On the reactivity of indium(III) benzenechalcogenolates (chalcogen = sulfur and selenium) towards organyl halides for the synthesis of organyl phenyl chalcogenides

Article abstract of DOI:10.1139/V09-043

The reactivity of indium(III) benzenechalcogenolates (chalcogen = sulfur, selenium) towards organyl halides (organyl = alkyl, allyl, benzyl, acyl) was examined. A practical one-pot method to prepare organyl phenyl chalcogenides indium metal and diphenyl dichalcogenide was found. The coupling is fairly broad in scope and generally works better organyl halides capable to produce stable carbocations.

Full text of DOI:10.1139/V09-043

678
On the reactivity of indium(III)
benzenechalcogenolates (chalcogen = sulfur and
selenium) towards organyl halides for the
synthesis of organyl phenyl chalcogenides
´
Clovis Peppe and Lierson Borges de Castro
Abstract: The reactivity of indium(III) benzenechalcogenolates (chalcogen = sulfur, selenium) towards organyl halides
(organyl = alkyl, allyl, benzyl, acyl) was examined. A practical one-pot method to prepare organyl phenyl chalcogenides
from indium metal and diphenyl dichalcogenide was found. The coupling is fairly broad in scope and generally works bet-
ter for organyl halides capable to produce stable carbocations.
Key words: diphenyl diselenide, diphenyl disulfide, indium(III) benzenechalcogenolates, organyl phenyl chalcogenides.
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Resume : On a etudie la reactivite des benzenechalcogenolates d’indium(III) (chalcogene = soufre, selenium) vis-a-vis des
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halogenures d’organyles (organyle = alkyle, allyle, benzyle, acyle). On a mis au point une methode monotope pratique de
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preparer des chalcogenures d’organyle et de phenyle a partir de l’indium metallique et du dichalcogenure de diphenyle. La
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portee de la reaction de couplage est assez large et elle fonctionne generalement mieux avec les halogenures d’organyle
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susceptibles de donner naissance a des carbocations stables.
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Mots-cles : diseleniure de diphenyle, disulfure de diphenyle, benzenechalcogenolates d’indium(III), chalcogenures d’or-
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ganyle et de phenyle.
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[Traduit par la Redaction]
Indium(III) chalcogenolates contain indium–chalcogen
bonds made of a hard In(III) cation10 and a soft thiolate and
(or) selenolate anions.11,12 Hard acids – soft bases com-
plexes possess intrinsic thermodynamic unstability, suggest-
ing that the chalcogenolate anion could effectively be used
as a nucleophile in organic reactions to produce new car-
bon–chalcogen bonds. Our group and other groups have in-
troduced the heteroleptic XIn(EPh)2 compounds as sources
of the benzenechalcogenolate nucleophiles to produce
organic chemicals of interest in reactions, such as ring open-
ing of epoxides to b–hydroxyselenides13 and sulfides,14 ring
opening of aziridines to selenocysteine and selenotreonine,15
hydrochalcogenation of alkynes16–18 to vinyl chalcogenides,
also obtained through Pd(0)-catalyzed coupling of IIn(SePh)2
with vinyl bromides19, and finally for coupling with
organyl halides to organyl phenyl chalcogenides.20,21
Recently, while trying to hydrochalcogenate aminoalkines
with the heteroleptic compounds, XIn(EPh)2, we observed
ineffectiveness.22 The task was accomplished with the
indium(III) benzenechalcogenolate complexes, In(EPh)3
(E = S, Se) generated by refluxing a 2:3 molar ratio of
the metallic element and the corresponding diphenyl
dichalcogenide in dichloroethane (DCE). The cleavage of
the chalcogen–chalcogen bond by indium metal in mild
conditions to the In(EPh)3 compounds capable to deliver
the benzenechalcogenolate nucleophiles is very attractive
to the synthetic chemist because of the nontoxic nature
and the stability of indium towards air and moisture. Fur-
thermore, to replace the air-sensitive indium(I) halides to
promote the cleavage of the chalcogen–chalcogen bonds is
also desirable because it will allow to conduct one-pot
Introduction
Indium(III) arylchalcogenolates, In(EAr)3 (E = S, Se),
were prepared by methathetical reactions,1,2 redox proc-
esses,3,4 and electrochemically by sacrificing indium electro-
des.5 Heteroleptic compounds bearing a halide ligand,
XIn(EPh)2 (X = Cl, Br, I; E = S, Se), were prepared by the
oxidative insertion of the corresponding indium monohalide
into the dichalcogenides.6 In(SePh)3 was found polymeric by
X-ray means, crystallizing in two polymorfic forms: a triclinic
containing five-coordinated indium centers with asymmetri-
cal bridging benzeneselenolate ligands7 and a monoclinic
containing six-coordinated indium atoms with symmetrical
bridging benzeneselenolate ligands.8 The sulfur analogue,
In(SPh)3, is also believed to be polymeric,2 but its X-ray
structure was not established until now. However, the steri-
cally hindered arylthiolate complex (2,4,6-t-Bu3C6H2S)3In,
soluble in organic solvents, was crystallized and had its
distorted trigonal planar structure determined by X-ray
methods.9 A common property relating both the homoleptic
In(EPh)3 and the heteroleptic XIn(EPh)2 compounds is that
they act as Lewis acids, forming stable molecular adducts
with several nitrogen,1–3,6,8 phosphorus,1,3,4 sulfoxide,1 and
halide1,3 ligands.
Received 6 November 2008. Published on the NRC Research
Press Web site at canjchem.nrc.ca on 1 May 2009.
1
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C. Peppe and L. Borges deCastro. Laboratorio de Materiais
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Inorganicos, Departamento de Quimica, Universidade Federal de
Santa Maria, Santa Maria – RS 97105-900, Brazil.
1Corresponding author (e-mail: peppe@quimica.ufsm.br).
Can. J. Chem. 87: 678–683 (2009)
doi:10.1139/V09-043
Published by NRC Research Press

Peppe and Borges de Castro
679
Scheme 1. One-pot preparation of organyl phenyl chalcogenides.
preparations directly from the stable metal. To gain a bet-
ter understanding on the reactivity pattern of the In(EPh)3
compounds generated by this method, we have examined
their reactions with organyl halides (Scheme 1). We also
compared the new results with the ones obtained using ear-
lier similar procedures leading to PhER compounds involv-
ing the cleavage of the dichalcogenides by InI20,21 and In
metal.23 A striking difference in reactivity, depending on
the organyl halides, was observed; this was interpreted in
terms of the polymeric nature of the In(EPh)3 compounds
and allowed to design experiments to the chemoselective
production of a desired PhER compound.
Scheme 2. Proposed pathway for reaction of In(EPh)3 and RX.
Results and discussion
The In(EPh)3 (E = S, Se) compounds were easily prepared
by refluxing 2:3 molar quantities of elemental indium and
the dichalcogenide in DCE. Typically, the metal was con-
sumed after 1–2 h, but sonication of a suspension of the
metal in DCE for 10 min prior to heating accelerated the
process. The selenium product remained in solution, while
the sulfur analogue precipitated as a white powder. Addition
of 3 equiv. of the organyl halides depicted in Table 1 af-
forded the corresponding organyl phenyl chalcogenides
products with condensation of up to three benzenechalcoge-
nolate ligands from the In(EPh)3 reagents. The nucleophilic
substitution is easily followed by TLC chromatography, and
in the case of the sulfur complex, reaction completeness is
verified just by observing the dissolution of the reagent in
the reaction media; in most cases, optimum yields were ob-
tained as soon as the white precipitate dissolved.
The reactivity trends of the organyl halides in condensa-
tions with the benzenechalcogenolate nucleophiles from the
IIn(EPh)2 (E = S, Se) compounds in dichloromethane was
investigated by Ranu and co-workers, who demonstrated
that primary, secondary, benzylic, and allylic chlorides, bro-
mides, and iodides as well as acid chlorides readily partici-
pated in the reaction to form the desired organyl phenyl
chalcogenides.20,21 Jang and co-workers examined the prob-
lem through a one-pot reaction involving metallic indium,
diphenyl diselenide, and organyl halides; in that work, they
found that the reaction is initiated by organyl radicals gener-
ated by a one-electron reduction of the R–X substrate by
metallic indium. Accordingly, a relative I > Br > Cl reactiv-
ity order was established for the organyl halides.23
There are remarkable differences in the reactivity of the
In(EPh)3 compounds towards organyl halides compared
with the reagents discussed above. In the present work, we
have verified that the nature of the organyl moiety of the
halide controls the efficiency of the process. Tertiary, ben-
zylic, allylic (leading exclusively to the a-coupling product),
and acyl halides (Table 1, entries 22–39) instantaneously re-
acted with the In(EPh)3 compounds at room temperature to
produce good yields of the desired product. Reactions in-
volving primary halides (Table 1, entries 1–17 and 40–42),
on the other hand, took several hours for completion even
with heating at 83 8C or completely resisted the transforma-
tion as observed for the chlorides (Table 1, entries 1 and 2).
We further note that only the higher members of the series
of bis(phenyl chalcogen)alkanes PhE(CH2)nEPh (n = 1, 2,
3, 5, or 10) were efficiently obtained from the corresponding
dibromo substrates (Table 1, entries 9–17). Secondary alkyl
halides (Table 1, entries 18–21) failed to undergo efficient
condensations, and surprisingly, from these reactions with
In(SePh)3 (Table 1, entries 19 and 21), we have isolated
1,4-bis(phenyl selanyl)butane, PhSe(CH2)4SePh (0.83 mmol
per 1 mmol of In(SePh)3), fully characterized by elemental
1
analysis, mass spectrometry, and H and 13C NMR spectro-
scopy; the actual course of the reaction leading to the butane
derivative is still undetermined, but it is important to notice
that we did not observe any direct reaction between
In(SePh)3 and the DCE solvent under these experimental
conditions, except perhaps in these two cases for which it
is reasonable to assume solvent participation in the process.
The experimental observations made above seem to indi-
cate that the polymeric nature of the In(EPh)3 compounds is
an important aspect ruling their reactivity pattern towards
organyl halides, and that allows one to understand the differ-
ences when compared with reactions involving the IIn(EPh)2
compounds20,21 and the proposed free-radical process initi-
ated by metallic indium.23 The polymeric nature involving
bridging benzenechalcogenolate ligands together with the
ability of the In(EPh)3 complexes to act as Lewis acids
strongly suggest that depolymerization to reactive mono-
meric intermediates is achieved by halide coordination to
the indium centers replacing the bridging chalcogenolate li-
gands responsible for holding the polymeric structures.
Thus, it is expected that organyl halides capable to produce
stable tertiary, benzylic, allylic, and acyl carbocations would
be the most reactive substrates and that these will react ac-
cording to an SN1 path, possibly through an ion-pair inter-
mediate. The instantaneous reactions at room temperature
involving these substrates together with the deep coloura-
tion, typical of carbocations, developed in the DCE solutions
particularly in reactions with benzylic and allylic halides,
are in agreement with this picture (Scheme 2). The enor-
mous difference in reactivity presented by primary alkyl
Published by NRC Research Press

680
Can. J. Chem. Vol. 87, 2009
Table 1. One-pot preparation of organyl phenyl chalcogenides.
Entry
1
2
3
4
5
6
7
8
R–X
n-C6H13Cl
n-C6H13Cl
n-C4H9Br
n-C4H9Br
n-C4H9I
n-C4H9I
n-C8H17Br
E
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
Se
S
T (8C)
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
83
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
83
83
83
Time
20 h
20 h
20 h
12 h
20 h
12 h
20 h
6 h
16 h
6 h
20 h
6 h
48 h
18 h
48 h
48 h
Yield (%)a
NRb
NR
65
54
56
55
83
78
80
80
52
57
NR
60
NR
NR
NR
Traces
25c
Traces
Tracesc
44
68
90
87
95
87
75
80
66
94
54
48
73
88
66
62
89
Reference
—
—
24
25
24
—
26
27
28
—
29
30
—
31
—
—
—
—
27
—
—
20
27
26
27
32
20
26
33
20
33
20
20
26
—
34
20
34
33
20
20
26
n-C8H17Br
9
Br(CH2)10Br
Br(CH2)10Br
Br(CH2)5Br
Br(CH2)5Br
I(CH2)3I
I(CH2)3I
Br(CH2)2Br
Br(CH2)2Br
CH2I2
CH3CH(Br)C2H5
CH3CH(Br)C2H5
C6H11Brd
C6H11Brd
(CH3)3CBr
(CH3)3CBr
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
48 h
24 h
6 h
20 h
18 h
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
3 min
24 h
PhCH2Br
PhCH2Br
PhCH(CH3)Br
PhCH(CH3)Br
H2C=CHCH2Br
H2C=CHCH2Br
(Z+E)-CH3HC=CHCH2Br
(Z+E)-CH3HC=CHCH2Br
(E)-PhHC=CHCH2Br
(E)-PhHC=CHCH2Br
H2C=C(CH3)CH2Br
H2C=C(CH3)CH2Br
CH3COCl
CH3COCl
PhCOCl
PhCOCl
C2H5OC(O)CH2Br
C2H5OC(O)CH2Br
PhC(O)CH2Br
87
50
80
78
24 h
24 h
aIsolated yield of analytically pure product.
bNR = No reaction.
cPlus 0.83 mmol of PhSeCH2(CH2)2CH2SePh per 1.00 mmol of indium.
dCyclohexyl bromide.
halides, which only reacted after prolonged refluxing in
DCE (83 8C), and the lack of reactivity of secondary alkyl
halides suggest an alternative pathway. We propose for these
cases that depolymerization to reactive monomeric inter-
mediates is achieved by formation of (PhE)3InÁX–R adducts
by coordination of the halogen atom of the organyl halide to
the indium centers. This description accommodates well the
failure of secondary alkyl halides to react efficiently due to
stereo-hindrance during adduct formation (Scheme 2). To-
gether with the product of the coupling between the first
equivalent of the phenyl chalcogenolate nucleophile with
the organyl halide leading to the first equivalent of the non-
symmetric PhE–R chalcogenide, occurs the simultaneous
production of the indium(III) heteroleptic product XIn(EPh)2
used by Ranu and co-workers in their earlier work,20,21
a
compound responsible for formation of the two extra equiv-
alents of the PhE–R final product. Considering these ideas,
one can understand the higher reactivity of the IIn(EPh)2
compared with the indium(III) benzenechalcogenolate re-
agents with primary and secondary alkyl halides in terms of
the degree of polymerization of the XIn(EPh)2 and the
In(EPh)3 reagents. Although In(EPh)3 are polymeric, there
Published by NRC Research Press

Peppe and Borges de Castro
681
must not be significant association of the XIn(EPh)2 com-
pounds in solutions.
specified in Table 1. The reactions were quenched with dis-
tilled water (10 mL), the organics extracted with dichloro-
methane (3 Â 10 mL), the extracts were sequentially dried
over sodium sulfate, evaporated to dryness (vaccum), and
the organyl phenyl chalcogenides purified by column chro-
matography over silica gel using hexanes/ ethyl acetate mix-
tures. The sulfur derivatives are colourless oils or solids,
while the selenium products are yellow compounds. All
products are known compounds, and they were identified by
comparison of their spectral data (1H and 13C NMR) with
those reported in the literature (see Table 1 for references).
The milder reactivity of the In(EPh)3, compared with the
XIn(EPh)2 reagents20,21 and with the radical species gener-
ated from the in situ reaction involving indium metal and
diphenyl diselenide,23 suggests that the indium(III) benzene-
chalcogenolates can chemoselectively produce R–EPh
t
(R = alkyl, allyl, or benzyl) in the presence of primary or
secondary alkyl halides. Accordingly, a competitive experi-
ment involving In(SePh)3 with 3 mol of allyl bromide and
n-bromobutane produced C3H5–SePh exclusively with no
n
signs of Bu–SePh being detected.
n-Butyl phenyl sulfide (Table 1, entries 3 and 5)
1H NMR (CDCl3) d: 7.25–7.04 (m, 5H), 2.81 (t, J =
7.5 Hz, 2H), 1.53 (qui, J = 7.5 Hz, 2H), 1.34 (sex, J =
7.5 Hz, 2H), 0.81 (t, J = 7.5 Hz, 3H). 13C NMR (CDCl3) d:
136.96, 128.70, 128.67, 125.48, 33.10, 31.11, 21.87, 13.57.
Conclusion
The development of a one-pot efficient synthesis of
organyl phenyl chalcogenides from alkyl halides and
diphenyl dichalcogenides with the cleavage of the chalcogen–
chalcogen bond performed by metallic indium is very at-
tractive to the synthetic chemists because of the easy
handling and accentuated stability of the metallic element
towards moisture and air. We have interpreted this process
as being intermediated by [In(EPh)3]n polymers whose as-
sociation must be broken to monomeric complexes by co-
ordination and (or) interaction with the halide atom of the
organyl halide. The degree of this coordination or interac-
tion determines the reactivity of these reagents towards the
organyl halide. Organyl halides, giving stable carbocations,
react promptly following an SN1-type reaction pathway
leading to high yields of the nonsymmetrical chalcoge-
nides, while primary alkyl halides require long periods of
continuous heating, possibly following an SN2-type process.
The striking difference in reactivity, depending on the na-
ture of the organyl halide, allows selective condensations
as we have demonstrated with the experiment involving
allyl bromide and bromobutane, which produced exclu-
sively the allyl selenide.
n-Butyl phenyl selenide (Table 1, entries 4 and 6)
1H NMR (CDCl3) d: 7.42–7.38 (m, 2H), 7.18–7.10 (m,
3H), 2.83 (t, J = 7.6 Hz, 2H), 1.61 (qui, J = 7.6 Hz, 2H),
1.34 (sex, J = 7.6 Hz, 2 H), 0.82 (t, J = 7.3 Hz, 3H). 13C
NMR (CDCl3) d: 132.29, 130.66, 128.90, 126.50, 32.19,
27.55, 22.89, 13.50.
n-Octyl phenyl sulfide (Table 1, entry 7)
1H NMR (CDCl3) d: 7.28–7.04 (m, 5H), 2.84 (t, J =
7.5 Hz, 2H), 1.58 (qui, J = 7.5 Hz, 2H), 1.32–1.16 (broad,
10H), 0.82 (t, J = 6.6 Hz, 3H). 13C NMR (CDCl3) d:
137.04, 128.94, 128.68, 125.46, 33.44, 31.73, 29.10, 29.06,
28.78, 22.58, 14.03.
n-Octyl phenyl selenide (Table 1, entry 8)
1H NMR (CDCl3) d: 7.44–7.39 (m, 2H), 7.20–7.12 (m,
3H), 2.84 (t, J = 7.3 Hz, 2H), 1.64 (qui, J = 7.3 Hz, 2H),
1.33–1.16 (broad, 10H), 0.82 (t, J = 6.6 Hz, 3H). 13C NMR
(CDCl3) d: 132.28, 130.70, 128.86, 126.46, 31.74, 30.09,
29.78, 29.11, 28.99, 27.87, 22.58, 14.03.
Experimental
1,10-Bis(phenylthio)decane (Table 1, entry 9)
Mp 64–65 8C. H NMR (CDCl3) d: 7.25–7.10 (m, 10H),
General
1
Indium powder and diphenyl disulfide were commercial
products from Aldrich. Diphenyl diselenide was prepared
from phenylmagnesium bromide and elemental selenium.35
DCE was dried over CaH2 and distilled before use. All the
organyl halides were obtained from commercial suppliers
2.82 (t, J = 7.4 Hz, 4H), 1.56 (qui, J = 7.3 Hz, 4H), 1.36–
1.15 (broad, 12H). 13C NMR (CDCl3) d: 136.98, 128.97,
128.73, 125.53, 33.46, 33.28, 29.31, 29.04, 28.72.
1,10-Bis(phenyl selanyl)decane (Table 1, entry 10)
1
and distilled, when necessary, before use. H and 13C NMR
1
Mp 67–68 8C. H NMR (CDCl3) d: 7.41–7.35 (m, 4H),
spectra were acquired on a Bruker DPX 200 and (or) Bruker
DPX 400 spectrometers.
7.18–7.10 (m, 6H), 2.81 (t, J = 7.4 Hz, 4H), 1.60 (qui, J =
7.2 Hz, 4H), 1.32–1.14 (broad, 12H). 13C NMR (CDCl3) d:
132.23, 130.63, 128.86, 126.46, 30.03, 29.70, 29.30, 28.94,
27.81.
Preparation of organyl phenyl chalcogenides
To a Schlenk tube truly dried (flame) was sequentially
added DCE (2 mL), diphenyl dichalcogenide (0.52 mmol),
and indium powder (0.35 mmol). The mixture was sonicated
for 10 min and then heated under reflux for 1–2 h. After all
the metal being consumed, a yellow solution is obtained for
the selenium derivative and a white precipitate for the sulfur
case. At this point, the reaction was brought to room tem-
perature, and the organyl halide (1 mmol) was added. The
substrates corresponding to entries 22–39 (Table 1) were im-
mediately (1–3 min) consumed as verified by TLC, while
the remaining were consumed after heating for the periods
1,5-Bis(phenylthio)pentane 7 (Table 1, entry 11)
1H NMR (CDCl3) d: 7.24–7.06 (m, 10H), 2.80 (t, J =
6.9 Hz, 4H), 1.61–1.41(m, 6H). 13C NMR (CDCl3) d:
136.62, 128.93, 128.77, 125.69, 33.33, 28.56, 27.78.
1,5-Bis(phenyl selanyl)pentane (Table 1, entry 12)
1H NMR (CDCl3) d: 7.38–7.34 (m, 4H), 7.15–7.08 (m,
6H), 2.76 (t, J = 7.3 Hz, 4H), 1.58 (qui, J = 7.6 Hz, 4H),
1.40 (m, 2H). 13C NMR (CDCl3) d: 132.34, 130.32, 128.86,
126.54, 29.72, 29.41, 27.49.
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682
Can. J. Chem. Vol. 87, 2009
1,3-Bis(phenyl selanyl)propane (Table 1, entry 14)
129.05, 128.90, 128.70, 127.46, 127.13, 126.03, 126.03,
125.96, 125.92, 36.79, 36.34, 17.95, 17.73.
1H NMR (CDCl3) d: 7.38–7.34 (m, 4H), 7.16–7.11 (m,
6H), 2.89 (t, J = 7.3 Hz, 4H), 1.95 (qui, J = 7.3 Hz, 2H).
Crotyl phenyl selenide, mixture of isomers, cis:trans =
1:4 + traces of 3-benzenoselanyl-butene-1 (Table 1, entry
31)
13C NMR (CDCl3) d: 132.59, 129.81, 128.95, 126.77, 30.10,
27.34.
1H NMR (CDCl3) d: 7.52–7.41 (m, 2H), 7.24–7.20 (m,
3H), 5.67–5.31 (m, 2H), 3.55(d, J = 7.8 Hz, 0.4H), 3.48
(dd, J = 7.0 Hz, 1.1 Hz, 1.6H), 1.61 (dd, J = 6.0 Hz,
1.1 Hz, 2.4H), 1.47 (dd, J = 5.2 Hz, 1.3 Hz, 0.6H). 13C
NMR (CDCl3) d: 133.53, 133.15, 131.39, 130.31, 129.07,
128.76, 128.74, 128.22, 127.59, 127.00, 126.92, 126.88,
126.82, 126.01, 29.99, 24.29, 17.60, 12.27.
sec-Butyl phenyl selenide (Table 1, entry 19)
1H NMR (CDCl3) d: 7.51–7.44 (m, 2H), 7.19–7.15 (m,
3H), 3.16 (sex, J = 6.8 Hz, 1H), 1.57 (m, 2H), 1.31 (d, J =
6.9 Hz, 3H), 0.92 (t, J = 7.3 Hz, 3H). 13C NMR (CDCl3) d:
134.78, 129.12, 128.77, 127.18, 41.44, 30.37, 21.53, 12.25.
tert-Butyl phenyl sulfide (Table 1, entry 22)
1H NMR (CDCl3) d: 7.48–7.41 (m, 2H), 7.28–7.19 (m,
3H), 1.22 (s, 9H). 13C NMR (CDCl3) d: 137.47, 128.62,
128.41, 127.13, 45.82, 30.92.
trans-Cinnamyl phenyl sulfide (Table 1, entry 32)
1
Mp 74–75 8C. H NMR (CDCl3) d: 7.39–7.11 (m, 10H),
6.40 (d, J = 15.8 Hz, 1H), 6.21 (d of t, J = 15.8 Hz,
6.9 Hz, 1H), 3.67 (d, J = 6.9 Hz, 2H). 13C NMR (CDCl3) d:
136.59, 135.36, 132.65, 130.05, 128.75, 128.42, 127.47,
126.27, 126.23, 124.91, 36.93.
tert-Butyl phenyl selenide (Table 1, entry 23)
1H NMR (CDCl3) d: 7.59–7.53 (m, 2H), 7.29–7.17 (m,
3H), 1.33 (s, 9H). 13C NMR (CDCl3) d: 138.11, 128.52,
128.36, 128.28, 43.00, 32.12.
trans-Cinnamyl phenyl selenide (Table 1, entry 33)
1
Mp 61–62 8C. H NMR (CDCl3) d: 7.45–7.37 (m, 2H),
Benzyl phenyl sulfide (Table 1, entry 24)
7.18–7.09 (m, 8H), 6.30–6.07 (m, 2H), 3.57 (d, J = 6.6 Hz,
2H). 13C NMR (CDCl3) d: 136.72, 133.81, 131.97, 129.77,
128.87, 128.41, 127.34, 127.23, 126.17, 125.79, 30.63.
1
Mp 39–40 8C. H NMR (CDCl3) d: 7.25–7.08 (m, 10H),
4.02 (s, 2H). 13C NMR (CDCl3) d: 137.37, 136.32, 129.71,
128.76, 128.74, 128.41, 127.09, 126.24, 38.93.
2-Methylallyl phenyl sulfide (Table 1, entry 34)
1H NMR (CDCl3) d: 7.34–7.15 (m, 5H), 4.81 (dd, J =
0.7 Hz, 2H), 3.51 (s, 2H), 1.84 (d, J = 0.7 Hz, 3H). 13C
NMR (CDCl3) d: 140.75, 136.40, 129.92, 128.66, 126.13,
113.90, 41.85, 21.09.
Benzyl phenyl selenide (Table 1, entry 25)
1
Mp 32–33 8C. H NMR (CDCl3) d: 7.35–7.31 (m, 2H),
7.14–7.05 (m, 8H), 3.98 (s, 2H). 13C NMR (CDCl3) d:
138.48, 133.37, 130.33, 128.85, 128.72, 128.29, 127.14,
126.73, 32.07.
2-Methylallyl phenyl selenide (Table 1, entry 35)
1H NMR (CDCl3) d: 7.42–7.38 (m, 2H), 7.18–7.13 (m,
3H), 4.63 (m, 1H), 4.61 (m, 1H), 3.42 (d, J = 0.8 Hz, 2H),
1.77 (dd, J = 0.8 Hz, 0.5 Hz, 3H). 13C NMR (CDCl3) d:
141.70, 133.42, 130.47, 128.80, 127.04, 113.38, 35.95,
21.26.
1-Phenylethyl phenyl sulfide (Table 1, entry 26)
1H NMR (CDCl3) d: 7.29–7.15 (m, 10H), 4.32 (q, J =
7.0 Hz, 1H), 1.61 (d, J = 7.0 Hz, 3H). 13C NMR (CDCl3) d:
143.14, 135.07, 132.40, 128.60, 128.31, 127.20, 127.05,
127.02, 47.91, 22.27.
1-Phenylethyl phenyl selenide (Table 1, entry 27)
S-Phenyl ethanethioate (Table 1, entry 36)
1H NMR (CDCl3) d: 7.44–7.38 (m, 2H), 7.23–7.12 (m,
8H), 4.42 (q, J = 7.0 Hz, 1H), 1.72 (d, J = 7.0 Hz, 3H).
1H NMR (CDCl3) d: 7.31 (s, 5H), 2.30 (s, 3H). 13C NMR
(CDCl3) d: 193.76, 134.29, 129.26, 129.04, 127.83, 30.01.
13C NMR (CDCl3) d: 143.48, 135.32, 129.76, 128.68,
128.19, 127.65, 127.12, 126.80, 42.33, 22.09.
Se-Phenyl ethaneselenoate (Table 1, entry 37)
1H NMR (CDCl3) d: 7.44–7.40 (m, 2H), 7.29–7.25 (m,
3H), 2.34 (s, 3H). 13C NMR (CDCl3) d: 196.55, 135.58,
129.24, 128.81, 126.54, 33.90.
Allyl phenyl sulfide (Table 1, entry 28)
1H NMR (CDCl3) d: 7.27–7.07 (m, 5H), 5.79 (d of sex,
J = 6.8 Hz, 3.0 Hz, 1H), 5.01 (m, 2H), 3.45 (d of t, J =
6.7 Hz, 0.9 Hz, 2H).
S-Phenyl benzothioate (Table 1, entry 38)
1H NMR (CDCl3) d: 8.06 (m, 2H), 7.64–7.46 (m, 8H). 13C
NMR (CDCl3) d: 190.07, 136.54, 135.04, 133.60, 129.47,
129.19, 128.69, 127.42, 127.26.
Allyl phenyl selenide (Table 1, entry 29)
1H NMR (CDCl3) d: 7.51–7.46 (m, 2H), 7.28–7.20 (m,
3H), 5.94 (d of sex, J = 7.0 Hz, 2.3 Hz, 1H), 4.95 (m, 2H),
3.51 (d, J = 7.4 Hz, 2H). 13C NMR (CDCl3) d: 134.35,
133.31, 129.15, 128.91, 127.10, 116.81, 30.65.
S-Phenyl benzoselenoate (Table 1, entry 39)
1H NMR (CDCl3) d: 7.96 (m, 2H), 7.65–7.60 (m, 3H),
7.52–7.42 (m, 5H). 13C NMR (CDCl3) d: 193.33, 138.44,
136.28, 133.84, 129.32, 129.02, 128.89, 127.28, 125.71.
Crotyl phenyl sulfide, mixture of isomers, cis:trans = 1:4
(Table 1, entry 30)
1H NMR (CDCl3) d: 7.26–7.04 (m, 5H), 5.53–5.39 (m,
2H), 3.48–3.44 (m, 1.6H), 3.22–3.18 (m, 0.4H), 1.59 (t, J =
4.8 Hz, 3H). 13C NMR (CDCl3) d: 130.22, 129.55, 129.25,
Ethyl 2-(phenylthio)acetate (Table 1, entry 40)
1H NMR (CDCl3) d: 7.43–7.18 (m, 5H), 4.16 (q, J =
7.2 Hz, 2H), 3.63 (s, 2H), 1.22 (t, J = 7.2 Hz, 3H). 13C
Published by NRC Research Press

Peppe and Borges de Castro
683
(13) Barros, O. S. D.; de Carvalho, A. B.; Lang, E. S.; Peppe, C.
NMR (CDCl3) d: 169.61, 134.94, 129.94, 128.93, 126.88,
61.45, 36.65, 14.00.
Lett.
Org.
Chem.
2004,
1,
43.
doi:10.2174/
1570178043488671.
Ethyl 2-(phenylseleno)acetate (Table 1, entry 41)
1H NMR (CDCl3) d: 7.59–7.55 (m, 2H), 7.30–7.23 (m,
3H), 4.10 (q, J = 7.2 Hz, 2H), 3.49 (s, 2H), 1.18 (t, J =
7.2 Hz, 3H). 13C NMR (CDCl3) d: 170.65, 133.23, 129.05,
128.97, 127.63, 61.08, 27.39, 13.86.
(14) Ranu, B. C.; Mandal, T. Can. J. Chem. 2006, 84, 762.
doi:10.1139/V06-065.
(15) Braga, A. L.; Schneider, P. H.; Paixa˜o, M. W.; Deobald, A.
M.; Peppe, C.; Bottega, D. P. J. Org. Chem. 2006, 71, 4305.
doi:10.1021/jo060286b. PMID:16709076.
(16) Peppe, C.; Lang, E. S.; Ledesma, G. N.; de Castro, L. B.;
Barros, O. S. D.; Mello, P. D. Synlett 2005, 3091. doi:10.
1055/s-2005-921931.
(17) For hydroselenation of alkynols with IIn(SePh)2, see: Barros,
O. S. D.; Lang, E. S.; de Oliveira, C. A. F.; Peppe, C.; Zeni,
G. Tetrahedron Lett. 2002, 43, 7921. doi:10.1016/S0040-
4039(02)01904-4.
(18) Barros, O. S. D.; Lang, E. S.; Peppe, C.; Zeni, G. Synlett
2003, 1725. doi:10.1055/s-2003-41006.
(19) Ranu, B. C.; Chattopadhyay, K.; Banerjee, S. J. Org. Chem.
2006, 71, 423. doi:10.1021/jo052087i. PMID:16388676.
(20) Ranu, B. C.; Mandal, T. J. Org. Chem. 2004, 69, 5793.
doi:10.1021/jo0493727. PMID:15307762.
2-(Phenylthio)acetophenone (Table 1, entry 42)
1H NMR (CDCl3) d: 7.76 (m, 2H), 7.41–7.01 (m, 8H),
4.09 (s, 2H). 13C NMR (CDCl3) d: 193.72, 135.01, 134.59,
133.18, 129.95, 128.77, 128.38, 128.35, 126.68, 40.80.
1,4-Bis(phenylselanyl)butane30 (Table 1, entries 19 and 21)
1H NMR (CDCl3) d: 7.37–7.34 (m, 4H), 7.16–7.10 (m,
6H), 2.77 (t, 4H), 1.70 (t, 4H). 13C NMR (CDCl3) d:
132.43, 130.13, 128.87, 126.61, 29.95, 27.01. Calculated for
C16H18Se2 (%): C, 52.18; H, 4.93. Found (%): C, 52.23; H,
4.77. MS (70 eV, EI, for 80Se) m/z (%): 3694 [M –1], 210
(100), 157,15 155 (64), 77.24
(21) Ranu, B. C.; Mandal, T.; Samanta, S. Org. Lett. 2003, 5,
1439. doi:10.1021/ol034178c. PMID:12713293.
Acknowledgements
(22) Peppe, C.; de Castro, L. B.; Mello, M. D.; Barros, O. S. D.
Synlett 2008, 1165. doi:10.1055/s-2008-1072725.
(23) Munbunjong, W.; Lee, E. H.; Chavasiri, W.; Jang, D. O. Tet-
rahedron Lett. 2005, 46, 8769. doi:10.1016/j.tetlet.2005.10.
025.
We thank the Conselho Nacional de Desenvolvimento
´
´
Cientıfico e Tecnologico (CNPq) for operating grants (to
C.P.) and for the award of a scholarship (to L.B.D.).
(24) Bates, C. G.; Gujadhur, R. K.; Venkataraman, D. Org. Lett.
2002, 4, 2803. doi:10.1021/ol0264105. PMID:12153239.
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(28) Awaleh, M. O.; Badia, A.; Brisse, F.; Bu, X. H. Inorg.
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