Microwave-assisted reaction of aryl diazonium fluoroborate and diaryl dichalcogenides in dimethyl carbonate: A general procedure for the synthesis of unsymmetrical diaryl chalcogenides

Article abstract of DOI:10.1039/c2gc35328h

A convenient, general and efficient procedure for the synthesis of unsymmetrical diaryl chalcogenides has been developed by the reaction of aryl diazonium fluoroborates and diaryl dichalcogenides in the presence of zinc dust in dimethyl carbonate under microwave irradiation. The reactions of a wide range of substituted aryl diazonium fluoroborates and diaryl dichalcogenides have been addressed. The zinc dust is required for the cleavage of diaryl dichalcogenides. The products are obtained in high purity after fast column chromatography of the crude residue after evaporation of dimethyl carbonate. The Royal Society of Chemistry 2012.

Full text of DOI:10.1039/c2gc35328h

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PAPER
Microwave-assisted reaction of aryl diazonium fluoroborate and diaryl
dichalcogenides in dimethyl carbonate: a general procedure for the synthesis
of unsymmetrical diaryl chalcogenides†
Debasish Kundu, Sabir Ahammed and Brindaban C. Ranu*
Received 6th March 2012, Accepted 30th April 2012
DOI: 10.1039/c2gc35328h
A convenient, general and efficient procedure for the synthesis of unsymmetrical diaryl chalcogenides has
been developed by the reaction of aryl diazonium fluoroborates and diaryl dichalcogenides in the
presence of zinc dust in dimethyl carbonate under microwave irradiation. The reactions of a wide range of
substituted aryl diazonium fluoroborates and diaryl dichalcogenides have been addressed. The zinc dust is
required for the cleavage of diaryl dichalcogenides. The products are obtained in high purity after fast
column chromatography of the crude residue after evaporation of dimethyl carbonate.
1. Introduction
The organochalcogenides, particularly selenium and tellurium as
structural motifs are found in a variety of molecules of biologi-
cal, pharmaceutical and material interest.1 They have useful
applications as intermediates in organic synthesis.2 Thus, a
Scheme 1 Synthesis of diaryl chalcogenide.
number of methods have been developed for their synthesis.3
Transition metal catalyzed aryl-chalcogen bond formation is one
dust in dimethyl carbonate (Scheme 1) under microwave
irradiation.
of the most common practices for the synthesis of aryl chalco-
genides.3 Several metals including palladium,4 nickel5 and
copper,6 have been employed to catalyze the reaction of aryl
halides with thiol and selenol/PhSeNa under basic conditions for
the synthesis of diaryl sulphides and selenidies although syn-
thesis of diayl tellurides by this protocol is not very successful.
However, due to the foul smell of thiols, instability of selenols
and toxicity of sodium selenolates, synthesis using stable and
easily accessible diaryl dichalcogenides is prefered.7 Recently, a
few greener procedures involving the reaction of diaryl dichalco-
genides/arylselenium halides/potassium aryltrifluoroborates and
aryl boronic acids catalyzed by benign metals such as Cu and Fe
or ionic liquid have been reported.8 In general, reaction with
diaryl dichalcogenides and aryl halides/boronic acids requires a
reductant for the generation of a chalcogenide anion and a metal
for a subsequent reaction. Usually, a metal such as Zn or In is
used as reducing agent or a strong base like NaOH is used for
the cleavage of dichalcogenides and a transition metal initiates
the reaction thereafter.7
The involvement of diazonium salts for the synthesis of diaryl
chalcogenides was reported earlier too.9 However these pro-
cesses used lithium, sodium or potassium salts of arene thiolate/
selenolate/tellurolate which are highly toxic.10 In addition, hazar-
dous solvents such as acetonitrile and DMSO have been
employed. Thus, these methods, although metal free, are not
appreciated from an industrial and environmental standpoint.
This prompted us to consider stable and nontoxic diaryl dichal-
cogenides in place of arene chalcogenates and Zn has been
employed for their cleavage to generate chalcogenide anion
in situ. The use of a strong base such as KOH for the cleavage of
dichalcogenides leads to the formation of a considerable amount
of phenol from diazonium fluoroborates and thus Zn remained as
an obvious choice.
2. Results and discussion
We report here a transition metal free synthesis of unsymmetri-
cal diaryl chalcogenides by a simple one-pot reaction of aryl dia-
zonium fluoroborate and diaryl dichalcogenide in presence of Zn
To standardise the reaction conditions a series of experiments
were performed under varying reaction parameters such as
solvent, temperature and time for a representative reaction of
4-methoxyphenyl diazonium fluoroborate and diphenyl ditelluride
in presence of zinc. Among a variety of solvents studied
dimethyl carbonate furnished the best results in terms of reaction
time and yield. Under microwave irradiation the reaction was
complete after 30 min, whereas conventional heating at 80 °C
Department of Organic Chemistry, Indian Association for the
Cultivation of Science, Jadavpur, Kolkata, 700 032, India.
E-mail: ocbcr@iacs.res.in
†Electronic supplementary information (ESI) available: See DOI:
10.1039/c2gc35328h
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Table 1 Optimization of reaction conditions
results are reported in Table 3 for selenides and in Table 4 for
sulfides. Functionalization of products with a wide range of
groups such as Br, CN, NO2, OMe, COOMe, Cl, COMe has
been successfully achieved using this procedure.
In general, the reactions are clean and high yielding. Micro-
wave heating made them faster too. The nature and position of
substituents did not have any effect on the reaction rates and
yields. The chalcogenides are obtained pure and are character-
ized properly by spectroscopic data. Several of these compounds
are new. The synthesis of diaryl tellurides is less explored com-
pared to those of other chalcogenides and a limited number of
synthetic methods for tellurides are available. This procedure
provides a practical alternative to the existing procedures. The
dimethyl carbonate has been recovered without any appreciable
loss and has been reused. Notably, dimethyl carbonate is con-
sidered one of the high priority green solvents.11
Entry
Solvent
Temp
Time (h)
Yieldd (%)
1
DMF
DMF
DMF
DMF
110 °C
80 °C
80 °C
80 °C
80 °C
60 °C
100 °C
80 °C
80 °C
90 °C
80 °C
60 °C
RT
8
8
84
86
85
Trace
72
20
Trace
35
80
87
2
3a
4b
5
0.5
8
12
12
12
35
8
8
8
15
8
8
DMSO
THF
Toluene
CH3CN
NMP
DMC
DMC
DMC
DMC
DMC
DMC
DMC
H2O
6
7
8
9
10
11
12
13
14b
15c
16a
17
18
88
42
—
A possible reaction pathway is outlined in Scheme 2. Initially
12
Zn reacts with diphenyl dichalcogenide to form Zn(XPh)2
80 °C
80 °C
80 °C
100 °C
100 °C
—
which then interacts with diazonium fluoroborate to provide the
product via release of N2. The involvement of zinc metal is vital
in the cleavage of diphenyl dichalcogenide. In absence of zinc
dust or in presence of ZnSO4, the progress of reaction is not
more than 10%.
8
0.5
8
Trace
87
—
H2O/TBAB
8
40
a Reaction is done in microwave (power = 170 W). b No Zn dust is used.
c ZnSO4 is used in presence of zinc dust. d Yield of isolated product
(1H and 13C).
3. Experimental
required 8 hours. The reaction did not initiate at room tempera-
ture. Surprisingly the reaction did not proceed at all in water
alone without any additive (Table 1, entry 17); however TBAB
(tetrabutyl ammonium bromide) facilitates the reaction to some
extent (Table 1, entry 18). Other polar solvents such as DMF,
DMSO, and NMP mediated the reaction quite efficiently.
Dimethyl carbonate (DMC) was chosen because of its environ-
mental acceptability, moderate boiling point and cost-
effectiveness.11
In a typical experimental procedure, a mixture of an aryl dia-
zonium tetrafluoroborate, diphenyl ditelluride/diselenide/
disulfide in DMC in presence of Zn was heated under microwave
irradiation for a required period of time (TLC). Evaporation of
solvent followed by the column chromatography of the crude
residue provided the pure product.
IR spectra were recorded on a Shimadzu 8300 FTIR spec-
1
trometer. H NMR and 13C NMR spectra were run on Bruker
DPX-300 and DPX-500 instruments. HRMS were acquired on a
Microtek Qtof Micro YA263 spectrometer. All commercial
reagents were distilled before use. Aryl diazonium tetrafluorobo-
rates were prepared from the corresponding anilines by diazotiza-
tion by following a previously reported protocol.13 A monomode
microwave reactor (Discover model from CEM Corporation,
USA) has been used for all the reactions. Zinc dust and DMC
(dimethyl carbonate) were purchased from Aldrich.
Representative experimental procedure for the reaction of
4-methoxy diazonium tetrafluoroborate and diphenyl ditelluride
(Table 2, entry 6)
A wide range of substituted phenyl diazonium fluoroborates
were reacted with diphenyl ditelluride using this procedure to
provide the corresponding products. The results are summarized
in Table 2. For comparison, all the reactions were performed in a
conventional oil bath heating as well as under microwave
irradiation. The reaction times are substantially reduced by
microwave heating, however the yields are comparable in both
heating modes. The substitution of electron withdrawing and
electron donating groups on the phenyl ring of diazonium fluoro-
borates did not have any appreciable influence on the outcome of
the reaction. Several functional groups such as COMe, COOMe,
COOH, OMe, CN, NO2, Br, F, OCF3, OH are compatible with
these reaction conditions. The naphthyl diazonium fluoroborate
also underwent reaction without any difficulty.
A mixture of 4-methoxy diazonium tetreafluoroborate (272 mg,
1 mmol), diphenyl ditelluride (200 mg, 0.5 mmol) and Zn dust
(32 mg, 0.5 mmol) in DMC (4 mL) was heated under microwave
irradiation for 30 min (By conventional heating the mixture was
stirred at 80 °C for 8 h) (TLC). The DMC was evaporated and
the corresponding diaryl telluride was obtained by column
chromatography as a white solid (276.35 mg, 87%), mp
1
60–62 °C, IR (KBr) 3062, 1880, 1585, 1488 cm−1; H NMR
(500 MHz, CDCl3) δ 3.76 (s, 3H), 6.78 (d, J = 8.5 Hz, 2H),
7.13–7.19 (m, 3H), 7.55 (d, J = 7.5 Hz, 2H), 7.71 (d, J = 8.5
13
Hz, 2H);
C NMR (125 MHz, CDCl3) δ 55.2, 103.3, 115.6
(2C), 116.0, 127.4, 129.4 (2C), 136.5 (2C), 141.3 (2C), 160.1.
This procedure was followed for all the reactions in Tables
2–4. A few of these products are known compounds (see the
references in Tables 2–4) and were easily identified by compari-
son of their spectroscopic data with those previously reported.
The same procedure was followed for the synthesis of diaryl
selenides and sulfides. Several substituted phenyl diazonium
fluoroborates have been employed for these reactions. The
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Table 2 Zn mediated reaction of diaryl ditellurides with aryl diazonium tetrafluoroborate
Conventional heating
Microwave heatingb
Yield (%)a
Entry
1
R
Product
Yield (%)a
90
Time (h)
8
Time (min)
30
Ref
4-Br
92
88
90
81
92
7m
2
3
4
5
4-COMe
4-COOMe
4-COOH
3-COMe
85
88
80
93
7.5
7
25
25
35
25
14a
7m
—
8.5
8
—
6
7
8
4-OMe
4-COOEt
4-NO2
88
82
72
8
7
8
87
85
78
30
35
30
7m
—
9a
9c
Naphthyl
95
7
97
25
7l
10
11
12
4-CN
86
90
82
8
90
88
87
30
25
25
14b
—
4-OiPr
8.2
10
3-CN, 4-F
—
13
14
2-Br
80
85
8
8
83
87
30
30
—
—
4-OCF3
15
16
4-Me
4-F
90
80
8.2
8
92
85
25
30
9a
14c
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Table 2 (Contd.)
Conventional heating
Microwave heatingb
Yield (%)a
Entry
17
R
Product
Yield (%)a
74
Time (h)
Time (min)
35
Ref
2-OH
8
78
—
18
2-NO2
72
8
73
35
9a
a Yields of isolated pure products (1H and 13C). b Microwave power = 170 W. c 1-Naphthyl diazonium tetrafluoroborate is used as electrophile.
The unknown compounds were fully characterized by their
6H), 4.40–4.43 (m, 1H), 6.66 (d, J = 8.5 Hz, 2H), 7.03–7.09 (m,
3H), 7.46 (d, J = 7 Hz, 2H), 7.60 (d, J = 8.5 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 12.1 (2C), 69.8, 102.9, 116.1, 117.3 (2C),
127.3 (2C), 129.4 (2C), 136.5, 141.3 (2C), 158.4; anal calcd for
C15H16OTe: C 53.01, H 4.74; found: C 53.13, H 4.62%.
1
IR, H NMR, 13C NMR and HRMS spectra, and C, H, N-ana-
lyses. These data are given below in order of their entries in
Table 2 and 3.
4-(Phenyltellanyl)benzoic acid (Table 2, entry 4)
2-Fluoro-5-(phenyltellanyl)benzonitrile (Table 2, entry 12)
Yellow solid; mp 160–162 °C; IR (KBr) 3300–2500 (broad),
1681, 1589, 1292, 759 cm−1
;
1H NMR (500 MHz, CDCl3)
Yellow viscous liquid; IR (neat) 3066, 2926, 2235, 1595, 1487,
δ 7.21 (t, J = 7.5 Hz, 2H), 7.31 (t, J = 7.5 Hz, 1H), 7.52 (d,
J = 8 Hz, 2H), 7.74–7.78 (m, 4H); 13C NMR (125 MHz, CDCl3)
δ 113.3, 125.3, 128.2, 129.0, 129.9 (2C), 130.6 (2C), 135.7
(2C), 139.9 (2C), 172.1; HRMS calcd for C14H14O2Te
[M + H]+: 328.9821; Found: 328.9816.
1242, 1118, 736 cm−1 1H NMR (500 MHz, CDCl3) δ
;
7.02–7.06 (m, 1H), 7.28 (t, J = 7.5 Hz, 2H), 7.36–7.39 (m, 1H),
7.76 (t, J = 7.5 Hz, 2H), 7.81–7.84 (m, 2H); 13C NMR
(125 MHz, CDCl3) δ 103.1, 110.2 (J = 5Hz), 113.3, 113.5,
117.5 (J = 6.25 Hz), 129.0, 130.1 (2C), 139.1 (2C), 141.8, 143.9
(J = 8.75 Hz), 162.0 (J = 258.2 Hz); anal calcd for C13H8FNTe:
C 48.07, H 2.48, N 4.31; found: C 47.92, H 2.53, N 4.28%.
1-(3-(Phenyltellanyl)phenyl)ethanone (Table 2, entry 5)
Yellow liquid; IR (neat) 3053, 3014, 1685, 1573, 1253,
2-Bromophenyl)(phenyl)tellane (Table 2, entry 13)
756 cm−1 1H NMR (500 MHz, CDCl3) δ 2.51 (s, 3H),
;
7.21–7.30 (m, 4H), 7.73 (d, J = 7 Hz, 2H), 7.81 (t, J = 8.5 Hz,
2H), 8.24 (s, 1H); 13C NMR (125 MHz, CDCL3) δ 26.6, 114.1,
115.6, 127.6, 128.3, 129.6, 129.7 (2C), 137.2, 137.9, 138.6
(2C), 141.9, 197.4; anal calcd for C14H12OTe: C 51.92, H 3.73;
found: C 51.86, H 3.69%.
Yellow viscous liquid; IR (neat) 3053, 2989, 1435, 1003,
1
746 cm−1; H NMR (500 MHz, CDCl3) δ 6.92 (d, J = 7.5 Hz,
1H), 6.99–7.05 (m, 2H), 7.37 (t, J = 7 Hz, 2H), 7.46 (t, J =
7 Hz, 2H), 7.96 (d, J = 7.5 Hz, 2H); 13C NMR (125 MHz,
CDCl3) δ 114.8, 124.0, 127.1, 127.9, 128.1, 129.3, 130.1 (2C),
132.1, 134.5, 141.3 (2C); HRMS calcd for C12H9BrTe [M]+:
361.8950; found: 361.8918.
Ethyl 4-(phenyltellanyl)benzoate (Table 2, entry 7)
Brown viscous liquid; IR (neat) 3018, 2983, 1712, 1280, 1215,
Phenyl(4-(trifluoromethoxy)phenyl)tellane (Table 2, entry 14)
1
756 cm−1; H NMR (500 MHz, CDCl3) δ 1.38 (t, J = 7.5 Hz,
3H), 4.37 (q, J = 7.5 Hz, 2H), 7.29 (t, J = 7.5 Hz, 2H), 7.38
(t, J = 7.5 Hz, 1H), 7.62 (d, J = 8 Hz, 2H), 7.80–7.84 (m, 4H);
13C NMR (125 MHz, CDCl3) δ 14.4, 61.1, 113.6, 123.1, 128.7,
129.6 (2C), 129.9 (2C), 130.2 (2C), 136.1 (2C), 139.5, 166.5;
anal calcd for C15H14O2Te: C 50.91, H 3.99; found: C 50.88,
H 3.93%.
Brown liquid; IR (neat) 3066, 2924, 1573, 1487, 1257, 1166,
1
732 cm−1; H NMR (500 MHz, CDCl3) δ 6.95 (d, J = 8.5 Hz,
2H), 7.14 (t, J = 8Hz, 2H), 7.22 (t, J = 8 Hz, 1H), 7.56–7.64 (m,
4H); 13C NMR (125 MHz, CDCl3) δ 112.8, 114.3, 119.6, 122.1
(2C), 128.4, 129.8 (2C), 130.6 (2C), 139.2 (2C), 149.3; anal calcd
for C13H9F3OTe: C 42.68, H 2.48; found: C 42.61, H 2.49%.
(4-Isopropoxyphenyl)(phenyl)tellane (Table 2, entry 11)
2-(Phenyltellanyl)phenol (Table 1, entry 17)
Brown liquid; IR (neat) 3053, 2976, 1581, 1485, 1242,
Yellow liquid; IR (neat) 3390, 3053, 2924, 1573, 1438 cm−1
;
1
731 cm−1; H NMR (500 MHz, CDCl3) δ 1.21 (d, J = 6 Hz,
1H NMR (500 MHz, CDCl3) δ 6.23 (s, 1H), 6.72 (t, J = 7.5 Hz,
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Table 3 Zn mediated reaction of diaryl diselenides with aryl diazonium tetrafluoroborate
Conventional heating
Microwave heatingb
Yielda (%)
Entry
1
R
H
Product
Yielda (%)
84
Time (h)
8
Time (min)
30
Ref
88
9a
2
3
4
5
6
4-Br
87
81
84
85
91
8
89
25
30
30
25
25
7m
9a
7m
9c
2-CN
9
85
83
88
93
4-COOMe
4-COMe
3-Cl, 4-Me
8.5
8
8
—
7
3-COMe
82
8
85
35
7b
8
9
4-OMe
3-NO2
90
80
8
94
82
25
30
7m
7b
10
10c
11d
4-Me
86
90
8
9
90
93
25
25
7b
7l
Naphthyl
12
13
4-CN
85
80
8
87
85
30
25
14d
3-CN, 4-F
10
—
14
3-Cl
90
8
89
25
9a
a Yields of isolated pure products (1H and 13C). b Microwave power = 170 W. c Di(4-methoxyphenyl) diselenide is used in place of diphenyl
diselenide. d 1-Naphthyl diazonium tetrafluoroborate is used as electrophile.
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Table 4 Zn mediated reaction of diaryl disulfides with aryl diazonium tetrafluoroborate
Conventional heating
Yielda (%)
Microwave heatingb
Yielda (%)
Entry
1
R
R′
Product
Time (h)
Time (min)
Ref
4-Br
4-Br
86
8
88
25
14e
2
3
4
5
4-OMe
4-COMe
4-CN
4-Me
90
86
83
81
8
8
8
8
94
87
88
85
25
25
25
25
14f
14g
14h
14i
4-OMe
4-OMe
4-Br
4-OMe
6
7
4-NO2
H
4-OMe
H
80
84
8
8
79
88
25
25
14j
7m
a Yields of isolated pure products (1H and 13C). b Microwave power = 170 W.
(d, J = 8 Hz, 1H), 7.28–7.31 (m, 4H), 7.48–7.50 (m, 3H);
13C NMR (125 MHz, CDCl3) δ 19.8, 127.6, 129.3, 129.5 (2C),
130.9, 131.5 131.7, 133.0, 133.3 (2C), 135.1, 135.5; anal calcd
for C13H11ClSe: C 55.44, H 3.94; found: C 55.51, H 3.88%.
2-Fluoro-5-(phenylselanyl)benzonitrile (Table 3, entry 13)
Yellow viscous liquid; IR (neat) 3070, 2922, 2235, 1577, 1487,
1242, 1118, 740 cm−1 1H NMR (500 MHz, CDCl3) δ 7.10
;
(t, J = 8 Hz, 1H), 7.32–7.38 (m, 3H), 7.50 (d, J = 7.5 Hz, 2H),
7.60–7.64 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 113.4,
117.4, 117.5, 128.5, 128.8, 129.2, 130.0 (2C), 134.3 (2C),
136.6, 138.8 (7.5 Hz), 162.5 (258.7 Hz); anal calcd for
C13H8FNSe: C 56.54, H 2.92, N 5.07; found: C 56.49, H 2.95,
N 4.97%.
Scheme 2 Probable mechanism.
1H), 6.99 (d, J = 8 Hz, 1H), 7.10 (t, J = 7.5 Hz, 2H), 7.16 (d,
J = 8 Hz, 1H), 7.24 (t, J = 8 Hz, 1H), 7.44 (d, J = 8 Hz, 2H),
7.68 (d, J = 7.5 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 103.9,
114.1, 116.3, 121.9, 127.9, 129.8 (2C), 132.3, 136.3 (2C),
141.5, 157.6; HRMS calcd for C12H10OTe [M + H]+: 300.9872;
found: 300.9867.
4. Conclusions
In conclusion, we have developed a general procedure for the
synthesis of diaryl chalcogenides (sulphides, selenides and tellu-
rides) by a reaction of aryl diazonium fluoroborates and diaryl
dichalcogenides in the presence of zinc in dimethyl carbonate
under microwave irradiation. The simplicity in operation, general
applicability to all three chalcogenides, scope of wide functiona-
lization, use of recyclable dimethyl carbonate as reaction
medium, energy efficiency (shorter reaction time under
(3-Chloro-4-methylphenyl)(phenyl)selane (Table 3, entry 6)
Yellow liquid; IR (neat) 3055, 2922, 1577, 1473, 1437,
736 cm−1; H NMR (500 MHz, CDCl3) δ 2.37 (s, 3H), 7.14
1
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microwave irradiation), employment of stable and readily avail-
able diaryl dichalogenide in place of foul smelling and toxic
thiols/selenols/thiolate/selenoate, transition metal-free reaction
and high yields of products make this procedure greener and
more cost-effective.
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2030 | Green Chem., 2012, 14, 2024–2030
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