Tributylstannyl aryl selenides as efficient arylselenating agents in the synthesis of seleno esters

Article abstract of DOI:10.1023/A:1013913816069

Tributyltin aryl selenides are convenient and highly efficient arylselenating agents in reactions with acyl chlorides. The activity of acetic anhydride is considerably lower but it can be involved into the arylselenation reaction in the presence of PdCl

Full text of DOI:10.1023/A:1013913816069

Russian Journal of Organic Chemistry, Vol. 37, No. 12, 2001, pp. 1703 1709. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 12, 2001,
pp. 1784 1790.
Original Russian Text Copyright
2001 by Beletskaya, Sigeev, Peregudov, Petrovskii.
Tributylstannyl Aryl Selenides as Efficient Arylselenating
Agents in the Synthesis of Seleno Esters*
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 convenient and highly efficient arylselenating agents in reactions
with acyl chlorides. The activity of acetic anhydride is considerably lower but it can be involved into the
arylselenation reaction in the presence of PdCl2(PPh3)2 or boron trifluoride etherate as catalysts.
Selenoesters are interesting due to extensive
opportunities to apply them as synthetic inter-
mediates. They can be used as building blocks in
preparation of oxazoles [1] and polyfunctional alkenes
[2]. The lability of the Se O bond is utilized in their
application as precursors of acyl radicals [3 10].
Scheme 1.
The arylselenation of benzoyl chloride readily
occurs at room temperature both with and without
palladium catalyst affording the corresponding
selenoester in nearly quantitative yield. The reaction
is of general character, and this synthetic procedure
can be extended to preparation of selenoesters of
The preparation procedures for selenoesters are
based on reactions between acyl chlorides and acid
anhydrides or esters with nucleophilic organoselenat-
ing reagents, as organoselenols in the presence of
bases, mercury bisarylselenolates, samarium and
aluminum organoselenolates [11 15]. The carboxylic
acids also can be converted into the corresponding
selenoesters through reaction with aryl selenocyanates
and tributylphosphine [16].
aromatic, aliphatic, and
, -unsaturated acids
(Table 1). In the most cases the yield of selenoesters
IIIa u is virtually quantitative; however with acyl
chloride it decreases presumably due to the enhanced
hydrolytic ability. The reaction progress was
monitored by 119Sn NMR spectroscopy. However the
time of spectrum recording was close to that of the
reaction, and therefore we used as arylselenating
agent also tributyltin 4-fluorophenyl selenide (IIb).
This provided a possibility to check the reaction time
for various acyl chlorides (Table 1) and to evaluate
their relative reactivity. Note that the activity of
Bu3SnSePh and its fluorinated analog with respect to
acyl chlorides was virtually the same as was shown
by an example of 4-fluorobenzoyl chloride arylselen-
ation. The electron-withdrawing substituents in the
acyl chloride molecule accelerate the reaction. This
effect is especially pronounced with the nitro group.
In reactions with 4-nitrobenzoyl chloride (Ie) and
(E)-4-nitrophenyl-2-propenoyl chloride (Ij) the
formation of selenoesters IIIi and IIIt was complete
within several minutes after mixing the reagents. Yet
the acyl chlorides with electron-donor substituents, as
4-methoxybenzoyl chloride (Ih) react notably shower
In the most of these methods are used highly toxic
compounds, unstable against oxygen and moisture,
and often difficult in handling. Therefore new stable,
easy to handle and efficient organoselenating reagents
are of obvious interest.
In the present report we describe a method for
selenoesters synthesis based on stable against mois-
ture and air tributyltin arylselenolates that are used as
a source of the arylseleno group (preliminary
communication see [17]).
Aryselenation of acyl chlorides with the use of
Bu3SnSeAr. We performed reactions of tributyltin
aryl selenides Bu3SnSeAr (Ar = Ph, 4-FC6H4) with
a series of acyl chlorides.
*
The study was carried out under financial support of the pro-
grams Leading Scientific School (grant no. 00-15-97406),
and Integration of High School with the Academy of
Sciences (grant AO-15).
1070-4280/01/3712-1703$25.00 2001 MAIK Nauka/Interperiodica

1704
BELETSKAYA et al.
Table 1. Reaction time and yields of arylselenation products from acyl chlorides RCOCl and tributyltin aryl selenides
Bu3SnSeAr
RCOSeAr
RCOCl
Compd. no.
Time, mina
Yield, %b
R
Ar
Ph
Ia
Ib
Ic
Id
Ph
Ph
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
60c
45d
35
37
60c
33
60c
37
5
99 (96)
98 (94)
99 (97)
99 (96)
98 (96)
97 (93)
99 (97)
98 (96)
96 (92)
95 (93)
98 (92)
92 (89)
99
99 (94)
92 (86)
87 (80)
95 (90)
97 (94)
98 (93)
(96)
4-FC6H4
Ph
4-FC6H4
Ph
4-FC6H4
Ph
4-FC6H4
4-FC6H4
Ph
4-FC6H4
Ph
Ph
4-FC6H4
4-FC6H4
4-FC6H4
4-FC6H4
Ph
4-FC6H4
4-FC6H4
4-ClC6H4
4-ClC6H4
4-BrC6H4
4-BrC6H4
Ie
If
4-NO2C6H4
4-(PhSeCO)C6H4
4-(4-FC6H4COSe)C6H4
4-(ClCO)C6H4
4-(PhSeCO)C6H4
4-(PhSeCO)C6H4
2-(4-FC6H4COSe)C6H4
2-(ClCO)C6H4
4-MeOC6H4
(E)-PhCH=CH
(E)-PhCH=CH
(E)-4-NO2C6H4CH= CH
Me
IIIj
IIIk
IIIl
60c
27
60c
60c
48
35
39
63
60c
38
15e
60c
15
If
IIIl
IIIj
IIIm
IIIn
IIIo
IIIp
IIIq
IIIr
IIIs
IIIt
IIIu
Ig
Ih
Ii
4-FC6H4
Ph
Ph
Ij
Ik
97 (90)
96 (85)
Me
4-FC6H4
a
b
c
d
e
Time of reaction between acyl chlorides and 4-FC6H4SeSnBu3 according to 19F NMR data.
Yield according to 19F and 77Se spectra. The preparative yield is given in parentheses.
After the indicated time according to 119Sn NMR data in the reaction mixture the signals of the initial Bu3SnSePh were lacking.
In the presence of 1.0 mol% Pd(PPh3)4 the reaction took 20 min.
Selenoester formed in virtually quantitative yield.
It was shown that in the presence of a palladium
ing agent II (0.85 equiv) for the reaction at equimolar
ratio of reagents affords considerable amount (up to
10 15%) of bis-arylselenated product IIIo.
catalyst the reaction rate somewhat increased. Addi-
tion of 1 mol% of Pd(PPh3)4 reduced the reaction
time for benzoyl chloride with 4-FC6H4SeSnBu3 from
45 to 20 min.
Although we have not studied in detail the reaction
mechanism we regard as the most probable that
presented in Scheme 3.
The reactivity of COCl group in the terephthaloyl
chloride (If) and in monoselenoester IIIl with respect
to tributyltin aryl selenides is sufficiently different to
provide a possibility to substitute a single halogen at
the equimolar reagents ratio (Scheme 2). Addition of
the second equiv of Bu3SnSePh gives rise to diseleno-
ester IIIj. Using in the second stage the fluoro-sub-
stituted tin selenide IIb afforded in a good yield
asymmetrical diselenoester IIIm. This reaction can
be performed without isolation of the intermediate
monoselenated product IIIl.
The addition of palladium catalyst changes the
reaction path, and the mechanism apparently becomes
Scheme 3.
A selective substitution of one chlorine in phthalo-
yl chloride (Ig) is performed at deficit of arylselenat-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 12 2001

TRIBUTYLTIN ARYL SELENIDES
1705
Scheme 4.
Table 2. Conditions of reaction between acetic
anhydride and 4-FC6H4SeSnBu3, and yield of the
selenoester
Solvent
vent
Tempera- Time, Yield,
Additive
a
ture,
C
h
%
CHCl3
DMF
DMF
DMF
25
24
24
14
4
25
100
100
25
95
97
1 mol% PdCl2(PPh3)2
CHCl3 2equiv KF + 5 mol%
BTEAC
24
DMF
DMF
THF +
+EtOHb
DMF
2 equiv CsF
2 equiv CsF
25
100
66
24
20
4
92
77c
similar to that commonly accepted for the cross-
coupling reaction (Scheme 4).
10 mol% BF3 Et2O
25
7
96
Arylselenation of acetic anhydride with the use
of Bu3SnSeAr. We used as acylating reagents also
acid anhydrides. They have some advantages over
acyl chlorides for they are cheeper and less aggressive
although considerably less reactive toward nucleo-
philes.
a
As arylselenating agent was used arylselenolate anion obtained
by reduction of an appropriate diaryl selenide with NaBH4.
Yield according to 19F NMR data.
b
c
Preparative yield 70%.
Another approach to initiation of this reaction may
The analysis of published data showed that acid
anhydrides are commonly used in reactions with
active nucleophiles, as samarium organoselenolates
in HMPA [18] or titanocene organoselenolates [19].
Yet the more active acyl chlorides react with much
less reactive mercury arylselenolates [14] and free
selenols [20]. In the latter case the reaction is assisted
by the presence of a base [11, 13].
consist in nucleophilic activation of 4-FC6H4SeSnBu3.
The activation of organotin derivatives with the use of
nucleophilic assistance by fluoride ion is well known
[21 26]. However in our case the presence of the
fluoride ions in the reaction mixture even decelerated
the process. For instance, the reaction time at 100 C
in the presence of CsF was 1.5 times longer than
when the reaction occurred without F . This fact
evidences that the coordination of anhydride oxygen
to tin atom is a significant factor for this reaction
(Scheme 5). It is an indirect indication that no free
RSe anion forms in the reaction in the presence of
fluoride ion as has been earlier presumed [21].
The conditions of reactions were selected using as
a model arylselenation of acetic anhydride (Table 2).
The reaction progress was monitored by 19F NMR
spectroscopy.
Scheme 5.
A simpler version of this reaction is treating with
acetic anhydride of arylselanolate anion obtained by
reduction of diaryl selenide with sodium tetrahydro-
borate (Scheme 6). Yet the selenoester yield in this
case is notably lower than in reactions with
Bu3SnSeAr.
At room temperature both in chloroform and DMF
product IIIu was not detected even after 24 h. The
heating to 100 C resulted in selenoester IIIu forma-
tion although the reaction rate was still slow.
Acid anhydrides can be activated for the nucleo-
philic attack by complexing with the Lewis acids. We
applied BF3 etherate since it had been shown before
that it had efficiently catalyzed reaction of Bu3SnSePh
with epoxides [27]. With the acetic anhydride BF3
Et2O also turned out to be very active. In contrast to
catalysis with palladium complexes that requires
heating the reaction in the presence of BF3 Et2O
We succeeded in considerable acceleration of the
reaction by applying as a catalyst PdCl2(PPh3)2 in
DMF. Under the chosen conditions the arylselenation
of acetic anhydride provided selenoester IIIu in good
yield within 4 h.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 12 2001

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BELETSKAYA et al.
1
Table 3. H and 13C NMR spectra (CDCl3) of selenoesters IIIa u
Compd.
no.
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
IIIa 7.39 m (3H), 7.61 m (4H), 7.75 (1H), 8.01(2H) 125.4 (C), 125.8 (CH), 127.58 (C), 127.67 (CH), 130.64 (CH),
132.98 (CH), 133.60 (CH), 135.88 (CH), 193.5 (CO)
IIIb 7.17 pseudo-t (2H), 7.54 d.d [2H, 3J 8.72, 117.45 (CH), 124.29 (C), 125.80 (CH), 132.98 (CH), 133.46
2J(1H 19F) 5.13 Hz], 7.61 m (3H), 7.94 m (2H) (CH), 134.85 (C), 135.88 (CH), 161.08 (C), 193.05 (CO)
IIIc 7.17 pseudo-t (2H), 7.44 m (3H), 7.60 m (2H), 116.11 d [C3,5, 4-FC6H4, 2J(13C 19F) 22.1 Hz], 125.52 (C1,
7.96 d.d [2H, 3J 8.72, 2J(1H 19F) 4.98 Hz] Ph), 129.17 (C4, Ph), 129.41 (Ph), 129.90 d [C2,6, 4-FC6H4,
3J(13C 19F) 9.6 Hz], 134.85 d [C1, 4-FC6H4, 4J(13C 19F)
1
2.8 Hz], 136.30 (Ph), 166.12 d [C4, 4-FC6H4, J(13C 19F)
255.8 Hz], 191.79 (CO)
IIId 7.14 pseudo- (2H), 7.49 m (4H), 8.11 d.d [2H, 114.77 (CH), 117.26 (CH), 122.11 (C), 124.29 (C), 133.46
3J 8.72, 2J(1H 19F) 5.08 Hz]
(CH), 138.53 (CH), 161.08 (C), 168.56 (C), 193.67 (CO)
IIIe 7.14 m (3H), 7.56 m (2H), 7.59 d (2H, J 8.73 125.79 (C), 128.46 (CH), 128.87 (CH), 128.96 (CH), 129.22
Hz), 7.77 d (2H, J 8.73 Hz)
(CH), 136.31 (CH), 136.83 (C), 139.73 (C), 190.63 (CO)
2
IIIf 7.17 pseudo-t (2H), 7.62 d (2H, J 8.73 Hz), 117.45 d [C3,5, 4-FC6H4, J(13C 19F) 22.0 Hz], 124.82 (C1,
7.76 d (2H, J 8.73 Hz) 7.96 d.d [2H, J 8.72, 4-ClC6H4), 129.17 (C4, 4-ClC6H4), 129.41 (4-ClC6H4), 129.62
3
2J(1H 19F) 5.01 Hz]
d.d [C2,6, 4-FC6H4, 3J(13C 19F) 9.6 Hz], 134.89 d [C1, 4-FC6H4,
4J(13C 19F) 3.0 Hz], 140.30 (4-ClC6H4), 166.16 d[C4, 4-FC6H4,
1J(13C 19F) 255.4 Hz], 192.19 (CO)
IIIg 7.44 m (3H), 7.58 m (2H), 7.63 d (2H, J 8.72 125.35 (C), 128.67 (CH), 128.96 (C), 129.22 (CH), 129.43
Hz), 7.79 d (2H, J 8.72 Hz)
(CH), 132.22 (CH), 136.25 (CH), 137.25 (C), 192.50 (CO)
2
IIIh 7.17 pseudo-t (2H), 7.62 d (2H, J 8.73 Hz), 117.49 d [C3,5, 4-FC6H4, J(13C 19F) 22.0 Hz], 124.81 (C1,
7.76 d (2H, J 8.73 Hz) 7.96 d.d [2H, J 8.72, 4-BrC6H4), 128.56 (C4, 4-BrC6H4), 129.41 (4-BrC6H4), 129.62
3
2J(1H 19F) 5.01 Hz]
d.d [C2,6, 4-FC6H4, 3J(13C 19F) 9.6 Hz], 134.89 d [C1,
4
4-FC6H4, J(13C 19F) 3.0 Hz], 138.30 (4-BrC6H4), 166.21 d
1
[C4, 4-FC6H4, J(13C 19F) 256.0 Hz], 192.19 (CO)
IIIi
7.14 pseudo-t (2H), 7.54 d.d [2H, 3J 8.72, 117.45 (CH), 122.38 (CH), 124.29 (C), 131.37 (C), 133.46
2J(1H 19F) 5.23 Hz], 8.05 d (2H, J 8.72 Hz), (CH), 133.71 (CH), 150.73 (C), 161.01 (C), 193.56 (CO)
8.31 d (2H, J 8.72 Hz)
IIIj 7.45 m (6H), 7.61 m (4H), 8.03 s (4H)
125.42 (C), 127.71 (CH), 129.28 (CH), 129.46 (CH), 136.12
(CH), 142.32 (C), 189.11 (CO)
IIIk 7.14 pseudo-t (4H), 7.55 d.d [4H, 3J 8.72, 117.45 (CH), 125.26 (C), 131.39 (C), 133.45 (CH), 136.11
2J(1H 19F) 5.29 Hz], 8.01 s (4H)
7.46 m (3H), 7.63 m (2H), 7.89 d (2H, J 8.72 127.56 (CH), 127.67 (CH), 130.64 (CH), 132.89 (C), 133.60
Hz), 8.23 d (2H, J 8.72 Hz) (CH), 138.59 (CH), 140.11 (C), 167.30 (COCl), 183.24
(CH), 161.08 (C), 189.51 (CO)
IIIl
IIIm 7.14 pseudo-t (2H), 7.45 m (3H), 7.55 d.d [2H, (COSe) 117.45 (CH), 124.29 (C), 127.58 (C), 127.67 (CH),
3J 8.72, 2J(1H 19F) 5.21 Hz], 7.64 m (2H), 130.64 (CH), 131.91 (C), 133.46 (CH), 133.6 (CH), 134.62
8.02 s (4H)
161.08 (C), 191.34 (CO)
IIIn 7.12 pseudo-t (4H), 7.49 d.d [4H, 3J 8.72, 116.29 (CH), 123.76 (C), 130.24 (CH), 134.68 (CH), 142.63
2J(1H 19F) 5.11 Hz], 8.11 m (2H), 8.23 m (2H) (C), 161.43 (C), 188.73 (CO)
IIIo 7.16 pseudo-t (4H), 7.52 d.d [4H, 3J 8.72,
2J(1H 19F) 5.15 Hz], 7.78 8.12 m (4H)
IIIp 3.81 s (CH3), 7.01 d (2H, J 8.72 Hz), 7.14 55.67 (CH3), 112.56 (CH), 117.21 (CH), 120.45 (C), 124.46
3
pseudo-t (4H), 7.49 d.d [4H, J 8.72, 2J(1H 19F) (C), 133.46 (CH), 136.49 (CH), 161.13 (C), 165.97 (C),
5.11 Hz], 7.89 d (2H, J 8.72 Hz)
193.5 (CO)
IIIq 6.85 d (1H, =CHCO, J 15.57 Hz), 7.46 m 126.00 (CH), 126.06 (C), 128.46 (CH), 128.84 (C), 128.88
(6H), 7.57 m (2H), 7.65 m (2H), 7.67 d (2H, (CH), 129.23 (CH), 130.77 (CH), 133.61 (CH), 135.71 (CH),
PhCH= , J 15.57 Hz)
140.91 (CH), 190.52 (CO)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 12 2001

TRIBUTYLTIN ARYL SELENIDES
Table 3. H and 13C NMR spectra(CDCl3) of selenoesters IIIa u
1707
1
Compd.
no.
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
IIIr 6.78 d (1H, =CHCO, J 15.57 Hz), 7.11 pseudo-t 117.27 (CH), 123.92 (C), 128.34 (CH), 128.47 (CH), 133.01
(2H), 7.41 m (3H), 7.54 m (4H), 7.63 d (2H, (CH), 135.71 (CH), 152.52 (CH), 161.33 (C), 192.17 (CO)
PhCH= , J 15.57 Hz)
IIIs 6.88 d (1H, CH=CHCO, J 15.8 Hz), 7.45 m 124.01 (CH), 125.47 (C), 128.86 (CH), 129.06 (CH), 129.29
(3H, Ph), 7.57 m (2H, Ph), 7.61 d (1H, (CH), 129.54 (CH), 135.48 (CH), 137.18 (CH), 139.80 (C),
CH=CHCO, J 15.8 Hz), 7.71 d (2H, 4-NO2C6H4, 148.38 (C), 190.43 (CO)
J 8.4 Hz), 8.25 d (2H, 4-NO2C6H4, J 8.4 Hz)
IIIt 2.26 s (3H, CH3), 7.31 m (3H), 7.61 m (2H) 31.18 (CH3), 127.75 (C), 127.91 (CH), 130.17 (CH), 133.03
(CH), 198.52 (CO)
2
IIIu 2.23 s (3H, CH3), 7.16 pseudo t-(2H), 7.54 d.d 31.18 (CH3), 116.98 d [C3,5, 4-FC6H4, J(13C 19F) 22.1 Hz],
3
[4H, 3J 8.72, 2J(1H 19F) 5.40 Hz]
132.89 d [C2,6, 4-FC6H4, J(13C 19F) 9.6 Hz], 133.45 d [C1,
4-FC6H4, 4J(13C 19F) 2.8 Hz], 166.02 d [C4, 4-FC6H4,
1J(13C 19F) 255.8 Hz], 198.79 (CO)
Table 4. Melting points, 77Se (CHCl3), 19F (CHCl3) NMR and mass spectra of selenoesters IIIa u
Compd.
no.
mp,
C
,
,
M+ ,
m/z
Compd.
no.
mp,
C
,
,
F
ppm
M+ ,
m/z
Formulaa
Formulaa
Se
F
Se
ppm
ppm
ppm
IIIa
[15]
IIIb
IIIc
IIId
48
168
262 C13H10OSe
IIIk
IIIl
112
39
110
188
192
186
196
201
162
154
0.78
482 C20H12F2O2Se2
324 C14H9ClO2Seb
464 C20H13FO2Se2
482 C20H12F2O2Se2
342 C14H8ClFO2Seb
310 C14H11FO2Se
288 C15H12OSe
51
52
55
172
170
173
8.64
280 C13H9FOSe
280 C13H9FOSe
298 C13H8F2OSe
IIIm
IIIn
IIIo
IIIp
IIIq
[31]
0.76
0.64
0.55
0.32
8.69,
0.56
38
42
IIIe
[16]
IIIf
IIIg
[15]
IIIh
IIIi
49
174
296 C13H9ClOSeb
53
55
178
174
0.44
314 C13H8ClFOSeb IIIr
340 C13H9BrOSec
44
84
158
161
201
0.12
0.37
306 C15H11FOSe
333 C15H11NO3Se
200 C8H8OSe
IIIs
IIIt
60
89
106
179
184
185
0.39
1.22
358 C13H8BrFOSec [32]
325 C13H8FNO3Se IIIu
446 C20H14O2Se2
204
218 C8H7FOSe
IIIj
a
The molecular ion is given for a molecule containing the most abundant natural isotope 80Se.
The molecular ion is given for a molecule containing the most abundant natural isotope 35Cl.
The molecular ion is given for a molecule containing the most abundant natural isotope 79Br.
b
c
affords selenoester within the same time at room
temperature.
etherate as catalyst. Catalysis with palladium
complexes requires more rigid conditions, and the
presence in the reaction medium of fluoride ions
hampers the reaction course.
Thus we considered three possible approaches to
the reaction of acetic anhydride with tributyltin
arylselenolates: catalysis with palladium complexes,
nucleophilic activation of tributyltin aryl selenides
with fluoride ion, and electrophilic activation of the
acetic anhydride for nucleophilic attack with the
Lewis acids (BF3 Et2O). The optimal procedure for
this reaction consists in the use of boron trifluoride
EXPERIMENTAL
119Sn and 77Se NMR spectra were registered from
chloroform solutions on spectrometer Bruker WP-200
SY at operating frequencies 74.6 and 38.19 MHz
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 12 2001

1708
BELETSKAYA et al.
respectively. 19F NMR spectra were recorded from
solutions in chloroform, DMF, or THF on Bruker
WP-200 SY and Bruker AMX-400 instruments at
operating frequencies 188.3 and 376.5 MHz re-
spectively. The resonance stabilization was performed
on D2O as external lock. Chemical shifts of 119Sn,
77Se, and 19F were measured relative to external
references Me4Sn, Ph2Se2, and fluorobenzene
in 1 ml of anhydrous solvent was added 1 mmol
(0.464 g) of 4-FC6H4SeSnBu3 in 1 ml of anhydrous
solvent. The reaction conditions are listed in Table 3.
After the end of the reaction the reaction mixture was
poured into KF solution and extracted with benzene.
The organic extract was filtered, dried on Na2SO4,
the solvent was removed in a vacuum. The seleno-
ester was purified by column chromatography on
SiO2, eluent hexane + 5% of CHCl3.
1
respectively. H and 13C NMR spectra were obtained
in CDCl3 solutions on spectrometer Bruker AMX-400
at operating frequencies 400.13 and 100.5 MHz
respectively. Mass spectra were measured on Kratos
MS 890 instrument.
Reaction of acetic anhydride with Bu3SnSeAr
catalyzed by PdCl2(PPh3)2. To a solution of 1 mmol
(0.102 g) of acetic anhydride in 1 ml of anhydrous
DMF and 1 mol% (0.01 mmol, 0.007 g) of
PdCl2(PPh3)2 in a Schlenk vessel equipped with a
magnetic stirrer in an argon flow was added 1 mmol
(0.464 g) of 4-FC6H4SeSnBu3 in 1 ml of anhydrous
DMF. The reaction mixture was stirred for 4 h at
100 C. Further workup was performed as in the
previous experiment. The yield of selenoester IIIu
0.196 g (90%).
All reactions were carried out under inert nitrogen
atmosphere. The workup of reaction mixtures did not
require inert atmosphere. Chloroform was dried by
distillation over P2O5, DMF was distilled over CaH2.
All the solvents were distilled under nitrogen just
before use. Pd(PPh3)4 [28] and PdCl2(PPh3)2 [29]
were prepared by known procedures. Tributyltin aryl
selenides were obtained by reaction between Bu6Sn2
and ArSeSeAr in benzene under daylight [30].
Reaction of acetic anhydride with Bu3SnSeAr in
the presence of inorganic fluorides. To a solution of
1 mmol (0.102 g) of acetic anhydride in 1 ml of
anhydrous solvent and 2 mmol (0.304 g) of CsF [or
2 mmol (0.116 g) of KF and 10 mol% (0.1 mmol,
0.0228 g) of benzyltriethylammonium chloride] in a
Schlenk vessel equipped with a magnetic stirrer was
added in an argon flow 1 mmol (0.464 g) of
4-FC6H4SeSnBu3 in 1 ml of anhydrous DMF. The
reaction conditions are indicated in Table 3. Further
workup was performed as in the previous method.
Reaction of acyl chlorides and Bu3SnSeAr.
General procedure for selenoesters synthesis. To a
solution of 1 mmol of acyl chloride in 1 ml of
anhydrous chloroform in a Schlenk vessel was added
1 mmol (0.85 mmol in reaction with acyl chloride Ig)
of Bu3SnSeAr in 1 ml of chloroform. In the synthesis
of disubstituted selenoesters IIIj, k, n was used a
solution of 2 mmol of Bu3SnSeAr in 2 ml of chloro-
form. The reaction mixture was stirred for 1.5 h, and
the solvent was removed in a vacuum. The residue
was diluted with 5 ml of acetone and poured into KF
solution. On extraction with benzene the organic layer
was filtered, dried with Na2SO4, and the solvent was
evaporated. The residue was recrystallized from
hexane (compounds IIIa k, p s) or subjected to
column chromatography (compounds IIIn, o, t, u).
Monoselenoester of terephthalic acid IIIl was
separated by recrystallization of the residue after
distillation of the solvent from the reaction mixture.
The spectral data and physical constants of com-
pounds obtained are given in Tables 3, 4.
Reaction of acetic anhydride with Bu3SnSeAr in
the presence of boron trifluoride etherate. To a
solution of 1 mmol (0.102 g) of acetic anhydride in
1 ml of anhydrous solvent and 10 mol% of BF3 Et2O
in a Schlenk vessel equipped with a magnetic stirrer
was added in an argon flow 1 mmol (0.464 g) of
4-FC6H4SeSnBu3 in 1 ml of anhydrous DMF. The
mixture was kept for 7 h at room temperature.
Further workup was performed as in the previous
method. Yield of selenoester IIIu 0,192 g (88%).
Reaction of acetic anhydride with (4-FC6H4Se)2
and NaBH4. To a solution of 1 mmol (0.348 g) of
(4-FC6H4Se)2 in 4 ml of anhydrous THF containing
15% of ethanol in a two-neck flask equipped with a
condenser was added at stirring under argon atmo-
sphere finely ground NaBH4 till the solution get
colorless (about 0.1 g). Then to the solution was
added 2 mmol (0.204 g) of acetic anhydride, and the
mixture was boiled for 4 h. On completion of the
reaction the reaction mixture was poured into water
and extracted with benzene. The extract was dried
Se1,Se4-Diphenylselenoester of 1,4-benzenedi-
carboxylic acid (IIIj). Found, %: Se 36.21.
C20H14O2Se2. Calculated, %: Se 35.55.
(Z)-3-(4-Nitrophenyl)-Se-phenyl-2-propene-
selenoate (IIIs). Found, %: Se 22.94. C15H11NO3Se.
Calculated, %: Se 23.77.
Reaction of acetic anhydride with Bu3SnSeAr.
To a solution of 1 mmol (0.102 g) of acetic anhydride
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 12 2001

TRIBUTYLTIN ARYL SELENIDES
1709
vol. 28, no. 21, pp. 3999 4002.
with Na2SO4, the solvent was removed in a vacuum.
The selenoester was purified by column chromato-
graphy on SiO2, eluent hexane + 5% of CHCl3.
Yield of selenoester IIIu 0.307 g (70%, according to
19F NMR data 77%).
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