversion of Bu3SnSePh was determined from 119Sn NMR
spectra.
Yield of ArSePh was determined from 77Se NMR spectra.
Preparative yield is given in parentheses.
d
e
4 equiv of LiBr.
Temperature 82 C.
f
Correlation between 77Se NMR chemical shift and
Alongside diphenyl selenide formed
,
Hammett s constant for aryl phenyl selenides (II).
diphenyl diselenide (60%).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

TRIBUTYLTIN ARYL SELENIDES AS EFFICIENT ARYLSELENATING AGENTS
1467
solvents affording diphenyl selenide in high yield
(Table 5). Reaction is very fast and does not require a
catalyst. The reaction is of general character and
occurs with aryldiazonium salts containing both
electron-donor and electron-withdrawing substituents,
and also with derivatives of 1-naphthyl and
1,4-phenylenediazonium. In the latter case the reac-
tion with two equiv of Bu3SnSePh gave rise to a pro-
duct of double substitution. Reaction with a double
mercury salt of phenyldiazonium (IIc) resulted in an
intractable mixture of products with insignificant
content of diphenyl selenide.
It was formerly reported [36] that aryl thiolates of
alkali metals react with aryldiazonium salts in water
solutions to furnish diazo sulfides IV (Scheme 7). We
showed that with Bu3SnSPh arose not diazo sulfide
IV but diphenyl sulfide (V). This difference in
behavior at the use of tributyltin phenyl sulfide is due
apparently to the Lewis acidity of compounds of
R3SnX type facilitating nitrogen evolution.
Scheme 6.
Scheme 7.
Solvent = DMF, acetone, CH3CN, CH3OH.
II, Y = H (a), 4-MeO (b), 4-NO2 (d), 4-PhSe (g),
4-I (q); YPh = 1-C10H7 (k). III, Y = H: X = BF4
(a), X = ZnCl24 (b), X = HgCl3 (c); Y = 4-NO2:
X = BF4 (d), X = ZnCl24 (e); Y = 4-CH3O: X =
BF4 (f), X = ZnCl24 (g); Y = 4-I: X = ZnCl24 (h),
YPh = 1-C10H7, X = BF4 (i); Y = N+2 , X = BF4 (j).
Reaction of Bu3SnSePh with activated aryl
fluorides. Polyfluoroaromatic compounds are attrac-
tive substrates for arylselenation since the expected
polyfluorodiaryl selenides are hard to prepare and
poorly studied. Their preparation methods are limited
Table 5. Yields of phenylselenation products from aryldiazonium salts ArN2X and Bu3SnSePha
ArN2X
Solvent
Ar in ArSePh
Yield,b
94
%
Compd. no.
Ar
X
IIIa
Ph
BF4
DMF
Ph
CH3OH
Acetone
THF
93 (89)
90 (85)
91
IIIb
ZnCl42
Acetone
DMF
95 (91)
96
CH3OH
THF
99 (96)
95
CH3CN
DMF
96
10
IIIc
IIId
HgCl3
BF4
4-NO2C6H4
4-MeOC6H4
Acetone
CH3OH
Acetone
CH3OH
CH3OH
CH3OH
CH3OH
CH3OH
CH3OH
4-NO2C6H4
4-MeOC6H4
(90)
(95)
(91)
(96)
(92)
(97)
(94)
(93)
IIIe
ZnCl24
IIIf
IIIg
IIIh
IIIi
BF4
ZnCl24
ZnCl42
BF4
4-IC6H4
1-Naphthyl
4-N2+ C6H4
4-IC6H4
1-Naphthyl
4-PhSeC6H4
IIIjc
BF4
(98)
a
b
c
Reaction conditions: 1 mmol of Bu3SnSePh, 1 mmol ofArN2X, 2 ml of solvent.
Yield from 77Se NMR data. Preparative yield is given in parentheses.
Reaction with two equiv of Bu3SnSePh.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

1468
BELETSKAYA et al.
Table 6. Effect of catalyst and solvent on product yield
the more polar DMF does not require for its initiation
an addition of the fluoride catalyst and is complete at
room temperature within 2 h. The yield of aryl
phenyl selenide is here virtually quantitative. In this
connection the published data on low activity of lead
arylselenolates under the same conditions were quite
unexpected [37].
in reaction of Bu3SnSePh with octafluorotoluenea
Solvent
Additive
Tempera- Time, Yield,
ture,
C
h
%
CHCl3
61
8
0
CHCl3 10% KF
CHCl3 10% KF + 10 mol%
BTEAC
61
61
14
12
10
78
Schema 8.
ArF + Bu3SnSeAr
ArSeAr + Bu3SnF
CHCl3 10% CsF + 10 mol%
BTEAC
61
61
61
25
12
12
12
2
81
(75)
79
VIa d
VIIa e
VI, Ar = tetrafluoro-4-pyridyl (a), 4-CF3C6F4 (b),
C6F5 (c), 4-NO2C6H4 (d), 4-AcC6H4 (e), 4-EtO2CC6H4
(f); VII, Ar = Ph: Ar = tetrafluoro-4-pyridyl (a),
4-CF3C6F4 (b), C6F5 (c); Ar = 4-FC6H4: Ar = tetra-
fluoro-4-pyridyl (d), 4-CF3C6F4 (e).
CHCl3 10% KF + 10 mol%
dibenzo-18-crown-6
CHCl3 10% CsF + 10 mol%
dibenzo-18-crown-6
DMF
82
97 (95)
a
Under the selected conditions the reaction was
carried out also with some other fluoroarenes
(Scheme 8). The results of reaction between
Bu3SnSePh and various aryl fluorides in chloroform
in the presence of fluoride ions or DMF are presented
in Table 7. The reaction of pentafluoropyridine with
Bu3SnSePh in the boiling chloroform goes faster and
affords higher yield of diaryl selenide VIIa than the
similar reaction with octafluorotoluene. In DMF the
difference disappears, and the yields of the phenyl-
selenation products obtained from octafluorotoluene
and pentafluoropyridine are virtually equal. Hexa-
fluorobenzene fails to be phenylselenated under the
described conditions. Thus after heating in DMF to
100 C for 15 h formed only negligible amount of
diaryl selenide VIIc. With 4-nitro-1-fluorobenzene
reaction in chloroform provided 4-nitrodiphenyl
selenide in a low yield. The main product in this case
was diphenyl selenide formed by oxidation of PhSe
anion. However in DMF at 100 C the yield of
4-nitrodiphenyl selenide sharply increased and attain-
ed 98%. Yet aryl fluorides with less electron-with-
drawing substituents, 4-fluoro-1-acetophenone and
ethyl 4-fluorobenzoate, failed to react with
Bu3SnSePh under the given conditions. The monitor-
ing of phenylselenation of monofluoro-substituted
arenes by means of 19F NMR was performed with the
use of fluorobenzene as internal reference inert under
the given conditions.
Reaction conditions: 1 mmol of Bu3SnSePh, 1 mmol of
C6F5CF3, 2 ml of solvent.
in number [37 39] and require stringent conditions.
At the same time including a polufluoroaryl substitu-
ent into a molecule of diaryl selenide may be interest-
ing from the viewpoint of biological activity.
We found that Bu3SnSePh reacted with activated
fluoroaromatic compounds in the presence of catalytic
amounts of inorganic fluorides providing the cor-
responding diaryl selenides in good yield. Note that
nucleophilic assistance of fluoride ion is well known
for reactions of organotin compounds, in particular,
of tin selenides [40 44].
The reaction conditions were selected by an
example of octafluorotoluene. The reaction monitor-
ing was performed by 19F NMR spectroscopy. The
conversion was evaluated from the ratio of signals
belonging to the original octafluorotoluene and the
reaction products. The reaction was carried on till the
fluorine signals from the original fluoroarene dis-
appeared. The reaction product purity was also
checked by 77Se NMR spectroscopy.
In Table 6 are presented the results of Bu3SnSeAr
reaction with octafluorotoluene in the presence of
various inorganic fluorides and phase-transfer catal-
ysts. Practically no aryl phenyl selenide formed in
the absence of fluoride ions and phase-transfer catal-
ysts. In the presence of benzyltriethylammonium
chloride or dibenzo-18-crown-6 the character of
inorganic cation hardly affected the yield of the
phenylselenation product although with potassium
fluoride the yield was commonly a little lower.The
reaction between Bu3SnSeAr and octafluorotoluene in
As a result of reactions carried out in the similar
way between activated fluorides VIa, b, d and
4-FC6H4SeSnBu3 were obtained in high yield aryl-
selenation products IIn and VIId, e (Table 7).
The phenylselenation of perfluoroaromatic com-
pounds occurs with high selectivity: exclusively
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

TRIBUTYLTIN ARYL SELENIDES AS EFFICIENT ARYLSELENATING AGENTS
1469
forms the product of fluorine atom substitution in the
para-position with respect to the substituent present
in the ring. The structure of products and regio-
selectivity of the reaction were proved by 19F and
77Se NMR spectra. No substitution of two or more
fluorine atoms in the presence of excess phenyl-
selenating agent was observed.
Table 7. Reaction conditions and yields of arylselenation
products from activated aryl fluorides and Bu3SnSeAr a
ArSeAr
Ar
Compd.
no.
Time, Yield,c
Methodb
h
%
Ar
4-C5F4N
4-CF3C6F4
C6F5
Ph
VIIa
A
B
B
A
B
B
A
C
A
C
C
C
C
5
2
2
98 (95)
97 (92)
97 (93)
4-FC6H4 VIId
Ph VIIb
12 82 (75)
2
2
10
15
10
5
5
12
12
97 (95)
96 (92)
4-FC6H4 VIIe
Ph
X = N, C-CF3.
VIIc
0
7
20
Although the detailed investigation of mechanism
was not performed the most probable is the classical
aromatic nucleophilic substitution with the nucleo-
philic assistance of a fluoride ion (Scheme 9).
4-NO2C6H4 Ph
IId
98 (92)
97 (93)
0
4-FC6H4 IIn
Ph
4-AcC6H4
4-EtO2CC6H4 Ph
IIh
IIi
In the dimethylformamide with no additives the
nucleophilic assistance is provided by the solvent
(Scheme 10).
0
a
Reaction conditions: 1 mmol of ArF, 1 mmol of Bu3SnSeAr,
2 ml of solvent.
Method A: 10% CsF + 10% BTEAC, CHCl3, 61 C; Method
B: DMF, 25 C; Method C: 10% CsF, DMF, 100 C.
Yield from 77Se NMR data. Preparative yield is given in
parentheses.
Reaction of Bu3SnSeAr with alkyl, allyl, benzyl,
and propargyl halides. The usual synthesis of alkyl
b
c
Scheme 9.
aryl selenides consists on arylselenation of alkyl
halides with arylselenols in the presence of bases or
by arylselenolates of alkali metals [45 47]. As
organoselenating reagents were also proposed
thallium arylselenolates [48]. Yet the difficulties in
handling selenols and toxicity of thallium compounds
call for a search of new more convenient in handling
arylselenating reagents. It was previously shown that
fluorodestannylation (R3SN)2Se could serve as a
convenient procedure for generation of an active
selenide dianion [40].
EWG = F5, 2,3,5,6-F4-4-CF3, 4-NO2, 2,3,5,6-F4-4-N.
Scheme 10.
We demonstrated that tributyltin aryl selenides
readily react with alkyl, allyl, benzyl, and propargyl
halides in the presence of fluoride ions affording the
corresponding aryl organyl selenides in high yield.
Scheme 11.
RHlg + ArSeSnBu3
RSeAr + Bu3SnF
KF
VIIIa e
IXa f
VIII, R = PhCH2 (a), 2-CH3C6H4CH2 (b), Et (c),
H2C=CHCH2 (d), HC CCH2 (e); IX, Ar = Ph: R =
PhCH2 (a); Ar = 4-FC6H4: R = PhCH2 (b),
2-CH3C6H4CH2 (c), Et (d), H2C=CHCH2 (e),
HC CCH2 (f).
EWG = 2,3,5,6-F4-4-CF3, 2,3,5,6-F4-4-N.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

1470
BELETSKAYA et al.
Table 8. Arylselenation conditions with 4-FC6H4SeSnBu3
of benzyl bromide, and yield of benzyl 4-fluorophenyl
selenidea
the reaction, and it completes in 2 h at room tempera-
ture. In boiling chloroform the reaction time is
reduced to 0.5 h.
It should be notes that the course of the reaction is
considerably affected by the mode of reagents mixing.
In case tributyltin aryl selenide is added to the mix-
ture of RHlg and KF, the reaction rate sharply de-
creases, and the yield of arylselenation product is
notably lower than if potassium fluoride is added to
the mixture of Bu3SnSeAr and RHlg.
Tempe- Time, Yield,b
Solvent
CHCl3
Additives
rature,
C
h
%
61
25
19
2
96 (92)
96 (90)
2 equiv KF + 10 mol%
BTEAC
2 equiv KF + 10 mol%
BTEAC
61
0.5 99 (95)
In going to more polar DMF the rate of benzyl
bromide arylselenation significantly grows. For
instance, without fluoride ions at room temperature
reaction completes in 11 h against 19 h in boiling
chloroform. The reaction rate sharply increases after
addition of potassium fluoride, and the complete
conversion of Bu3SnSeAr is attained already in 0.5 h.
In all cases the yield of 4-fluorophenyl benzyl
selenide was close to quantitative.
DMF
25
25
11
95 (90)
DMF 2 equiv. KF
0.5 99 (96)
a
Reaction conditions: 1 mmol of 4-FC6H4SeSnBu3, 1 mmol of
PhCH2Br, 2 ml of solvent.
Yield from 19F NMR data. Preparative yield is given in
parentheses.
b
Thus the reaction between Bu3SnSeAr and alkyl
halides easily goes in the presence of KF at room
temperature in DMF or in boiling chloroform with
addition of a phase-transfer catalyst.
Table 9. Arylselenation conditions with Bu3SnSeAr of
benzyl, alkyl, allyl, and propargyl halides RHlg, and yield
of reaction productsa
RSeAr
Yield,c
%
In reaction with benzyl bromide was also used as
organoselenating agent Bu3SnSePh whose reactivity
was on the same level as that of 4-FC6H4SeSnBu3.
Methodb
R
Ar
Into reaction with tributyltin aryl selenides was
also involved a number of the other organyl halides
(Table 9). Among all the bromides studied (VIIIa,
c d) the most active was benzyl bromide. Reactivity
of propargyl bromide was somewhat higher than that
of allyl bromide; however in the more polar DMF
the difference is levelled. The least active was ethyl
bromide: the reaction in DMF took 2 h against 0.5
1 h in the other cases. Also chloromethyl-2-methyl-
benzene was involved into the reaction; however,
here the yield of diorganyl selenide IXc was some-
what lower than with unsubstituted benzyl bromide,
probably due to steric hindrances.
PhCH2
Ph
IXa
A
B
A
B
A
B
A
B
A
B
2
97 (94)
0.5 98 (93)
99 (95)
0.5 99 (94)
4-FC6H4 IXb
2
2-CH3C6H4CH2 4-FC6H4 IXc
Et 4-FC6H4 IXd
H2C= CHCH2 4-FC6H4 IXe
4
2
4
1
3
1
91 (82)
93 (81)
82 (78)
93 (84)
90 (81)
97 (89)
HC=CCH2
4-FC6H4 IXf
a
Reaction conditions: 1 mmol of 4-FC6H4SeSnBu3, 1 mmol of
RHlg, 2 ml of solvent.
Method A: 2 equiv of KF + 10 mol% BTEAC, CHCl3, 25 C;
method B: 2 equiv of KF, DMF, 25 C.
Yield from 19F NMR data. Preparative yield is given in
parentheses.
Hence tributyltin aryl selenides are highly efficient
arylselenating reagents in reactions with aryl iodides
and aryl triflates under catalysis with complexes of
Pd and Ni respectively, and also in reactions with the
stable aryldiazonium salts. They can be used also as
efficient source of active arylselenolate anion in the
presence of fluoride ions in arylselenation reactions
of alkyl halides and activated alkyl fluorides.
b
c
The preliminary experiments were carried out by
the example of arylselenation of benzyl bromide with
tributyltin 4-fluorophenyl selenide. In the absence of
fluoride ions the reaction rate is low, and complete
conversion in boiling chloroform is reached in 19 h.
The addition of 2 equiv of KF and 10 mol% of
benzyltriethylammonium chloride strongly facilitates
EXPERIMENTAL
All reactions save those with aryldiazonium salts
were carried out under inert nitrogen atmosphere.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

TRIBUTYLTIN ARYL SELENIDES AS EFFICIENT ARYLSELENATING AGENTS
1471
The workup of reaction mixtures and separation of
reaction products does not require inert atmosphere.
The solvents were dried by standard methods [31] and
distilled under nitrogen just before use. The NMR
monitoring of reactions was performed by carrying
out the process in sealed NMR tubes. Aryl triflates
[49], aryldiazonium salts [50], Pd(PPh3)4 [51],
PdCl2(PPh3)2 [52], NiCl2(PPh3)2 [53] were synthesiz-
ed along described procedures. Tributyltin aryl
selenides were obtained by reaction of Bu6Sn2 with
ArSeSeAr in benzene under irradiation with daylight
[54].
Table 10. 1H and 13C NMR spectra of diaryl selenides
IIa q (acetone-d6)
1H NMR spectrum,
, ppm
13C NMR spectrum,
C, ppm
IIa 7.32 7.41 m (6H),
127.13, 127.79, 127.93,
130.24
7.49 7.57 m (4H)
IIb 3.57 s (3H), 6.89 d (2H, 56.05, 116.47, 120.62,
J 8.72 Hz), 7.15 7.22 m 127.72, 130.47, 130.71,
(3H), 7.28 7.31
m
131.95, 134.1, 137.81
(2H), 7.48 d (2H, J
8.72 Hz)
77Se and 199Sn NMR spectra were recorded on
spectrometer Bruker WP-200 SY at operating frequ-
encies 38.19 and 74.6 MHz respectively from solu-
tions in benzene or chloroform. 19F NMR spectra
were registered on spectrometers Bruker WP-200 SY
and Bruker AMX-400 at operating frequencies 188.3
and 376.5 MHz respectively from solutions in
chloroform or DMF. The stabilization was performed
from external D2O sample. As external references
were used Me4Sn (119Sn), Ph2Se2 (77Se), and tri-
IIc 2.9 s (6H), 6.6 d (2H, 40.77, 114.41, 127.05,
J 10 Hz), 7.01 7.18 m 130.02, 130.29, 132.37,
(3H), 7.21 7.24 m (2H), 135.91, 138.05, 152.03
7.42 d (2H, J 10 Hz)
IId 7.44 d (2H, J 8.76 Hz), 125.1, 128.57, 130.53,
7.4 7.47 m (3H), 7.62
7.65 m (2H), 8.02 d
(2H, J 8.76 Hz)
131.22, 131.32, 136.84,
144.59, 147.62
IIe 7.4 7.7 m (6H), 8.0
122.83, 126.41, 130.1,
8.2 m (2H), 8.1 s (1H) 131.22, 131.58, 135.7,
135.93, 138.21, 155.44,
1
fluoroacetic acid (19F). H and 13C NMR spectra were
measured on Bruker AMX-400 instrument at operat-
ing frequencies 400.13 and 100.5 MHz respectively
from solutions in acetone-d6 or CDCl3. Mass spectra
were measured on Kratos MS 890 spectrometer.
167.8
IIf 7.30 7.33 m (3H), 7.32 d 122.24, 129.19, 130.9,
(2H, J 8.72 Hz), 7.44 d 131.18, 131.83, 133.64,
(2H, J 8.72 Hz), 7.43
134.63, 135.41
7.48 m (2H)
Reaction of aryl iodides with Bu3SnSePh.
Method A. To a solution of 1 mmol of ArI and
0.015 mmol of Pd(PPh3)4 (1.5 mol%, 17 mg) in 1 ml
of anhydrous toluene in a Schlenk vessel under argon
atmosphere was added 1 mmol of Bu3SnSeAr in 1 ml
of anhydrous toluene. The arising brown-red mixture
was heated to 100 C for 5 h. On evaporating the solu-
tion the residue was dissolved in acetone and poured
into water solution of KF. After treating with toluene
the organic layer was filtered and dried with Na2SO4.
The solvent was removed in a vacuum, diaryl selenide
was purified by column chromatography on silica gel
[eluent hexane (IIa, b, f, h, k, l, m, p), hexane +
5% of chloroform (IIc, d, e, i, j, n, o)] or by re-
crystallization from hexane (IIg). The spectral data
of compounds obtained are presented in Tables 10
and 11.
IIg 7.33 s (6H), 7.37 m 127.54, 129.33, 130.38,
(4H), 7.54 m (6H) 130.53, 133.17, 133.30
IIh 2.58 s (3H), 7.38 7.42 m 26.64, 128.56, 128.69,
(3H), 7.43 d (2H, J 128.89, 129.70, 130.50,
8.23 Hz), 7.62 7.64 m 135.02, 135.39, 140.12,
(2H), 7.83 d (2H, J 197.03
8.23 Hz)
IIi 1.33 t (3H, J 6.1 Hz), 14.32, 60.99, 128.96,
4.31 q (2H, J 6.1 Hz), 129.13, 129.40, 130.19,
7.39 m (5H), 7.58 m 130.39, 130.74, 135.17,
(2H), 7.87 d (2H, J 139.58, 165.76
7.8 Hz)
IIj 7.02 d (2H, J 4.8 Hz), 123.45, 127.13, 127.79,
7.3 7.4 m (3H), 7.55
6 m (2H), 8.2 br.s 146.65
(2H)
128.77, 131.86, 132.87,
IIk 7.1 8.4 (12H)
127.45, 127.80, 128.26,
128.34, 128.68, 129.89,
129.96, 130.06, 130.66,
130.72, 132.79, 132.91,
135.26, 135.59
Method B. To a solution of 1 mmol of ArI and
0.015 mmol of PdCl2(PPh3)2 (1.5 mol%, 11 mg) in
1 ml of anhydrous DMF in a Schlenk vessel under
argon atmosphere was added 1 mmol (0.446 g) of
Bu3SnSeAr in 1 ml of anhydrous DMF. The arising
brown-red mixture was heated to 100 C for 5 h. On
finishing the heating the reaction mixture was poured
into water. Further workup was carried out as in
method A.
IIl 7.29 7.39 m (3H), 7.51 114.76, 124.6, 127.13,
7.59 m (2H), 7.46 d.d 127.79, 129.70, 130.24,
[2H, J 8.56, J(1H 19F) 161.10
5.60 Hz], 6.99 pseudo-t
(2H)
3
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

1472
BELETSKAYA et al.
Table 11. 77Se and 19F NMR spectra and molecular ions of
Table 10. (Contd.)
diaryl selenides IIa q
1H NMR spectrum,
, ppm
13C NMR spectrum,
C, ppm
Compd. 77Se NMR spectrum, 19F NMR spectrum, [M]+ a
no.
Se, ppm
F, ppm
IIm 3.57 s (3H), 6.89 d (2H, 54.50, 113.46, 114.28,
8.72 Hz), 7.05 121.17, 124.52, 129.79,
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
IIj
IIk
IIl
IIm
IIn
IIo
IIp
IIq
46.5
61.9
68.6
25.7
28.3
46.4
46.6
36.5
36.5
39.3
108.5
48.1
70.2
35.7
41.2
111.6
46.3
234
264
277
279
279
312
390
276
306
235
284
255
282
297
253
302
360
J
pseudo-t (2H), 7.46 d.d 131.09, 161.01
3
3
[2H, J 8.51, J(1H 19F)
5.64 Hz], 7.44 d (2H,
J 8.72 Hz)
IIn 7.01 pseudo-t (2H), 7.44 115.06, 122.01, 122.44,
d (2H, J 8.76 Hz), 7.49 126.34, 129.7, 136.31,
d.d [2H, 3J 8.55 Hz, 145.54, 161.06
3J(1H 19F) 5.61 Hz],
8.05 d (2H, J 8.76 Hz)
IIo 7.02 d (2H, J 4.8 Hz), 114.89, 123.45, 125.47,
7.11 pseudo-t (2H), 7.49 131.33, 133.58, 146.56,
1.06
0.45
2.39
2.25
0.22
3
3
d.d [2H, J 8.47, J(1H 161.12
19F) 5.54 Hz], 8.2 br.s
(2H)
IIp 7.01 pseudo-t (2H), 7.1 116.61, 124.12, 124.43,
8.4 (9H)
125.12, 125.46, 125.72,
126.06, 126.76, 128.30,
129.91, 130.76, 133.15,
161.09
a
Molecular ion corresponds to diaryl selenide molecule
containing the most abundant natural isotope 80Se.
1,4-Bis(phenylseleno)benzene (IIg). Colorless
needles. mp 102 C (from hexane) [56].
IIq 7.16 d (2H, J 7.83 Hz), 92.88, 127.93, 129.63,
7.27 7.35 m (3H), 7.46 131.6, 133.37, 133.61,
7.54 m (2H), 7.57 d 134.34, 138.37
(2H, J 7.83 Hz)
4-Phenylselenoacetophenone (IIh). Light-yellow
needles. mp 60 C (from 60% ethanol) [19].
4-Methoxy-4 -fluorodiphenyl
selenide (IIm).
Light-yellow needles. mp 51 C (from hexane).
Method C. To a solution of 1 mmol of ArI and
0.015 mmol of PdCl2(PPh3)2 (1.5 mol%, 11 mg) in
1 ml of anhydrous DMF in a Schlenk vessel under
argon atmosphere was added 0.5 mmol (0.29 g) of
Bu3SnSnBu3 and a solution of 0.5 mmol of PhSeSePh
in 1 ml of anhydrous DMF. The solution obtained
was kept under light for 1.5 h and then heated for
5 h to 100 C. Further workup was carried out as in
method A.
4-Nitro-4 -fluorodiphenyl selenide (IIn). Yellow
needles. mp 72 C (from hexane).
Reaction of aryl triflates with Bu3SnSePh.
General procedure. To a solution of 1 mmol of
ArOTf, 4 mmol of LiBr (4 equiv, 0.348 g), and
0.015 mmol of Ni(PPh3)2Cl2 (9.8 mg, 1.5% mol) in
2 ml of butanol in a Schlenk vessel equipped with a
magnetic stirrer was added under inert atmosphere
1 mmol (0.446 g) of Bu3SnSePh. Purple-colored
reaction mixture was heated to 100 C at stirring for
12 h, and then it was poured into a water solution of
KF. The mixture obtained was treated with benzene,
the water layer was filtered and extracted with
benzene. The combined benzene extracts were dried
with MgSO4, the solvent was removed under reduced
pressure. The diaryl selenide was isolated from the
residue by column chromatography on SiO2, eluent
hexane.
4-Methoxydiphenyl selenide (IIb). Colorless
needles. mp 46 C (from ethanol) [34].
4-Dimethylaminodiphenyl selenide (IIc). Light-
yellow needles. mp 68 C (from 60% ethanol) [55].
4-Nitrodiphenyl selenide (IId). Yellow needles.
mp 59 C (from 60% ethanol) [20].
3-Nitrodiphenyl selenide (IIe). Yellow crystals.
mp 40 C (from 40% ethanol) [55].
4-Bromodiphenyl selenide (IIf). Colorless
crystals. mp 31 C (from 40% ethanol) [15].
Reaction of aryldiazonium salts with Bu3SnSePh.
General procedure. To a mixture of 1 mmol of aryl-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

TRIBUTYLTIN ARYL SELENIDES AS EFFICIENT ARYLSELENATING AGENTS
1473
diazonium fluoborate ArN2BF4 and 2 ml of solvent
was added by portions at stirring 1 mmol (0.446 g) of
Bu3SnSePh. The mixture was stirred 10 min till the
end of gas evolution and then it was poured into a
water solution of KF. Further workup was as
described before.
Table 12. 1H and 13C NMR spectra of aryl organyl
selenides IXa f (acetone-d6)
1H NMR spectrum,
, ppm
13C NMR spectrum,
C, ppm
4-Iododiphenyl selenide (IIq). Colorless prisms.
mp 43 C (from hexane).
IXa 4.01 br.s (2H, CH2), 7.15 31.77, 126.42, 127.83,
br.s (5H, C6H5CH2), 7.22 128.80,
7.35 m (3H), 7.52 7.57 m 128.99,
128.87,
130.76,
Diphenylsulfide V was prepared by reaction of
1 mmol (0.192 g) of PhN2BF4 with 1 mmol (0.399 g)
of Bu3SnSPh in 2 ml of acetone. The reaction mixture
was treated as above. Yield of pure diphenyl sulfide
(2H) 132.85, 137.97
IXb 4.1 s (2H, CH2), 6.99 33.45, 116.13, 127.47,
pseudo-t (2H), 7.22 m (3H), 127.83,
128.8,
1
7.29 m (2H), 7.45 d.d [2H, 128.96,
133.11,
0.187 g (90%). H NMR spectrum (CDCl3), , ppm:
3
3J 8.47, J (1H 19F) 5.60 137.97, 160.74
7.00 t (1H, H4, J 7.34 Hz), 7.06 t (2H, H3,5, J 8.04
Hz), 7.20 d (2H, H2,6, J 8.04 Hz).
Hz]
IXc 2.24 s (3H, CH3), 3.99 17.63, 28.09, 116.10,
Reaction of activated fluoroarenes with
Bu3SnSePh. Method A. To a mixture of 15 mg of
CsF (10 mol%, 0.1 mmol) and 22.7 mg of benzyltri-
ethylammonium chloride (BTEAC)in a Schlenk
vessel under argon atmosphere was added 1 mmol of
ArF in 2 ml of anhydrous chloroform and 1 mmol
(0.446 g) of Bu3SnSePh. The mixture was heated to
boiling. On cooling the reaction mixture was diluted
with 25 ml of benzene and filtered. On removing the
solvent in a vacuum the diaryl selenide was isolated
from the residue by column chromatography.
br.s (2H, CH2), 6.89
126.48,
126.74,
129.2,
133.11,
136.93,
pseudo-t(2H), 7.00 7.05 m 129.06,
(1H), 7.19 7.29 m (3H), 129.47,
7.38 d.d [2H, 3J 8.47, 136.43,
3J(1H 19F) 5.60 Hz]
160.86
IXd 1.39 t (3H, J 6.1 Hz), 15.41, 20.95, 115.66,
2.44 q (2H, J 6.1 Hz), 127.64,
132.54,
6.57 pseudo-t (2H), 7.67 160.98
3
3
d.d [2H, J 8.47, J(1H
19F) 5.60 Hz]
IXe 3.52 d (2H, SeCH2, J 7.0 30.30, 115.95, 116.2,
Hz), 4.93 d.d (1H, =CH2- 126.61, 132.8, 134.1,
Method B. A mixture of 1 mmol of ArF and
1 mmol of Bu3SnSePh in 2 ml of anhydrous DMF
was stirred at room temperature. On completion of
the reaction the reaction mixture was worked up as
in method A.
trans, 2J 2.1, 3Jcis
160.89
10.61 Hz), 5.28 d.d (1H,
3
=CH2-trans, 2J 2.1, Jcis
17.41 Hz), 5.76 m (1H,
CH=), 6.64 pseudo-t (2H),
7.46 d.d [2H, 3J 8.47,
Method C. To 15 mg of CsF (10 mol%, 0.1 mmol)
in a Schlenk vessel under argon was added 1 mmol
of ArF in 2 ml of DMF and 1 mmol (0.446 g) of
Bu3SnSePh. The mixture obtained was heated to
100 C on an oil bath at stirring. On completion of
the reaction the reaction mixture was poured in water
and extracted with benzene (3 25 ml). The extracts
were dried on MgSO4, and the solvent was removed
in a vacuum.
3J (1H 19F) 5.60 Hz]
4
IXf 1.84 t (1H, HC C, J 2.36 18.18, 71.41, 115.76,
Hz), 3.61 d.d (2H, C CCH2, 127.08,
4J 2.36, 2J 12.57 Hz), 161.00
6.59 pseudo-t (2H), 7.47
134.62,
d.d [2H, 3J 8.47,
3J (1H 19F) 5.60 Hz]
4-(Phenylseleno)-2,3,5,6-tetrafluoropyridine
7.52 m (2H). 19F NMR spectrum (CHCl3), F, ppm:
21.10 t (3F, CF3, J 22 Hz), 48.69 m (2F), 62.91 m
(2F). 77Se NMR spectrum (CHCl3), Se, ppm: 158.
Mass spectrum, m/z: 374 [M]+ .
(VIIa). Light-yellow oily substance with a specific
1
odor. H NMR spectrum (CDCl3), , ppm: 7.35 m
(3H), 7.65 m (2H). 19F NMR spectrum (CHCl3),
,
F
ppm: 13.25 m (2F, F3,5), 53.8 m (2F, F2,6).
77Se NMR spectrum (CHCl3), Se, ppm: 126. Mass
spectrum, m/z: 307 [M]+ .
2,3,5,6-Tetrafluoro-4-(4-fluorophenylseleno)-
pyridine (VIId).Light-yellow oily substance with
1
a specific odor. H NMR spectrum (CDCl33), , ppm:
1-Trifluormethyl-4-phenylseleno-2,3,5,6-tetra-
fluorobenzene (VIIb). Yellow oily substance.
1H NMR spectrum (CDCl3), , ppm: 7.32 m (3H),
3
6.87 pseudo-t (2H), 7.46 d.d [2H, J 8.47, J(1H 19F)
5.60 Hz]. 19F NMR spectrum (CHCl3), F, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001

1474
BELETSKAYA et al.
Table 13. 77Se and 19F NMR spectra and molecular ions
of aryl organyl selenides IXa f
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Compd. 77Se NMR spectrum, 19FNMR spectrum, [M]+ a
no.
Se, ppm
F, ppm
IXa
IXb
IXc
IXd
IXe
IXf
89.6
85.0
92.2
125.2
94.6
92.1
248
266
280
204
216
214
36.36
37.22
34.56
37.42
35.86
a
Molecular ion corresponds to diaryl selenide molecule
containing the most abundant natural isotope 80Se.
19.22 m (2F, F3,5), 37.61 s (1F, 4-FC H ),
6 4
51.42 m (2F, F2,6). 77Se NMR spectrum (CHCl3),
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1-Trifluoromethyl-2, 3, 5, 6-tetrafluoro-4-(4-
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fluorophenylseleno)benzene (VIIe). Yellow oily
1
substance. H NMR spectrum (CDCl3), , ppm: 6.96
3
pseudo-t (2H), 7.52 d.d [2H, J 8.42, 3J(1H 19F)
5.60 Hz]. 19F NMR spectrum (CHCl3), F, ppm:
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6 4
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[M]+ .
Reaction of organyl halides with Bu3SnSeAr.
Method A. To a solution of 1 mmol of Bu3SnSeAr
and 1 mmol of alkyl halide in 2 ml of chloroform
was added 2 mmol (0.116 g) of KF and 10 mol%
(0.1 mmol, 0.21 g) of BTEAC. The reaction mixture
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