Straightforward microwave-assisted synthesis of organochalcogen amines by reductive amination

Article abstract of DOI:10.1016/j.jorganchem.2018.08.007

Organoselenium and organotellurium amines have been shown to present a broad range of interesting properties for both synthetic and biological applications. Despite the current interest in this class of compounds, only few methods to access organochalcogen amines are described in literature, most which involve restrictive conditions associated with displacement reaction, metal-assisted reactions or enzymatic approach. In general, these methods produce organochalcogen amines in poor yields, by long reactions that require protective groups. In this regard, a set of aryl chalcogen (Se, Te) amines were prepared by reductive amination employing a microwave-assisted one-pot protocol. This approach offered a convenient and versatile method to synthesize primary and secondary organochalcogen amines with significantly short time reactions (5–10 min) and satisfactory yields (40–89%).

Full text of DOI:10.1016/j.jorganchem.2018.08.007

Accepted Manuscript
Straightforward microwave-assisted synthesis of organochalcogen amines by
reductive amination
Mara C. Dalmolin, Pamela T. Bandeira, Matheus S. Ferri, Alfredo R.M. de Oliveira,
Leandro Piovan
PII:
S0022-328X(18)30431-5
10.1016/j.jorganchem.2018.08.007
JOM 20534
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 29 May 2018
Revised Date: 8 August 2018
Accepted Date: 10 August 2018
Please cite this article as: M.C. Dalmolin, P.T. Bandeira, M.S. Ferri, A.R.M. de Oliveira, L. Piovan,
Straightforward microwave-assisted synthesis of organochalcogen amines by reductive amination,
Journal of Organometallic Chemistry (2018), doi: 10.1016/j.jorganchem.2018.08.007.
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Journal of Organometallic Chemistry
www.elsevier.com/locate/jorganchem
Straightforward microwave-assisted synthesis of organochalcogen amines by
reductive amination
Mara C. Dalmolin,a Pamela T. Bandeira,a Matheus S. Ferri,a Alfredo R. M. de Oliveiraa and Leandro
Piovan*a
a Department of Chemistry, Universidade Federal do Paraná, Paraná, Brazil.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Organoselenium and organotellurium amines have been shown to present a broad range of
interesting properties for both synthetic and biological applications. Despite the current interest
in this class of compounds, only few methods to access organochalcogen amines are described
in literature, most which involve restrictive conditions associated with displacement reaction,
metal-assisted reactions or enzymatic approach. In general, these methods produce
organochalcogen amines in poor yields, by long reactions that require protective groups. In this
regard, a set of aryl chalcogen (Se, Te) amines were prepared by reductive amination employing
a microwave-assisted one-pot protocol. This approach offered a convenient and versatile method
to synthesize primary and secondary organochalcogen amines with significantly short time
reactions (5-10 min) and satisfactory yields (40-89%).
Available online
Keywords:
Selenoamine
Telluroamine
Reductive amination
Microwave
2009 Elsevier Ltd. All rights reserved
.
Primary and secondary chalcogen amines
———
* Corresponding author. Tel.: +55-041-3361-3178; e-mail: lpiovan@quimica.ufpr.br

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Journal of Organometallic Chemistry
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1. Introduction
Organochalcogenated compounds are biologically relevant,
since oxygen, sulfur and selenium are ubiquitous in biomolecules
[1]. Selenium and tellurium-containing substances have a broad
range of interesting properties for biological, pharmaceutical, and
material applications [2, 3]. Selenium, besides being an essential
micronutrient, is the pivotal component of the active site of a
series of antioxidant Se-dependent enzymes [4]. There is not
report about Te-containing biomolecules occurrence, but
synthetic organotellurated substances have been described as
biologically active in several systems [5]. In this context,
nitrogenated chalcogen compounds, particularly chalcogen
amines, present a wide range of biological activities, acting as
glutathione peroxidase mimics [6-9], antioxidants [10-12],
antimicrobials [13], anti-inflammatory [14, 15] and anticancer
agents [4, 16]. In some cases, spatial arrangement of nitrogen and
chalcogen in organochalcogenated compounds allows
intramolecular interactions that can modulate biological
properties of the compounds [1, 5, 7]. Moreover, chalcogen
amines are important to organic synthesis, being applied as
homogeneous catalysts for coupling reactions [6, 18], in
asymmetric catalysis [19-21] and as semiconductor materials [22,
23]. From a synthetic point of view, organochalcogen amines are
mainly prepared by using chalcogenolate anions in aziridine
ring-opening [24, 25], nucleophilic displacement in mesylates
[26, 27] and nitrogenated haloalkanes [28, 29, 30] (Scheme 1-a).
Scheme 1. Known methodologies for the synthesis of chalcogen
Curiously, reductive amination (RA), a well consolidated
approach for synthesis of superior amines by combination of
aldehydes or ketones with a nitrogen source, namely ammonia or
other amines, either primary or secondary [31], is practically
ignored as a route to synthesize chalcogen amines. These
reactions are carried out using acid catalysis and present some
peculiarities, such as: i) the reducing agent should reduce the
imine (or iminium ion) preferentially to the ketone or aldehyde
[32]; ii) structure of the carbonyl compound, iii) the amine used
in the reaction [33]. To the best of our knowledge, only one
example of metal-assisted RA has been reported to date [34]. A
concise series of ortho, meta and para-arylseleno amines was
prepared with 19-73% yield after 24 h under conventional
heating, using NH3 in ethanol and in presence of titanium
tetraisopropoxide, followed by reduction with sodium
borohydride (Scheme 1-b). As an alternative, a biocatalytic
approach employing ω-transaminase can be used for
organoseleno amine synthesis [35] (Scheme 1b). However, the
need for N-protection/deprotection steps, long reaction times,
poor yields, narrow structural diversity, or a particular enzyme-
cofactor recycling system are the main drawbacks of this method.
An important point to be considered is the constant search for
alternative synthetic approaches employing environmentally
friendly reactants, as well as faster reactions and more efficient
conditions [35]. In this context, a widely used approach in
organic synthesis is microwave-assisted reactions, which
generally lead to a considerable increase of the reaction kinetics,
implying in shorter reaction times when compared to
conventional heating [36-44]. Herein we present a two-step, easy
to manipulate and fast methodology for the synthesis of
chalcogen amines via microwave-assisted reductive amination
reaction (Scheme 1-c). This methodology was applied to primary,
secondary and tertiary chalcogen amines synthesis in just 5-10
min with 40-89% isolated yields.
amines
2. Results and discussion
Aminoacetophenones 1-3 were converted into aryldiazonium
salts and immediately captured by lithium butylselenolate to
generate the corresponding arylseleno ketone 4-6, with 38-55%
isolated yields [45]. This approach was not efficient to prepare
aryltelluro amines 16-18, so a longer synthetic route was needed.
Bromoacetophenones 7-9 were first protected by generating the
corresponding bromoacetals 10-12 with 69-98% isolated yields
and employed as precursors for Grignard reagents or Br/Li
exchange reactions to provide ditellurides 13-15 with 51-67%
isolated yields after the oxidative step. One pot cleavage of 13-
15, alkylation and deprotection steps led to aryltelluro ketones
16-18 with 57-99% isolated yields (Scheme 1).
To obtain the desired compounds, chalcogen ketones 4-6 and
16-18 were submitted to reductive amination conditions. It is
known that, in general, reductive amination reactions require
heating and long reaction times. Since several advantages are
well-known to microwave irradiation heating in organic
synthesis, including large reductions in the reaction times and
minimization of side reactions, this alternative approach was also
adopted [46]. To investigate the efficiency of microwave-assisted
synthesis,
a preliminary set of reactions was performed
employing arylchalcogen ketones 4-6 and 16-18, comparing
microwave irradiation versus conventional heating. Initially, we
decided to begin with the most challenging interconversion:
ketones to primary amines. We chose easily manipulated solid
reagents (AcONH4 and NaBH3CN) and a green solvent (ethanol),
as described by Dong [46]. This method has the benefit of
avoiding need for metals to assist the catalysis. The results
obtained for synthesis of primary arylchalcogen amines are
summarized in Table 1.

Journal of Organometallic Chemistry
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Scheme 2. Synthesis of arylchalcogen ketones 4-6 and 16-18
5), while under microwave irradiation the yield of 17a was
generously improved to 89% (Table 1- Entry 5).
Table 1. Comparison between conventional heating and
microwave-assisted reactions in reductive amination of
arylchalcogen ketones 4-6 and 16-18.
Reductive amination of o-substituted arylchalcogen ketones 4
and 16 employing previous reaction conditions (NH4OAc (15
equiv), NaBH3CN (1.2 equiv)) failed to produce primary amines 4a
and 16a under both conventional and microwave-assisted
conditions. Since 4a is also a novel arylseleno amine, we decided
to investigate other RA conditions to synthesize this product
employing only microwave irradiation. To find the best
conditions, the stoichiometry of the reducing agent, reaction time
and temperature were evaluated (results not shown). After
increasing the amount of NaBH3CN from 1.2 to 3 equiv and the
reaction time from 5 to 10 min, arylseleno amine 4a was
successfully obtained with 67% isolated yield under microwave-
assisted heating to 80 oC. The change of reaction time from 10 to
20 min did not improve the yields for this reaction. It is
important to highlight that this apparent lack of reactivity of
ortho-substituted selenoacetophenones is not unprecedented,
since it was also observed by Andrade and coworkers [47] and by
Comasseto and coworkers [48] in various attempts to perform the
bioreduction of selenoacetophenones employing several fungal
strains. Furthermore, all attempts to synthesize the o-substituted
tellurium amine 16a in this work have failed. All these results
corroborate the existence of severe stereo or stereoeletronic
effects in arylchalcogen ketones 4-6 and 16-18 that need to be
better investigated.
Conventional
heating
Microwave
Entry
YBu
Product
Time
(min)
180
Yield
(%)
-
Time
(min)
Yield
(%)
67
1
2
3
4; o-SeBu
5; m-SeBu
6; p-SeBu
4a
5a
6a
10
180
180
25
5
5
51
43
30
(19)*
-
4
5
6
16; o-TeBu
17; m-TeBu
18; p-TeBu
16a
17a
18a
-
10
5
-
180
180
9
89
73
30
5
Reaction conditions: Chalcogen ketone (100 mg), NH4OAc (15 equiv),
NaBH3CN (1.2 equiv) and EtOH (1.0 mL). *Yield reported in reference [34].
Reductive amination of p-substituted arylseleno ketone 6
under conventional heating (180 min, Table 1 – Entry 3) led to
the corresponding amine 6a with 30% yield. Alternatively, just 5
min was enough to produce 6a having 43% yield under
microwave irradiation. In the literature, this arylseleno amine was
prepared with 19% yield after 12 h using NH3 in ethanol and
titanium tetraisopropoxide under conventional heating followed
by an additional 12 h for the reduction step using NaBH4 [34].
When p-substituted tellurium analogue (18) was employed as
starting material under conventional heating, tellurium amine 18a
was obtained with 30% yield, the same result observed to
selenium derivative 6a (Table 1 – Entry 6). Despite the similar
yields for assays under conventional heating, microwave-assisted
synthesis led to 18a with 73% yield and selenium analogue with
only 43%.
Motivated by the exciting results with RA of arylseleno
ketones, we also decided to apply the microwave-assisted
approach for the syntheses of aryltelluro amines 16a-18a from
the corresponding aryltelluro ketones 16-18. In this case,
completely opposite results were obtained to our surprise. RA of
aryltelluro ketones 17-18 provided corresponding primary amines
17a and 18a in considerably higher yields (89 and 73% yields,
respectively; Table 1 – entries 5-6) than corresponding reactions
employing arylseleno ketones 5 and 6 (Table 1 – entries 2-3). On
the other hand, unlike RA of arylseleno ketone 4, we failed in all
attempts to synthesize aryltelluro amine 16a from 16 (Table 1,
entry 4). Besides the stoichiometry of reducing agent, reaction
time and temperature, in this case the change of NaBH3CN to
NaBH4 was also evaluated but no desired product (16a) was ever
detected. These results suggest conflicting effects of Te atoms
according to the substitution pattern on the aromatic ring. At
present, we are investigating possible interactions/effects of YBu
groups on the aromatic ring on RA rates.
A novel m-substituted arylseleno amine 5a was synthesized
with 51% yield under microwave irradiation after 5 min. Using
conventional heating, the best yield was 25% after 3 h (Table 1 –
entry 2). No relevant yield improvements were observed by
changing microwave irradiation from 5 to 10 min in reactions
involving arylseleno ketones 5 and 6. For tellurium congener 17,
conventional heating synthesis furnished the m-substituted
aryltelluro amine 17a with only 9% yield after 3 h (Table 1- entry
The results presented in Table 1 demonstrate that synthesis of
primary chalcogen (Se, Te) amines under microwave irradiation
led to significant improvements in time reactions and yields
when compared to conventional heating conditions. It is well-

4
Journal of Organometallic Chemistry
ACCEPTED MANUSCRIPT
described that microwave operation in chemical reactions
Regardless of the discussion about the existence of microwave
occurs by supplying energy directly to molecules, unlike other
heating methods, such as oil baths, which rely on the
propagation, convection, and conduction of energy in the form of
heat. The microwave heating occurs by two main mechanisms,
dipole polarization effect and ionic conduction, which could
justify the shorter reaction times than those observed under
conventional heating methods [49]. However, some authors
question the microwave effect on reactions and believe that, if
temperature and pressure under microwave conditions were
reproduced in conventional heating, similar yields can be
observed [50].
effects, the excellent preliminary results in the synthesis of
primary arylchalcogen amines 4a-6a and 17a-18a, encouraged us
to change from ammonium acetate to primary and secondary
amines, aiming to synthesize secondary and tertiary
arylchalcogen amines. p-Substituted arylchalcogen ketones 6 and
18 were chosen as models for microwave-assisted RA. For the
synthesis of the arylchalcogen amines 6b-d, 6g, 18b-d and 18g
the reaction temperature was set at 50 °C due to because of the
boiling temperature of the amines. In these reactions the addition
of an acid (acetic acid) for protonation of ketone and/or imine
was also necessary. The results are shown in Table 2.
Table 2. Yields of RA reactions for syntheses of arylchalcogen amines 6b-i, 18b-i.
Entry
Amine
Product
Y
Yield (%)
1
Se; 6b
40
2
3
Te; 18b
Se; 6c
86
56
4
5
Te; 18c
Se; 6d
-
10*
6
7
Te; 18d
Se; 6e
50
-
8
9
Te; 18e
Se; 6f
70
-
N
H
10
Te; 18f
44
n-BuY
11
12
Se; 6g
9*
-
Te; 18g
13
14
Se; 6h
-
-
Te; 18h
15
16
Se; 6i
-
-
Te; 18i
* conversion determined via GC-MS
When isobutylamine was used as a nucleophile, secondary
arylchalcogen amines 6/18b were obtained with 40% (Se) and
86% (Te) isolated yields, respectively (Table 2, entries 1-2). In
contrast, when s-butylamine was used as the nucleophile for
synthesis of arylchalcogen amines 6c (Se) and 18c (Te), only 6c
(Se) was obtained with 56% yield, Table 2, entries 3-4), while no
traces of tellurium analogue (18c) were observed. When allyl
amine was employed as nucleophile, completely opposite results
were observed, since arylchalcogen amines 6d (Se) and 18d (Te)
were obtained with 10% conversion and 50% yields,
respectively, (Table 2, entries 5-6). When n-butylamine and
benzylamine were used as nucleophiles, aryltelluro amines 18e
and 18f were obtained with 70% and 44% yields, respectively,
while no traces of selenium analogues (6e and 6f) were observed
(Table 1 – Entries 7-10).
Tertiary chalcogen amines synthesis was more challenging,
since secondary amines employed as nucleophiles are sterically
hindered, besides their higher nucleophilicity. In this case only
9% conversion of arylseleno amine 6g was observed (Table 2,
entries 11-15). We were not able to synthesize tertiary
arylchalcogen amines employing diisopropylamine and

Journal of Organometallic Chemistry
5
o
diphenylamine as nucleophile (Table 2, entries 13-16), for both
selenium and tellurium compounds. Since these amines are the
most sterically hindered of the series evaluated, the nucleophilic
attack of these amines in arylchalcogen ketones 6 and 18 in the
reductive amination reaction is more difficult.
To a cooled solution (0 C) of aminoacetophenone of interest
ACCEPTED MANUSCRIPT
(405 mg, 3 mmol) containing sulfuric acid (0.8 mL) and water
(0.8 mL), 1.0 mL of an aqueous solution of sodium nitrite (276
mg, 4 mmol) was added dropwise, followed by slow addition of
an aqueous solution of Na2CO3 until pH 7. This reaction mixture
then received the addition of lithium butylselenolate (288,3 mg,
4.5 mmol) dissolved in 5 mL of THF, which gave a biphasic
mixture that was continuously stirred at room temperature for 1
h. Afterwards, the mixture was diluted with brine (20 mL) and
extracted with ethyl acetate (5 × 20 mL). The organic phase was
separated, dried over anhydrous magnesium sulphate and filtered.
The solvent was removed under reduced pressure and the crude
material was purified by flash chromatography using a mixture of
n-hexane and ethyl acetate (9:1) as eluent.
Results suggest the nature of chalcogen atom (Se or Te) in
para position influences the reactivity of the species and
amination reductive reactions rates, since contradictory results
were obtained under the same reaction conditions. Further
investigations are needed to explain this abnormal behavior.
3. Conclusions
We successfully applied a microwave-assisted method to
prepare a set of primary and secondary arylseleno- and aryltelluro
amines having satisfactory yields. The use of solid reagents
(NaBH3CN and NH4OAc), ethanol as solvent and microwave
irradiation allowed a drastic change in the manipulation of
reactants, yields of products and short reaction times. Secondary
arylchalcogen amines were also prepared with moderate yields,
but we were unable to synthesize tertiary arylchalcogen amines
with appreciable yields. Finally, effects of Se and Te atoms,
according to the substitution pattern on the aromatic ring, exert a
dramatic effect on chemical behavior of the species involved in
reductive amination reaction, and suggest the need for a more
profound investigation of possible stereochemical effects of these
chalcogens.
4.2.1. 1-(2-(butylselanyl)phenyl)ethanone 4
Yield: 55%. Yellow solid. 1H NMR (200 MHz, CDCl3, TMS), δ
(ppm): 7.90 (dd, JA = 7.8; JB = 1.5 Hz, 1H); 7.50 (m, 1H); 7.40
(td, JA = 7.0; JB = 1.5 Hz, 1H); 7.24 (td, JA = 7.0; JB = 1.5 Hz,
1H); 2.84 (t, J = 7.5 Hz, 2H); 2.62 (s, 3H); 1.73 (m, 2H); 1.50 (m,
2H); 0.95 (t, J = 7.3 Hz, 3H). 13C NMR (50 MHz, CDCl3): 198.8;
133.1; 132.3; 131.7; 128.6; 128.4; 124.2; 30.7; 27.6; 24.8; 23.4;
13.7. GC-MS (70 eV), m/z (relative abundance): 256 (M+, 21);
241 (1); 199 (100); 182 (11); 169 (3); 157 (9); 130 (1); 117 (2);
105 (5); 91 (25); 77 (12); 65 (3); 51 (3); 43 (35). IR (cm-1): 2957,
2928, 2870, 2123, 1666, 1585, 1454, 1248, 756.
4.2.2. 1-(3-(butylselanyl)phenyl)ethanone 5
4. Experimental
1
Yield: 38%. Orange oil. H NMR (200 MHz, CDCl3, TMS), δ
4.1. General
(ppm): 7.89 (dd, JA = 7.7; JB = 1.2 Hz, 1H); 7.48 (d, J = 7.9 Hz,
1H); 7.39 (dt, JA = 7.4; JB = 1.0 Hz, 1H); 2.83 (t, J = 7.5 Hz, 2H);
2.61 (s, 3H); 1.74 (m, 2H); 1.50 (m, 2H); 0.95 (t, J = 7.3 Hz, 3H).
13C NMR (50 MHz, CDCl3): 198.8; 138.3; 135.5; 132.2; 131.7;
128.4; 124.2; 30.7; 27.5; 24.8; 23.4; 13.7. GC-MS (70 eV), m/z
(relative abundance): 256 (M+, 71); 252 (14); 241 (3); 227 (1);
213 (1); 200 (64); 185 (53); 181 (12); 156 (14); 130 (2); 117 (4);
105 (3); 91 (10); 77 (14); 63 (4); 57 (30); 43 (100). IR (cm-1):
2959, 2930, 2870, 1944, 1686, 1585, 1464, 1252, 785.
1H and 13C NMR analyses were carried out at room temperature
with a Bruker AVANCE 200 or AVANCE 400 spectrometer
operating at 4.7 or 9.4 T and observing 1H at 200.13 or 400.26
MHz and 13C at 50.03 MHz or 100.06 MHz, respectively.
Chemical shifts, expressed in ppm, are related to the
tetramethylsilane (TMS) signal at 0.00 ppm used as internal
1
reference. H NMR data are reported as follows: chemical shift
4.2.3. 1-(4-(butylselanyl)phenyl)ethanone 6
(δ), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet,
m = multiplet), coupling constant (Hz) and relative intensity
(integral). GC-MS spectra were recorded with a Shimadzu QP-
2010 Plus apparatus, equipped with an RTX-5 capillary column
(30m x 0.25mm x 0.25µm film thickness) and operating in
ionization mode by electron impact (70 eV). This was coupled to
a Shimadzu CG-2010 gas chromatograph operating with a helium
flow rate of 1 mL minute-1 and an injector temperature set to 200
°C. The temperature was programmed to 50 oC for 1 min,
1
Yield: 55%. Orange oil. H NMR (200 MHz. CDCl3. TMS). δ
(ppm): 7.81 (dt, JA = 8.6; JB = 1.9 Hz, 2H); 7.48 (dt, JA = 8.6; JB =
1.9 Hz, 2H); 3.00 (t, J = 7.4 Hz. 2H); 2.57 (s, 3H); 1.73 (m, 2H);
1.43 (m, 2H); 0.93 (t, J = 7.2 Hz. 3H). 13C NMR (50 MHz.
CDCl3): 197.3; 139.2; 134.7; 133.0; 130.2; 128.6; 128.3; 31.9;
26.7; 26.4; 22.9; 13.5. CG-MS (70 eV). m/z (relative
abundance): 256 (M+, 86); 241 (18); 200 (58); 185 (94); 181
(21); 156 (18); 130 (3); 117 (6); 105 (16); 91 (14); 77 (22); 63
(7); 57 (55); 43 (100). IR (cm-1): 2959, 2930, 2872, 1680, 1587,
1427, 1267, 816.
o
o
increased at 10 oC min-1 up to 250 C and kept at 250 C for 10
min. The synthesize compounds were analyzed by Fourier-
transform infrared spectroscopy (FTIR) with
a BOMEM
Michelson MB100 spectroscope in the spectral range of 4000-
400 cm-1, with 64 and 32 scans for solid and liquid samples
respectively, and resolution of 4 cm-1. KBr pellets were used for
the analysis of solids, while liquid samples were deposited on
KBr crystals.
4.3. Synthesis of the organotellurium ketones 16-18
The
solution
of
1,2-bis(4-(2-methyl-1,3-dioxolan-2-
yl)phenyl)ditellane (1.74 g, 3 mmol) and butyl bromide (9 mmol,
0.98 mL) in THF (40 mL) was cooled to 0 °C and treated slowly
with NaBH4 (15mmol, 567 mg) dissolved in water (10 mL).
After stirring for 10 min, an aqueous NH4Cl solution was added
4.2. Synthesis of the organoselenium ketones 4-6

6
Journal of Organometallic Chemistry
ACCEPTED MANUSCRIPT
(20 mL) and the resulting mixture extracted with
dichloromethane (3 x 20 mL) and concentrated under reduced
pressure. The crude product was dissolved in acetone (20 mL), p-
toluenesulfonic acid (30 mg) was added and the mixture was
refluxed for 3 h. Then acetone was removed under reduced
pressure, water (10 mL) was added and the product was extracted
with dichloromethane (3 x 20 mL). The combined organic phases
were dried with concentrated and product was purified by flash
chromatography using hexane and ethyl acetate (9:1) as eluent.
4.4.1. 1-(2-(butylselanyl)phenyl)ethanamine 4a
1
Yield: 67%. Yellow liquid. H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 7.46 (m, 2H); 7.27 (m, 1H); 7.18 (dd, JA = 7.4; JB = 1.7
Hz, 1H); 4,58 (q, J = 6.6 Hz, 1H); 2.91 (t, J = 7.3 Hz, 2H); 1.70
(m, 2H); 1.46 (m, 2H); 1.38 (d, J = 6.6 Hz, 3H); 0.92 (t, J = 7.3
Hz, 3H). 13C NMR (50 MHz, CDCl3): 147.9; 131.0; 130.6;
129.6; 129.1; 124.0; 51.2; 32.3; 27.5; 25.3; 22.9; 13.6. GC-MS
(70 eV), m/z (relative abundance): 257 (M+, 44); 242 (21); 238
(6); 200 (93); 183 (79); 179 (16); 157 (6); 131 (2); 119 (93); 104
(100); 91 (28); 72 (30); 65 (4); 51 (8); 44 (23). IR (cm-1): 3360,
3288, 2959, 2928, 2870, 1906, 1591, 1454, 1257, 822.
4.3.1. 1-(2-(butyltellanyl)phenyl)ethanone 16
Yield: 99%. Solid yellow. 1H NMR (200 MHz, CDCl3, TMS), δ
(ppm): 8.02 (dd, JA = 7.4; JB = 1.9, 1H), 7.68 (d, J = 7.9, 1H),
7.25 – 7.42 (m, 2H), 2.69 (t, J = 7.5, 2H), 2.65 (s, 3H), 1.71 –
1.91 (m, 2H), 1.36 – 1.59 (m, 2H), 0.96 (t, J = 7.4, 3H). 13C
NMR (50 MHz, CDCl3): 198.6, 136.8, 132.7, 132.5, 132.2,
125.1, 124.6, 32.2, 26.6, 25.6, 13.6, 7.2. IR (cm-1): 3053, 2955,
2924, 2870, 2856, 1651, 1582, 1553, 1450, 1298, 1269, 1252,
1026, 956, 754, 716, 600.
4.4.2. 1-(3-(butylselanyl)phenyl)ethanamine 5a
1
Yield: 51%. Yellow liquid. H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 7.47 (s, 1H) 7.34 (dt, JA = 6.4; JB = 1.8 Hz, 1H); 7.20
(m, 2H); 4.08 (q, J = 6.6 Hz, 1H); 2.93 (t, J = 7.5 Hz, 2H); 1.70
(m, 2H); 1.44 (m, 2H); 1.37 (d, J = 6.6 Hz, 3H); 0.91 (t, J = 7.3
Hz, 3H). 13C NMR (50 MHz, CDCl3): 148.6; 130.9; 130.6;
129.6; 129.1; 124.0; 51.2; 32.3; 27.5; 25.6; 23.0; 13.6. GC-MS
(70 eV), m/z (relative abundance): 257 (M+, 34); 242 (100); 214
(1); 200 (5); 185 (28); 158 (5); 137 (1); 120 (16); 106 (22); 91
(9); 78 (21); 65 (3); 55 (10); 44 (48). IR (cm-1): 3360, 2959,
2928, 2870, 1940, 1688, 1587, 1464, 1454, 1254, 785.
4.3.2. 1-(3-(butyltellanyl)phenyl)ethanone 17
Yield: 73%. Pale yellow oil. 1H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 8.02 (s, 1H), 7.74 – 7.93 (m, 2H), 7.28 (t, J = 7.6, 2H),
2.95 (t, J = 7.6, 2H), 2.59 (s, 3H), 1.79 (quint, J = 8.0, 2H), 1.40
(sext, J = 7.3, 2H), 0.90 (t, J = 7.3, 3H). 13C NMR (50 MHz,
CDCl3): 197.6, 142.4, 137.7, 129.1, 112.4, 127.3, 33.8, 26.6,
25.0, 13.3, 8.9. IR (cm-1): 3051, 2957, 2926, 2870, 2862, 1686,
1578, 1560, 1408, 1356, 1254, 1182, 1171, 1059, 959, 789, 689,
652, 592.
4.4.3. 1-(4-(butylselanyl)phenyl)ethanamine 6a
1
Yield: 43%. Yellow liquid. H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 7.45 (dt, JA = 8.3; JB = 1.8 Hz, 2H); 7.23 (dt, JA = 8.3; JB
= 1.8 Hz, 2H); 4.08 (q, J = 6.6 Hz, 1H); 2.90 (t, J = 7.3 Hz, 2H);
1.77 (m, 2H); 1.68 (m, 2H); 1.37 (s, 3H); 0.90 (t, J = 7.3 Hz, 3H).
13C NMR (50 MHz, CDCl3): 146.3; 138.6; 133.0; 130.2; 128.6;
126.4; 50.9; 32.2; 27.8; 26.4; 22.9; 13.5. GC-MS (70 eV), m/z
(relative abundance): 257 (M+, 22); 241 (100); 214 (1); 200 (5);
186 (20); 158 (4); 133 (1); 120 (22); 106 (23); 91 (6); 78 (17); 65
(2); 55 (4); 42 (15). IR (cm-1): 3354, 3288, 2959, 2928, 2870,
1906, 1591, 1493, 1454, 1257, 822.
4.3.3. 1-(4-(butyltellanyl)phenyl)ethanone 18
Yield: 57%. Pale yellow oil. 1H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 0.91 (t, J = 7.3 Hz, 3H), 1.41 (sext, J = 7.7 Hz, 3H),
2.57 (s, 3H), 1.82 (quint, J = 7.7 Hz, 2H), 2.97 (t, J = 7.7 Hz,
2H), 7.67 – 7.78 (s, 4H). 13C NMR (50 MHz, CDCl3): 8.7, 13.4,
25.1, 26.4, 33.7, 120.9, 128.5, 135.8, 136.6, 197.7. GC-MS (70
eV), m/z (relative abundance): 306 (M+, 12), 250 (9), 234 (8), 206
(6), 120 (2), 105 (15), 91 (4), 77 (17), 73 (4), 57 (28), 43 (100).
IR (cm-1): 3346, 2957, 2926, 2870, 1682, 1582, 1423, 1391,
1358, 1269, 1182, 1080, 1009, 967, 816, 743, 679, 600.
4.4.4. N-(1-(4-(butylselanyl)phenyl)ethyl)-2-
methylpropan-1-amine 6b
1
Yield: 40%. Yellow liquid. H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 7.43 (dd, JA = 8.3; JB = 1.9 Hz, 2H), 7.20 (dt, JA = 8.1;
JB = 1.8 Hz, 2H), 3.69 (q, J = 6.6 Hz, 1H), 2.91 (t, J = 7.2 Hz,
2H), 2.26 (m, 2H ), 1.69 (m, 3H), 1.43 (m, 2H), 1.32 (d, J = 6.6
Hz, 3H), 0.90 (t, J = 7.3 Hz, 3H), 0.88 (dd, JA = 6.6; JB = 0.6 Hz,
6H). 13C NMR (50 MHz, CDCl3): 144.8, 132.5, 128.5, 127.3,
58.0, 55.9, 32.3, 28.5, 27.7, 24.4, 22.9, 20.8, 20.6, 13.5. GC-MS
(70 eV), m/z (relative abundance): 315 (M+, 1), 298 (39), 270
(4), 241 (100), 207 (2), 185 (22), 157 (2), 132 (2), 104 (39), 78
(10), 65 (1), 57 (11), 44 (5). IR (cm-1): 3321, 2957, 2928, 2870,
1466, 1128, 822.1014, 824.
4.4. Synthesis of the organochalcogen amines 4a – 6a-d, g and
18a, b, d, e, f
To a microwave vial, the appropriate amine (2 equiv.), acetic acid
(0.525 mg, 8.7 mmol) and sodium cyanoborohydride (1.2 equiv.)
were added to a solution of organochalcogen ketone of interest
(100 mg, 0.390 mmol) in ethanol (1 mL). The mixture was
heated in the microwave reactor at 80 °C for 5 or 10 min under
magnetic stirring. After the solvent was removed under reduced
pressure, the crude material was treated with a 1 mol L-1 sodium
hydroxide solution until pH = 10 and the product was extracted
with dichloromethane (3 x 5 mL). The organic portions were
combined, dried over magnesium sulfate and filtered. The solvent
was removed under reduced pressure and the crude material was
purified by flash chromatography using a mixture of ethyl acetate
and ethanol (9:1) as eluent.
4.4.5. N-(1-(4-(butylselanyl)phenyl)ethyl)butan-2-
amine 6c
1
Yield: 56%. Yellow liquid. H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 7.43 (dd, JA = 8.2; JB = 1.8 Hz, 2H), 7.18 (dt, JA = 8.1;
JB = 1.8 Hz, 2H), 3.86 (m, 1H), 2.90 (t, J = 7.3 Hz, 2H), 2.38 (m,

Journal of Organometallic Chemistry
ACCEPTED MANUSCRIPT
7
1H ), 1.69 (m, 2H), 1.35 (m, 7H), 0.91 (m, 9H). 13C NMR (50
4.4.11. N-(1-(4-(butyltellanyl)phenyl)ethyl)prop-
2-en-1-amine 18d
MHz, CDCl3): 144.9, 132.5, 128.5, 127.3, 54.6, 51.3, 32.3, 27.7,
25.0, 24.6, 22.9, 20.7, 19.6, 13.5, 10.3, 9.8. GC-MS (70 eV), m/z
(relative abundance): 313 (M+, 4), 298 (37), 284 (12), 256 (2),
241 (100), 199 (2), 185 (27), 157 (2), 146 (1), 120 (3), 104 (50),
78 (14), 57 (9), 44 (19). IR (cm-1): 3319, 2959, 2928, 2872, 1902,
1485, 1464, 1371, 1014, 824.
1
Yield: 54%. Yellow oil. H NMR (200 MHz, CDCl3, TMS), δ
(ppm): 7.70 (sl, NH), 7.64 – 7.68 (dd, JA = 8.2; JB = 2.0, 2H),
7.13 – 7.17 (dd, JA = 8.2; JB = 2.0, 2H), 5.78 – 5.98 (m, 1H), 5.05
– 5.16 (m, 2H), 3.78 (q, J = 6.6, 1H), 3.09 (d, J = 6.0, 2H, 2.90 (
t, J = 7.7, 2H), 1.78 (quint, J = 7.7, 3H), 1.25 – 1.48 (m, 1H),
1.35 (d, J = 6.6, 3H), 0.89 (t, J = 7.2, 3H). 13C NMR (50 MHz,
CDCl3): 144.8, 138.4, 136.6, 128.5, 127.6, 116.0, 57.2, 50.1,
33.9, 25.0, 24.1, 13.4, 8.4. GC-MS (70 eV), m/z (relative
abundance): 347 (M+, 26), 330 (100), 289 (11), 275 (86), 271
(58), 232 (22), 205 (6), 146 (60), 117 (34), 104 (90), 77 (36), 56
(20), 51 (10). IR (cm-1): 3391, 3074, 2936, 2798, 1638, 1176,
989, 929.
4.4.6. N-(1-(4-(butylselanyl)phenyl)ethyl)prop-2-
en-1-amine 6d
Conversion: 10%. Yellow liquid. GC-MS (70 eV), m/z (relative
abundance): 297 (M+ 10), 282 (100), 241 (36), 225 (23), 185
(26), 157 (7), 146 (11), 105 (24), 104 (62), 78 (21), 68 (8), 55
(13), 42 (18).
4.4.12. N-(1-(4-(butyltellanyl)phenyl)ethyl)butan-1-
amine 18e
4.4.7. N-(1-(4-(butylselanyl)phenyl)ethyl)prop-2-
en-1-amine 6g
Yield: 70%.
Orange oil. 1 H NMR (200 MHz,
Conversion: 9%. Yellow liquid. GC-MS (70 eV), m/z (relative
abundance): 313 (M+ 2), 300 (17), 298 (91), 241 (100), 213 (2),
185 (27), 162 (4), 145 (2), 132 (3), 105 (22), 104 (60), 78 (16),
56 (10), 44 (13).
CDCl3 , TMS), δ (ppm): 7.69 (dd, JA = 8.1; JB = 1.7
Hz, 2H), 7.17 (dd, JA = 8.1; JB = 1.7 Hz, 2H), 3.74
(q, J = 6.6 Hz, 1H), 2.92 (t, J = 7.5 Hz, 2H), 2.47
(m, 2H), 1.81 (quint, J = 7.6, 2H), 1.41 (m, 6H),
1.35 (d, J = 6,6, 3H), 0.91 (m, 6H). 1 3 C NMR (50
MHz, CDCl3 ): 145.5, 138.4, 127.5, 109.5, 58.1,
47.6, 33.9, 32.4, 25.0, 24.3, 20.5, 14.0, 13.4, 8.4 .
GC-MS (70 eV), m/z (relative abundance): 363
(M+, 21), 348 (96), 291 (100), 243 (13), 162 (7),
104 (42), 78 (10), 57 (8), 41 (8). IR (cm- 1 ): 3315,
3191, 2950, 2929, 2860, 1466,1121, 1003, 817.
4.4.8. 1-(3-(butyltellanyl)phenyl)ethanamine 17a
1
Yield: 89%. Yellow oil. H NMR (200 MHz, CDCl3, TMS), δ
(ppm): 9.50 (sl, NH2), 7.68 (s, 1H), 7.56 (d, J = 7.3, 1H), 7.08 –
7.26 (m, 2H), 4.08 (q, J = 6.5, 1H), 2.95 (t, J = 7.5, 2H), 1.72 –
1.90 (m, 2H), 1.40 (d, J = 6.5, 3H), 1.25 – 1.53 (m, 2H), 0.93 (t, J
= 7.4, 3H). 13C NMR (50 MHz, CDCl3): 148.4, 136.5, 129.1,
124.9, 112.1, 51.1, 33.9, 25.5, 25.0, 13.4, 8.4.
4.4.13. N-benzyl-1-(4-
(butyltellanyl)phenyl)ethanamine 18f
Yield: 44%. Pale orange oil. NMR 1H (200 MHz, CDCl3, TMS):
7.58 – 7.78 (dd, JA = 8.1 e JB = 1.9, 2H), 7.24 – 7.40 (m, 5H),
7.06 – 7.22 (dd, JA = 8.1 e JB = 1.9, 2H), 3.77 (q, J = 6.6, 1H),
3.61 (d, J = 4.8, 2H), 2.90 ( t, J = 7.2, 2H), 1.79 (quint, J = 7.2,
2H), 1.61 (sl, NH), 1.37 – 1.48 (m, 2H), 1.34 (d, J = 6.6, 3H),
0.89 (t, J = 7.2, 3H). 13C NMR (50 MHz, CDCl3): 145.1, 140.5,
138.4, 128.3, 128.1, 127.6, 126.9, 109.7, 57.2, 51.6, 33.9, 25.0,
24.4, 13.4, 8.4. GC-MS (70 eV), m/z (relative abundance): 397
(M+, 21), 382 (40), 325 (13), 291 (3), 234 (2), 196 (5), 104 (11),
91 (100), 65 (5), 41 (3). IR (cm-1): 3032, 2963, 2922, 2839, 1622,
1452, 996, 707.
4.4.9. 1-(4-(butyltellanyl)phenyl)ethanamine 18a
Yield: 73%. Pale yellow oil. 1H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 7.65 – 7.69 (dd, JA = 8.2; JB = 1.9, 2H), 7.16 – 7.20 (dd,
JA = 8.2; JB = 1.9, 2H), 4.08 (q, J = 6.6, 1H), 2.89 ( t, J = 7.8,
2H), 1.77 (m, 3H), 1.57 (sl, NH2), 1.37 (d, J = 6.6, 3H), 1.23 –
1.49 (m, 3H), 0.89 (t, J = 7.3, 3H). 13C NMR (50 MHz, CDCl3):
147.3, 138.5, 126.6, 109.5, 51.0, 33.9, 25.7, 25.0, 13.4, 8.4. GC-
MS (70 eV), m/z (relative abundance): 307 (M+, 84), 292 (82),
249 (8), 235 (63), 206 (2), 120 (51), 104 (100), 91 (14), 77 (44),
65 (4), 44 (78), 41 (39). IR (cm-1): 3343, 3280, 2963, 2915, 2874,
1569, 1481, 1003, 817.
Supplementary Material
4.4.10. N-(1-(4-(butyltellanyl)phenyl)ethyl)-2-
methylpropan-1-amine 18b
Supplementary material is available (Methods, 1H and 13C
NMR, IR and mass spectra).
Yield: 86%. Pale orange oil. 1H NMR (200 MHz, CDCl3, TMS),
δ (ppm): 7.67 (dd, JA = 8.1; JB = 1.6, 2H), 7.20 (dd, JA = 8.1; JB =
1.6, 2H), 4.85 (sl, NH), 3.84 (q, J = 6.7, 1H), 2.90 (t, J = 7.5,
2H), 2.32 (m, 2H ), 1.78 (quint, J = 7.5, 3H), 1.44 (d, J = 6.7,
Acknowledgments
The authors would like to thank the Brazilian National
Council for Scientific and Technological Development (CNPq,
Conselho Nacional de Desenvolvimento Científico e Tecnológico
Proc. 456834/2014) and the Coordination for the Improvement of
Higher Education Personnel (CAPES, Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior) for financial
support and fellowships.
3H), 1.37 (m, 2H), 0.89 (t, J = 7.2, 3H), 0.88 (d, J = 6.6, 6H). 13
C
NMR (50 MHz, CDCl3): 142.5, 138.3, 127.8, 110.8, 58.5, 55.1,
33.9, 27.7, 25.0, 23.1, 20.7, 20.5, 13.4, 8.4. GC-MS (70 eV), m/z
(relative abundance): 363 (M+, 12), 346 (28), 291 (100), 234
(18), 207 (7), 105 (81), 78 (22), 41 (21). IR (cm-1): 3315, 2963,
2915, 2874, 1459, 1121, 1010, 824.

8
Journal of Organometallic Chemistry
ACCEPTED MANUSCRIPT
27. C. Y. Kawasoko, P. Foletto, O. E. D. Rodrigues, L. Dornelles, R. S.
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ACCEPTED MANUSCRIPT
Straightforward microwave-assisted synthesis of organochalcogen
amines by reductive amination
Mara C. Dalmolin,a Pamela T. Bandeira,a Matheus S. Ferri,a Alfredo R. M. de Oliveiraa and
Leandro Piovan*a
Highlights
•
Synthesis of primary and secondary chalcogen amines by microwave-assisted
amination reductive;
•
•
•
Reactions were performed with significantly short time and satisfactory yields;
Clean and efficient procedure according to the principles of Green Chemistry;
Se and Te atoms exert a dramatic effect on the chemical behavior of the species;